TA Instruments

THERMAL ANALYSIS
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Differential Scanning Calorimetry (DSC) Vapor Sorption Analysis
VTI-SA+ 58
VTI-SA+ Technology 60
Q2000 4
Q5000 SA 64
Q20 6
Q5000 SA Technology 66
DSC Technology 8
Applications 72
Accessories 10
Temperature Control Options 14
Tzero® & MDSC® Technology 18

Thermogravimetric Analysis (TGA) Dynamic Mechanical Analysis (DMA)

Q500 32
Q50 34
Q800 78
Q500/Q50 Technology 36
Deformation Modes & Sample Size 80
TGA Accessories & Options 38
Subambient Operation 81
Applications 44
Q800 Technology 82
Modes of Deformation 84
Accessories 86
DMA Theory 90
Modes of Operation 91

Simultaneous DSC/TGA Thermomechanical Analysis (TMA)

Q600 50 Q400EM/Q400 98
SDT Technology 52 Q400 Technology 100
Applications 54 Modes of Deformation 102
TMA Theory/Modes of Operation 104
Applications 108
Differential Scanning Calorimetry (DSC) Vapor Sorption Analysis
VTI-SA+ 58
VTI-SA+ Technology 60
Q2000 4
Q5000 SA 64
Q20 6
Q5000 SA Technology 66
DSC Technology 8
Applications 72
Accessories 10
Temperature Control Options 14
Tzero® & MDSC® Technology 18

Thermogravimetric Analysis (TGA) Dynamic Mechanical Analysis (DMA)

Q500 32
Q50 34
Q800 78
Q500/Q50 Technology 36
Deformation Modes & Sample Size 80
TGA Accessories & Options 38
Subambient Operation 81
Applications 44
Q800 Technology 82
Modes of Deformation 84
Accessories 86
DMA Theory 90
Modes of Operation 91

Simultaneous DSC/TGA Thermomechanical Analysis (TMA)

Q600 50 Q400EM/Q400 98
SDT Technology 52 Q400 Technology 100
Applications 54 Modes of Deformation 102
TMA Theory/Modes of Operation 104
Applications 108
 Differential Scanning Calorimetry

Differential Scanning Calorimeters offering superior performance

and unmatched flexibility for the widest range of applications
 DSC Q2000 SPECIFICATIONS

Technologies
Tzero® Technology Advanced
MDSC® Available
Direct Cp Measurement Included
Platinum™ Software Included

The Q2000 is a research-grade DSC with superior Hardware Features

Color Touch Screen Included
performance in baseline flatness, precision,
User Replaceable Tzero Cell Yes
sensitivity, and resolution. Advanced Tzero® 50-Position Autosampler Available
technology and multiple exclusive hardware and Autolid Included
software features make the Q2000 powerful, Dual Digital Mass Flow Controllers Included
flexible, and easy-to-use. Modulated DSC® and Full Range of Cooling Accessories (LNCS, RCS90, RCS40, FACS, QCA) Available
a reliable 50-position autosampler are available Pressure DSC Available
as options. An additional high-value feature is Photocalorimeter Available
Platinum™ software, which permits automatic Performance
scheduling of tests designed to keep the Q2000 Temperature Range Ambient to 725°C
consistently in top operating condition. Available With Cooling Accessories -180 to 725°C
accessories, such as a new photocalorimeter, Temperature Accuracy +/- 0.1°C
pressure DSC, and the widest array of cooling Temperature Precision +/- 0.01°C
devices, make the Q2000 a DSC well-equipped Calorimetric Reproducibility (indium metal) +/- 0.05%
Calorimetric Precision (indium metal) +/- 0.05%
to satisfy the most demanding researcher.
Dynamic Measurement Range >+/- 500 mW
Baseline Curvature (Tzero; -50 to 300˚C) 10 µW
Baseline Reproducibility with Tzero +/- 10 µW
Sensitivity 0.2 µW
Indium Height/Width 60 mW/°C

*Indium height/width ratio: 1.0 mg In heated at 10˚C/min in N2 atmosphere. (A larger number denotes better performance).

4 5
 DSC Q20 SPECIFICATIONS

Hardware Features Q20 AQ20 Q20P

Tzero® Cell (fixed position) Included Included —
User Replaceable Cell — — Yes
50-Position Autosampler — Included —
Autolid — Included —
The Q20 (Q20, AQ20, Q20P) is a cost-effective, Dual Digital Mass Flow Controllers Included Included —
easy-to-use, general-purpose DSC module, with Full Range of Cooling Accessories
Available Available QCA Only
calorimetric performance superior to many (LNCS, RCS90, RCS40, FACS, QCA)
competitive research-grade models. These are Pressure DSC — — Yes
Platinum Software — Included —
entry-level instruments not based on performance,
MDSC Available Available —
but on available options. The Q20 is ideal
for research, teaching, and quality control Performance
applications that require a rugged, reliable, Temperature Range Amb to 725°C Amb to 725°C Amb to 550°C
basic DSC. The AQ20 is designed for unattended With Cooling Accessories -180 to 725°C -180 to 725°C -130 to 550°C
analysis of up to 50 samples in a sequential Temperature Accuracy +/- 0.1°C +/- 0.1°C +/- 0.1°C
manner. The Q20 and AQ20 include dual digital Temperature Precision +/- 0.05°C +/- 0.05°C +/- 0.05°C
mass flow controllers and are available with Calorimetric Reproducibility (indium metal) +/- 1% +/- 1% +/- 1%
Calorimetric Precision (indium metal) +/- 0.1% +/- 0.1% +/- 0.1%
MDSC®. The Q20P is designed for studies of
Dynamic Measurement Range +/- 350 mW +/- 350 mW +/- 350 mW
pressure-sensitive materials or samples that may
Digital Resolution >0.04 µW >0.04 µW >0.04 µW
volatilize on heating.
Baseline Curvature (-50 to 300°C) <0.15 mW <0.15 mW —
Baseline Reproducibility < 0.04 mW <0.04 mW —
Sensitivity 1.0 µW 1.0 µW 1.0 µW
Indium Height/Width* 8.0 mW/°C 8.0 mW/°C —

*Indium height/width ratio: 1.0 mg In heated at 10˚C/min in N2 atmosphere. (A larger number denotes better performance).

6 7
 Q Series™ DSC Technology Tzero Thermocouple

Furnace

Tzero® Cell Design Cooling Rods & Ring

The Tzero cell is designed for excellence in both heating and cooling. The unique design features an array of nickel cooling rods
The heat flow sensor is machined for symmetry from a single piece of that connect the silver furnace with the cooling ring. This
durable, thin wall, high response constantan and directly brazed to design produces superior cooling performance over a wide
the silver heating block. Design benefits include faster signal response, temperature range, higher cooling rates and better agility from
flat and reproducible baselines, superior sensitivity and resolution, heating to cooling operation. Lower subambient temperatures
improved data precision, and unmatched ruggedness. Constantan Sensor Chromel Area Thermocouple and faster turnaround time can be obtained with our expanded
range of cooling accessories in isothermal, programmed or
A chromel/constantan Tzero thermocouple is located symmetrically ballistic cooling, and MDSC® experiments.
between the sample and reference sensor platforms, and acts as an
independent measurement and furnace control sensor. Matched
chromel area thermocouples are welded to the underside of each
Furnace
sensor platform, providing independent sample and reference heat The Tzero® transducer is enclosed in a high thermal conductivity,
flow measurements that result in superior DSC and MDSC® results. silver furnace, which uses rugged, long-life Platinel® windings.
Purge gases are accurately and precisely metered by digital
mass flow controllers, and preheated prior to introduction to
Autolid the sample chamber. Long furnace life and a highly uniform
environment at the sample and reference sensors are ensured, Cooling Rods
The Q2000 and AQ20 have a new and improved autolid assembly
that consists of dual silver lids, an innovative lifting/venting mechanism, as well as accurate isothermal temperatures, true linear heating
and a dome-shaped heat shield. More accurate and reproducible rates, rapid temperature response, and the ability to heat at
measurements result from improved thermal isolation of the cell. rates up to 200°C/min.
Platinel® is a trademark of the BASF Group

Mass Flow Controllers

High quality DSC experiments require precise purge gas flow rates.
Mass flow controllers, along with integrated gas switching, provide
flexible control as part of individual methods. Purge gas flow rates
can be set from 0-240 mL/min in increments of 1 mL/min. The system
is precalibrated for helium, nitrogen, air and oxygen and suitable Cooling Ring
calibration factors may be entered for other gases.

8 9
 Q Series™ Accessories

Autosampler
The patented* DSC autosampler is a powerful performance and
productivity enhancer for the Q Series DSC modules. It provides reliable,
unattended operation of the AQ2000 and AQ20 modules. Unique in its
ability to exchange up to 5 reference pans as well as 50 sample pans,
the Q Series autosampler enables laboratories to reliably analyze samples
“around-the-clock” in sequential order. An optical sensor guides the Tzero® DSC Sample Encapsulation Press
sample arm, ensuring precise pan placement and automatic calibration A key contributor to the quality of DSC results is the sample preparation.
of the system. Maximum productivity from the DSC autosampler is The new Tzero press takes sample encapsulation to a higher level of
achieved when paired with our intelligent Advantage™ software that performance and convenience in conventional and hermetic sealing of
permits pre-programmed analysis, comparison, and presentation of a wide variety of materials. The press kit includes die sets (4) for the
results. new Tzero aluminum and Tzero hermetic pans & lids and also for our
upgraded standard and hermetic pans & lids. Optional die sets are
*U.S. Patent No. 6,644,136; 6,652,015; 6,760,679; 6,823,278
available for hi-volume DSC pans and Discovery TGA sealed pans.
The die sets are magnetically attached with no tools or user adjustments
Platinum™ Software required. In addition, each die set is color-coded to the box containing
the compatible Tzero or standard aluminum or hermetic pans and lids.
To further assure high-quality data, Q Series DSC modules equipped with
the DSC autosampler (AQ20, AQ2000) can take full advantage of the
Platinum features inherent in our Advantage software. These permit a
user to automatically schedule a variety of calibration, verification and
diagnostic tests to ensure that the DSC is constantly kept in optimum
operating condition. Platinum software allows all Q Series DSC
instruments to provide email notification of the completion of an analysis.
Also included is the ability to view and download any new software
versions that TA Instruments develops as upgrades to its standard
Advantage software.

10 11
 Photocalorimeter
The Photocalorimeter Accessory (PCA), for the Q2000 DSC, permits
characterization of photocuring materials between -50 and 250°C.
UV/Visible light (250-650 nm) from a 200 W high pressure mercury
source is transmitted to the sample chamber via an extended range,
dual-quartz light guide with neutral density or band pass filters.
Tzero® technology permits direct measurement of light intensity at both
the sample and reference positions. It also provides for simultaneous
measurement of two samples.

Pressure DSC
The Q20P is a dedicated pressure DSC system that provides heat flow
measurements on pressure sensitive materials from -130 to 550°C, at pressures
from 1 Pa (0.01 torr) to 7 MPa (1 000 psi). The pressure cell employs standard
heat flux DSC technology and incorporates pressure control valves, a pressure
gauge, and over-pressure protection. This pressure DSC cell is also an accessory
for the Q2000 DSC and can be used as a standard (ambient pressure) cell
from -180 to 550°C.

12 13
 Temperature Control Options
RCS40

Refrigerated Cooling Systems (RCS90 and RCS40)

The RCS is frequently selected as the preferred cooling device by thermal analysts for trouble-free, unattended DSC and MDSC® operation
over a broad temperature range. Because it is a sealed system requiring only electrical power, the RCS has advantages for operation in
areas where other refrigerants are difficult or expensive to obtain. TA Instruments offers two complementary models: the RCS90 and the
RCS40. Both use the same cooling head, which fits snugly over the Q Series™ DSC Cell and completely eliminates frosting issues typical in
competitive designs. Both controlled and ballistic cooling is achievable.

RCS90 RCS40
The RCS90 employs a two-stage refrigeration system, The RCS40 employs a single-stage refrigeration system,
which permits convenient DSC/MDSC operation over the which permits convenient DSC and MDSC® operation
temperature range from -90 to 550°C. Typical RCS90 over the temperature range from -40°C to 400°C.
controlled cooling rates are detailed in the table below. Typical RCS40 controlled cooling rates are detailed in
Ballistic cooling from 500°C to ambient is achieved the table below. Ballistic cooling from 400°C to ambient
in about 7 minutes. The RCS90 is compatible with all is achieved in about 7 minutes. The RCS40 is compatible
ambient pressure Q Series™ DSC Systems. with all ambient pressure Q Series™ DSC Systems.

RCS90 Controlled Cooling Rates, from 550°C (upper limit)* RCS40 Controlled Cooling Rates, from 400°C (upper limit)*

Controlled Rate To Lower Temperature Controlled Rate To Lower Temperature

100°C/min 300°C 65°C/min 250°C
50°C/min 120°C 50°C/min 175°C
20°C/min -20°C 20°C/min 40°C
10°C/min -50°C 10°C/min 0°C
5°C/min -75°C 5°C/min -15°C
2°C/min -90°C 2°C/min -40°C

RCS90
* Performance may vary slightly, depending on laboratory conditions.

14 15
 Temperature Control Options

Liquid Nitrogen Cooling System Finned Air Cooling System

The Liquid Nitrogen Cooling System (LNCS) provides the highest performance and greatest flexibility in cooling. It has the lowest operational The Finned Air Cooling System (FACS) is an innovative
temperature (to -180°C), greatest cooling rate capacity (to 140°C/min), and an upper temperature limit of 550°C. Typical LNCS controlled cooling accessory for all the Q Series™ DSC modules that
cooling rates are detailed in the table below. Ballistic cooling from 550°C to ambient is achieved in about 5 minutes. Its autofill capability allows offers a cost-effective alternative to the RCS or LNCS cooling
the LNCS to be automatically refilled from a larger liquid nitrogen source for continuous DSC operation. The LNCS is available for all ambient systems. The FACS can be used for controlled cooling
pressure Q Series™ DSC Systems. experiments, thermal cycling studies, and to improve sample
turnaround time. Stable baselines and linear heating and
cooling rates can be achieved between ambient and 725°C.

LNCS Controlled Cooling Rates, from 550°C (upper limit)* Quench Cooling Accessory
Controlled Rate To Lower Temperature The Quench Cooling Accessory (QCA) is a manually
operated cooling accessory, whose primary use is with
100°C/min 200°C
the Q20 and Q20P DSC to quench cool a sample to a
50°C/min 0°C subambient temperature prior to heating to an upper limit.
20°C/min -100°C The recommended temperature of operation of the QCA is
from –180 to 400°C. The QCA reservoir is easily filled with
10°C/min -150°C ice water, liquid nitrogen, dry ice, or other cooling media.
5°C/min -165°C
2°C/min -180°C

* Performance may vary slightly, depending on laboratory conditions.

16 17
 Tzero® Technology Provides: MDSC® Technology Provides:

• Flat reproducible baselines with better than an order of • Separation of complex transitions into more easily interpreted
magnitude improvement on competitive designs, especially components
in the subambient temperature range • Increased sensitivity for detecting weak transitions and melts
• Superior sensitivity due to flatter baselines and better
• Increased resolution without loss of sensitivity
signal-to-noise ratio
• Direct measurement of heat capacity
• Best available resolution
(better than power compensation devices) • More accurate measurement of crystallinity
• Faster MDSC experiments
®

• Direct measurement of heat capacity (Q2000)

Tzero technology represents a fundamentally more accurate system for In MDSC, a sinusoidal temperature oscillation is overlaid on the traditional
measuring heat flow, by incorporating cell resistance and capacitance linear ramp. The net effect is that heat flow can be measured simultaneously
characteristics which were previously assumed to be negligible. The with, and independently of, changes in heat capacity. In MDSC, the DSC
inclusion and compensation of these effects dramatically improves the heat flow is called the Total Heat Flow, the heat capacity component is the
baseline response and reproducibility. The heat flow resolution is also Reversing Heat Flow, and the kinetic component is the Nonreversing Heat
improved by directly measuring the heating rate difference between Flow. The Total Heat Flow signal contains the sum of all thermal transitions,
the sample and reference, and compensating for its effect on heat just as in standard DSC. The Reversing Heat Flow contains glass transition and
flow. This Tzero approach to measuring heat flow is a proprietary melting transitions, while the Nonreversing Heat Flow contains kinetic events
and patented* technology, only available on TA Instruments DSC like curing, volatilization, melting, and decomposition. The Q2000 uniquely
instruments. permits increased MDSC productivity of high quality data by its ability to
operate at standard DSC heating rates (e.g., 10°C/min).
*U.S. Patent No. 6,431,747; 6,488,406; 6,523,998

18 19
 Tzero® DSC Performance Applications

0.5 1.85

Baseline Stability (Flatness) 0.25

Q2000 Sensitivity (Lactose Tg) 1.80
5 Weight %

Heat Capacity (J/(g. ˚C))

Conventional DSC 115.35˚C (H) 2.5 Weight %
The figure to the right shows a comparison of a Q2000

Heat Flow (mW)

This figure illustrates the high level of sensitivity in a pharmaceutical 0.051J/(g.˚C) 117.66˚C (H)
empty cell baseline with that from a traditional heat flux application. The detection of small amounts of amorphous lactose 0.031J/(g.˚C)
DSC. The data shows that the Q2000 baseline is superior in 0.00 1.75
is critical for drug development and is easily achieved on a 10 mg
every way. The start-up offset is much smaller, the baseline is sample at 20°C/min using the Q2000. The direct measurement of
dramatically straighter, and the slope is greatly reduced. heat capacity allows the step change in Cp to be quantified, which
This contrasts markedly with results from other DSC designs, -0.25 1.70 120.23˚C (H)
is found to be directly proportional to the amount of amorphous 0.013J/(g.˚C)
where a baseline curvature 1 mW over the same temperature material present in the sample. 1 Weight %
range is often considered acceptable.
-0.5 1.65
-100 25 150 275 400 80 100 120 140 160
Temperature (˚C) Temperature (˚C)

-0.1 5˚C/min 190.89˚C

Resolution 0
Sensitivity (Polymer Tg) -18˚C
The figure to the right shows the excellent resolution inherent in the -2.3
This figure shows a Q2000 high sensitivity glass transition -0.2 10˚C/min -10

Heat Flow (mW)

Tzero® heat flow signal. This pharmaceutical compound contains

Heat Flow (mW)

(Tg) measurement, as a function of heating rate, for a very -17˚C a series of polymorphic transitions. Note that each peak is easily
-2.4
156.08˚C
small (1 mg) sample of polypropylene, whose Tg is not resolved, while simultaneously maintaining sensitivity for the subtle

Heat Flow (mW)

-2.5
easily measured by DSC due to its highly crystalline nature. -20 168.40˚C
-0.3 glass transition at lower temperature (inset). -2.6
The data shows that the Tg is easily detected even at a slow
5°C/min heating rate. The excellent Q2000 baseline is the -2.7 160.75˚C
-30
essential key for accurate measurements of glass transitions 20˚C/min
-0.4 -13˚C -2.8
and heat capacity from materials that exhibit weak and 150 152 154 156 158 160 162 164 166 168
Temperature (˚C)
192.59˚C
broad transitions. -40
-40 -30 -20 -10 0 10 20 150 160 170 180 190 200 210
Temperature (˚C) Temperature (˚C)

20 21
 MDSC® Applications

-0.4 -0.4 0.0

-36.08˚C Nonreversing

Nonreversing Heat Flow (mW)

Nonreversing Heat Flow (mW)
Separation of Complex Transitions Improved Data Interpretation -0.2 0.0

Reversing Heat Flow (mW)

5.704 J/g
-0.6 0.0 -0.6

Rev. Heat Flow (mW)

Heat Flow (mW)
The figure to the right shows the MDSC results for a thermoplastic The figure shows an application of interest in studies of foods or -0.2

Heat Flow (mW)

-43.66˚C
alloy blend of polycarbonate (PC) and polybutylene terephthalate pharmaceuticals, in which the MDSC® total heat flow signal and
-0.8 Total -0.2 -0.8 -41.54˚C(H)
(PBT). This material exhibits a variety of overlapping transitions, its reversing and non-reversing components are displayed for a -0.4 -0.2
and interpretation of the Total Heat Flow is complicated. MDSC quenched 40% aqueous sucrose sample. The reversing signal
-39.4˚C
effectively separates the crystallization of the PBT component PBT Tg Reversing clearly indicates a Tg for sucrose between -43.6 and -39.4°C. -0.4
into the Nonreversing Heat Flow, thereby allowing for accurate -1.0 -0.4 -1.0 The exothermic nonreversing signal relates to crystallization of
determination of the glass transition temperatures of each PC Tg free water that could not crystallize during quench cooling of the -0.6 -0.4
polymer in the Reversing Heat Flow. Melting Onset sample due to a significant increase in mobility and diffusion of
-1.2 -1.2 the material at the glass transition. -0.6
0 50 100 150 200 -60 -50 -40 -30 -20
Temperature (˚C)
Temperature (˚C)

1.5 2.6
Quasi-Isothermal Heat Capacity 50.73 min
Improved Signal Sensitivity Total Heat Flow One of the major benefits of Modulated DSC is the ability 1.0 350 2.4

MDSC provides improved sensitivity for measuring very to measure heat capacity in a quasi-isothermal mode, i.e. 300 2.2

Heat Flow (mW)

0.5

Temperature (˚C)
broad and weak transitions, such as glass transitions in highly isothermal with the exception of a small temperature modulation.

Rev. Cp (J/g/˚C)
256.4 J/g

Heat Flow (mW)

crystalline polymers or where the Tg is hidden beneath a second Quasi-isothermal MDSC is particularly beneficial when studying 250 2.0
overlapping thermal event. This data was generated using a curing systems. The figure below contains the quasi-isothermal 0.0
75.30 min 200 1.8
very small (2.2 mg) sample of a polymer coating. The total heat Reversing Heat Flow 109˚C (H) analysis of thermosetting epoxy resin. In the first part of the
flow shows no transitions in the region where a Tg would be 0.009 mW experiment, the curing is monitored at 100°C for 160 min, and -0.5
150 1.6
expected, though the large endotherm around 40°C indicates is evident as a decrease in Cp and a large exotherm in the Total
solvent loss. The Reversing Heat Flow does indicate a very weak Heat Flow. The second stage involved heating the sample under -1.0 100 1.4
MDSC conditions at 3°C/min to measure the Tg of the cured 31.06 J/g
(8.5 µW) Tg around 109°C, confirming the sensitivity of the
MDSC technique. system, as well as residual cure. -1.5 1.2
0 20 40 60 80 100 120 140 0 50 100 150 200 250
Temperature (˚C) Time (min)

22 23
 Tzero® Pans/Lids Applications Standard Pans/Lids Applications

0
Fabricated using advanced technology and to extremely
-2 DSC pans & lids are available in aluminum, alodine-coated aluminum, gold, platinum, graphite, and stainless steel versions. They can be used

Heat Flow (mW)

tight tooling specifications, the Tzero pans offer a significant
under a variety of temperature and pressure conditions. Samples can be run in the standard DSC mode in open pans, pressed or hermetically
improvement over previous generations, as well as competitors’
sealed pans/lids or in pressure capsules. Samples in open pans can also be run at controlled pressures using the PDSC Cell. All aluminum
technology, in standard performance tests on indium metal. -4
standard pans have the same temperature and pressure rating. General details of the pans are shown here.
In the figure to the right, note the improvement in signal
-6 Tzero Pan Standard Pan
response and peak quality when using the Tzero pan versus
a standard pan.
-8

-10
154 155 156 157 158 159 160 Standard Temperature (°C) Pressure
Temperature (˚C) Aluminum -180 to 600 100 kPa
Platinum -180 to 725 100 kPa
-2.5 Gold -180 to 725 100 kPa
The utility of the Tzero hermetic pan is shown here. Tzero Hermetic Pan Graphite -180 to 725 100 kPa
In this example, DSC results for casein are shown using
both a hermetic pan and a standard pan. Casein contains a -3.0 96.70˚C
108.40˚C(l) Hermetic Temperature (°C) Pressure
significant amount of adsorbed moisture, which is evolved

Heat Flow (mW)

when heating in a standard pan. The resultant data only 114.97˚C Aluminum -180 to 600 300 kPa
exhibits the large evaporation endotherm. However, when -3.5 Alodined Aluminum -180 to 200 300 kPa
analyzed in a Tzero hermetic pan, the volatilization is Gold -180 to 725 600 kPa
suppressed, and the glass transition of the casein is clearly Standard Pan
High Volume -100 to 250 3.7 MPa
identified. -4.0 Stainless Steel Amb. to 250 10 MPa

-4.5
40 60 80 100 120 140
Temperature (˚C)

24 25
 DSC Applications

1.5
Transition Temperatures Thermal History
DSC provides rapid and precise determinations of transition Oxidation DSC is an excellent tool for determining the thermal history of 1.0

Heat Flow –> exothermic

temperatures using minimum amounts of a sample. Common or Cool
Decomposition a polymer sample. In this experiment, the sample is subjected

Heat Flow (mW/mg)

temperature measurements include the following: to a “heat-cool-reheat” cycle and a comparison is made 0.5
between the two heating cycles. This figure contains the
Melting 0.0 Second Heat
• Melting • Crystallization heat-cool-reheat results for a polyester sample. By comparing First Heat
Glass
• Glass Transition • Polymorphic Transition Transition Crystallization Crosslinking the first heating cycle (unknown thermal history) to the
• Thermal Stability • Liquid Crystal (Cure) second heating cycle (known thermal history), information -0.5
• Oxidation Onset • Protein Denaturation can be derived concerning the original morphology of the
• Cure Onset • Solid-Solid Transition -1.4
material. This can be useful in troubleshooting problems in
performance or processing conditions.
This composite shows typical shapes for the main transitions -1.5
20 60 100 140 180 220 260
observed in DSC. Temperature
Temperature (˚C)

Kinetics
-4 0.5
Heat Flow Kinetics is the study of the effects of time and temperature
Glass Transition Polymorphic Conversion on a reaction. Isothermal crystallization is an example of an
Heat Flow is the universal detector, as all physical and -5 experiment in which kinetic information can be derived. 0.4
1.67 min
chemical processes involve the exchange of heat. As such, This data shows the isothermal crystallization results for a

Heat Flow (mW)

Heat Flow (mW/g)

the DSC Heat Flow signal is commonly used to measure -6 polymer sample which is being crystallized at a variety of 0.3
and quantify a wide variety of transitions and events, often temperatures below the melting point. By analyzing the
occurring in the same material as a function of temperature. time to peak heat flow for each temperature, various kinetic
-7 0.2 2.50 min
This example shows a pharmaceutical material which is factors can be calculated including activation energy, rate
undergoing a variety of physical changes as it is heated from Crystallization Melting constant, and conversion percent. 3.49 min
subambient through its melting temperature. DSC is sensitive -8 0.1
6.35 min
to all of these events.
-9 0.0
0 50 100 150 200 0 2 4 6 8 10 12
Temperature (˚C) Time (min)

26 27
 DSC Applications

0.6 -0.04
Pressure (and Time) Sample A Degree of Cure
Sample B
Pressure DSC accelerates Oxidation Induction Time (OIT) analyses The degree of thermoset cure can dramatically affect the processing -0.08 155.93˚C
Sample C First
and resolves the onset of the oxidation process. The figure to the 0.4 Sample D and end-use conditions. DSC is often used to investigate and
Tg

Heat Flow (mW/mg)

right shows a comparative study of a series of two component

Heat Flow (W/g)

quantify the degree of cure for epoxy and other thermosetting
polymer dispersions containing different levels of the same -0.12 Residual Cure
materials. This figure contains the data for the first and second heats
antioxidant. Clear performance differences are readily seen. The 0.2 of a thermoset material. The exotherm in the first heat indicates
tests provided the same answer in under two days that took up that the sample was not fully cured as received. By quantifying the -0.16 Second 102.64˚C
to two months of traditional “field exposure” to obtain. Other residual cure, as well as comparing the glass transition temperatures 20.38J/g
common PDSC applications include thermoset resin cures, catalyst 0.0 of the two cycles, the degree of cure is easily determined.
studies, and micro-scale simulations of chemical reactions. -0.20

-0.2 -0.24
0 50 100 150 200 250 0 50 100 150 200 250 300
Time (min) Temperature (˚C)

Photocuring
5
The Photocalorimeter Accessory (PCA) provides a convenient Pharmaceutical Polymorph Analysis
tool to assess reactions initiated with UV/Visible light. This figure Pharmaceutical materials often exist in multiple crystal forms called 125.91˚C
compares two different acrylic formulations under the same polymorphs. These have the same chemical structure but a different 0 0.63J/g
conditions. The data shows that formulation A cures rapidly upon A

Heat Flow (mW/mg)

crystalline structure which can result in significant differences in

Heat Flow (mW)

exposure to UV radiation, while formulation B reacts slower, and physical properties such as solubility, bioavailability, and storage
has both a longer time-to-peak and lower energy. In all PCA stability. DSC is the prevalent technique for the detection of -5
experiments, the peak shapes and transition energies are affected pharmaceutical polymorphism. The DSC analysis of a pharmaceutical
by the formulation chemistry, additives, initiators, and the purge material in which three distinct polymorphs are detected on heating
gas used. the amorphous compound is shown here.
B -10

128.39˚C
-15
0 1 2 3 4 5 50 100 200 250
Time (min) Temperature (˚C)

28 29
 Thermogravimetric Analysis

A TGA designed to meet the most demanding research applications

 TGA Q500
SPECIFICATIONS

Temperature Compensated Thermobalance Included

Maximum Sample Weight 1g
Weighing Precision +/- 0.01%
Sensitivity 0.1 µg
Baseline Dynamic Drift* < 50 µg
The Q500 is the world’s best-selling, research-grade Furnace Heating Resistance Wound
thermogravimetric analyzer. Its field-proven performance Evolved Gas Analysis Furnace (EGA) Optional
arises from a responsive low-mass furnace, ultra- Temperature Range Ambient to 1 000°C
sensitive thermobalance, and efficient horizontal purge Isothermal Temp Accuracy +/- 1°C
gas system with mass flow control. Its convenience, Isothermal Temp Precision +/- 0.1°C
Controlled Heating Rate 0.01 to 100°C/min
expandability and powerful, results-oriented software
Furnace Cooling (forced air/N2) 1 000 to 50°C < 12 min
make the Q500 ideal for the multi-user laboratory
Temperature Calibration Curie Point
where a wide variety of TGA applications are 16 Position Autosampler Optional
conducted, and where future expansion of analytical Hi-Res TGA™ Optional
work is anticipated. Auto Stepwise TGA Included
Modulated TGA™ Optional
TGA/MS Operation Optional
TGA/FTIR Operation Optional
Platinum™ Software Included
Sample Pans Platinum 50, 100 µL
Ceramic 100, 250, 500 µL
Aluminum 100 µL
* From 50 to 1 000˚C at 20˚C/min using empty platinum pans, no baseline/blank subtraction.

32 33
 TGA Q50 SPECIFICATIONS

Temperature Compensated Thermobalance Included

Maximum Sample Weight 1g
Weighing Precision +/- 0.01%
Sensitivity 0.1 µg
Baseline Dynamic Drift* < 50 µg
The rugged, reliable, and cost-effective Q50 Furnace Heating Resistance Wound
TGA, with many features of the Q500, offers EGA Furnace Optional
exceptional value as a compact, general-purpose Temperature Range Ambient to 1 000°C
thermogravimetric analyzer that typically out- Isothermal Temp Accuracy +/- 1°C
Isothermal Temp Precision
performs competitive research-grade models.
+/- 0.1°C
Its integral mass flow control, gas switching
Controlled Heating Rate 0.1 to 100°C/min
capability, superb software, and ease-of-use Furnace Cooling (forced air/N2) 1 000 to 50°C < 12 min
make the Q50 ideal in basic research, teaching, Temperature Calibration Curie Point
or in industrial laboratories that need quality Auto-Loader Included
results at a modest cost. Auto Stepwise TGA Included
TGA/MS Operation Optional
TGA/FTIR Operation Optional
Platinum™ Software Included
Sample Pans Platinum 50, 100 µL
Ceramic 100, 250, 500 µL
* From 50 to 1 000˚C at 20˚C/min using empty platinum pans, no baseline/blank subtraction.

34 35
 Photodiode
Q500/Q50 Technology

Sensitive, precise, rugged, and automated all describe the TA Instruments Q500 and Thermobalance Flag
Q50 Thermogravimetric Analyzers (TGA). These are fourth generation products from the The heart of a Q500/Q50 TGA is the accurate and reliable vertical
world leader in thermogravimetric analysis. Each represents an unparalleled investment thermobalance housed in a temperature-compensated environment. Unlike
because it delivers outstanding performance, is designed with the customer in mind, and competitive instruments, no expensive circulator is required for optimal
is backed by superior support that is the hallmark of our company. performance. It uses the field-proven and industry-standard null-balance
principle, which is free from the baseline complications also inherent in
competitive designs. The Q500/Q50 balance provides the best accuracy
and precision in weight change detection from ambient to 1 000˚C, low
baseline drift, and sensitive, reliable operation over the entire weight range.
Furnace
Sample Arm Tare Arm
Our custom-designed furnace is a key element of a Q500/Q50 TGA. It features low
mass, rugged heater windings, and proprietary heater control technology. User benefits
include rapid, accurate, and precise temperature and rate programming, plus optimized
use in the Q500 of advanced techniques such as Hi-Res™ TGA and Modulated TGA™. Meter Movement
Our reliable, long-life furnaces also increase the value of your investment.

Temperature Control and Measurement

Our unique, custom-designed system features a single control/sample thermocouple Purge Gas System
positioned immediately adjacent to the sample. A second thermocouple is located slightly An efficient horizontal purge gas system allows accurately metered purge
above in the same sleeve. The design ensures that simultaneous heating rate control gas to flow directly across the sample, and is expertly integrated into the
and sample temperature measurement are accurately and precisely accomplished. This vertical thermobalance/furnace design. A regulated portion of the gas is
innovative “control and feedback” design enables the system controller to program also directed through the balance chamber to eliminate backflow, and the
and maintain the temperature environment and heating rate selected by the operator. combined gases plus any sample effluent exit the system by a side arm.
The second thermocouple also serves as a safeguard to automatically disable the furnace The design minimizes buoyancy effects, and optimizes removal of
should the temperature difference between the thermocouples exceed a set value. decomposition products from the sample area. The digital mass flow
controllers improve data quality.
Mass Flow Control (with automatic gas switching)
Dual digital mass flow controllers (standard on all TA Instruments TGAs) provide accurate
and precise purge gas metering. The automatic low volume, high-speed switching valves
deliver instantaneous change of purge gas that is critical when converting between inert
and oxidizing atmospheres. Gas flow rates are available as stored data file signals.

36 37
 TGA Accessories & Options
Quartz Liner
Thermocouple
Furnace Heating Element Autosampler
The Q500 Autosampler accessory is a programmable, multi-position sample carousel that allows fully automated analysis of up to 64 samples
(16 samples per tray). All aspects of sample testing are automated and software controlled, including pan taring and loading, sample
weighing, furnace movement, pan unloading, and furnace cooling. The autosampler has the flexibility to meet the needs of both research and
Evolved Gas Port QC laboratories. Autosampler productivity is maximized by our Advantage™ software, which permits pre-programmed analysis, comparison,
and presentation of results.

Evolved Gas Analysis (EGA) Furnace

The rugged and reliable EGA is an optional, quartz-lined furnace for
the Q500 or Q50. The liner is chemically inert to products produced
from decomposition of the sample, resistant to adsorption of offgas
products, and its reduced internal volume ensures rapid exit of these
materials from the sample chamber. These features make the EGA an
ideal furnace for use in combined TGA/MS or TGA/FTIR studies.

Sample Pan

Purge Gas Inlet

38 39
 Evolved Gas Analysis EGA Applications

Evolved gas analysis involves the qualitative investigation of the evolved gas products from a TGA experiment. These products are generally the result of
decomposition, but can also evolve from desorption, evaporation or chemical reactions. Evolved gas analysis is typically performed by interfacing a mass 120 1
amu
spectrometer (MS) or Fourier transform infrared spectrometer (FTIR) to the exit port of the TGA furnace. Through the use of a heated transfer line, the evolved TGA-MS: Polymer Analysis 100 45
gas stream is delivered to the MS or FTIR instrument, and the compositional analysis is performed in real time. TA Instruments offers a 300 amu bench-top,
quadrapole mass spectrometer with a heated capillary interface, and TGA module-specific interface kits for its Discovery TGA, Q500 and Q50 modules. A This data shows the TGA-MS results for the decomposition 55 0.1
of ethylene vinyl acetate copolymer. The first step involves 56
variety of FTIR suppliers provide gas cells and interfaces for use with all our TGA modules. 80

Ion Current (nA)

57
the decomposition of the vinyl acetate phase, resulting in the

Weight (%)
60
TA Instruments Thermogravimetric Analyzers are the ideal platform for evolved gas analysis studies. Each TA Instruments TGA features a horizontal purge stream production of acetic acid. By monitoring signals typical of acetic 60 0.01
over the sample and a short path to the exit port. This eliminates dead volume in the furnace thereby reducing product dilution and optimizing EGA sensitivity. acid, the production of the offgas compound is readily detected.
The Q500 and Q50 can be equipped with the quartz-lined evolved gas analysis (EGA) furnace which minimizes adsorption of effluent gases onto the furnace. The second step involves the thermal decomposition of the 40
The Discovery TGA features heated EGA adapters designed to interface directly with the MS or FTIR transfer line. These adapters ensure continuous heating of polyethylene phase, and its unique decomposition products are 0.001
the offgas stream through the furnace wall, dramatically reducing offgas condensation and improving EGA sensitivity. easily identified and recorded. 20

TA Instruments Universal Analysis software supports the importation of MS (trend analysis) and FTIR data (Gram-Schmidt and Chemigram reconstructions), 0 0.0001
allowing TGA and EGA data to be displayed on a common axis of temperature and/or time. 0 100 200 300 400 500 600 700
Temperature (˚C)

TGA-FTIR: Phenolic Resin Decomposition

This figure contains the TGA-FTIR results for the thermal 34.945min
0.4 100
decomposition of a phenolic resin adhesive. A Gram-Schmidt 442.78˚C
reconstruction of the time-resolved FTIR spectra is compared to 1.5

the weight loss signal as a function of time and temperature. 0.3 1.3

1.1
80
The inset image contains the FTIR spectrum of the offgas

Weight (%)
0.9

Intensity

Absorbance
composition at 34.95 minutes, near the point of the maximum 0.2 0.7

0.5
rate of decomposition. The FTIR spectrum corresponding to this
60
0.3

temperature indicates that the offgas products are primarily 0.1

composed of phenols, including bisphenol A, which is included 0.1 4000 3500 300 2500 2000 1500 1000 500
Wavenumbers (cm-1)

as a comparison spectrum. This level of chemical specificity

is useful in comparing similar products, quality control, and 0.0 Temperature (˚C) 40
100 200 300 400 500
fingerprint analysis.
0 10 20 30 40 50
Time (min)

40 41
 Advanced TGA Techniques Sample Pans

TA Instruments has been the pioneer in advancing the science of improved resolution
TGA techniques and in providing powerful but easily used software to accelerate
material decomposition kinetic studies while preserving data quality.

High Resolution TGA™ (Hi-Res™ TGA)

Hi-Res TGA* is a patented furnace control technology that produces significant
improvements over standard linear heating rate TGA in the separation of closely
occurring decomposition events. Both the Discovery TGA and the Q500 designs are
ideal for this purpose, with rapid response furnaces for precise temperature control Platinum (50 and 100 µL), and new style ceramic (100, 250, and 500
and sensitive thermobalances designed to quickly detect small weight changes. µL) pans are available for use with the Q500 and Q50 TGA modules
Specific control algorithms (constant reaction rate and dynamic rate) are supplied from ambient to 1 000˚C. Platinum pans are recommended in most
with the Discovery TGA and are available for the Q500. Auto-stepwise isothermal cases due to its inertness and ease of cleaning. The larger ceramic
is a third high resolution technique, and is supplied with all the TA Instruments TGA pans are best for analysis of higher volume / low density samples such
models. as foams. They are also advised for use with samples that react with
or form alloys with platinum. The aluminum (100 µL) pans are cost-
*U.S. Patent No. 5,165,792 effective substitute pans but cannot be used above 600˚C.
Canadian Patent No. 2,051,578
European Patent No. 0494492

Modulated TGA™ (MTGA™)

MTGA** is another TA Instruments innovation that offers advantages for material
decomposition studies. Its development arose from the proprietary heater control
technology developed for Hi-Res TGA and MDSC®. MTGA produces model-free kinetic
data, from which activation energy can be calculated and studied as a function of time,
temperature, and conversion. It is easy-to-use and produces in a single run the kinetic
data needed to improve industrial process productivity.

**U.S. Patent Nos. 6,113,261 and 6,336,741

42 43
 Applications
  120
High Resolution™ TGA 3RO\XUHWKDQH6WDQGDUG7*$ Compositional Analysis Latex Flat Paint
 3RO\XUHWKDQH+L5HV7*$ Latex Gloss Paint
This figure compares the decomposition profile plots of a TGA is used to determine sample composition by measuring 100 Oil Based Gloss Paint
polyurethane material by standard and by Hi-Res™ TGA. 6WDQGDUG7*$` Û&PLQ 
the weight of each component as it volatilizes or decomposes Weight Loss: 1st 2nd

'HULY:HLJKW Û &
 +L5HV7*$` Û&PLQ5HV 
The resolution superiority of the Hi-Res technique is clearly 1LWURJHQ3XUJHP/PLQ under controlled conditions of temperature, time, and 80 Latex Flat: 56% 8%

:HLJKW
evident in both the TGA and first derivative (DTG) signals. Latex Gloss: 51% 30%

Weight (%)
atmosphere. This figure shows quantitative differences in
The latter signal is especially useful in defining the onset and   Oil Based Gloss: 45% 32%
type, amount, and decomposition mechanism of the main 60
endset of the individual weight loss segments, as well as (10˚C/min.; Nitrogen Purge)
polymers in three paint samples. More detailed examination
indicating subtle events that help to provide a “fingerprint” of 
of the profiles below 150°C may reveal further information 40
the sample under the analysis conditions. 
on the amount and possible nature of the carrier solvent
 (aqueous or oil) used in each paint. 20
 
        0
0 100 200 300 400 500 600
7HPSHUDWXUHÛ& Temperature (˚C)

120 400 105 0.8

131˚C Organic Salt Hydrate
Modulated TGA™ 100 100 Loss 1 3.57%
Loss 1 0.6
350 Volatiles Analysis Loss 2 2.31%

Activation Energy (kJ/mol)

The figure to the right shows data from a MTGA™ kinetic 80 Loss 2 Loss 3 9.64%

Deriv. Weight (%/˚C)

study of the effect of temperature on the decomposition of TGA determinations of absorbed, bound, or occluded 95 Total 15.52%
300 0.4

Weight (%)
60% ethylene vinyl acetate (EVA) in a single experiment. The

Weight (%)
60 moisture, and organic volatiles are important analyses
plot quantitatively shows the EVA decomposition profile and for product performance and environmental acceptance. 90 Loss 3
changes in activation energy as functions of temperature. 40 250 Analysis of an organic salt hydrate in nitrogen atmosphere 0.2
The data supports a dual-step decomposition mechanism. shows a bound-water content of 9.6%, and two lower 85 59˚C 101˚C
MTGA can also monitor activation energy as a function of 20
temperature weight losses of 3.6% and 2.3% respectively.
conversion, which indicates the mechanism involved. MTGA 200 80 0.0
0 These losses are likely due to adsorbed moisture at the salt
is available for the Q500. surface or held to it by weak attractive forces.
-20 150 75 -0.2
200 250 300 350 400 450 20 40 60 80 100 120 140 160 180 200
Temperature (˚C) Temperature (˚C)

44 45
 Applications

100
Effect of Additives Quantification of Filler Content 100

This figure compares the decomposition profiles of a poly- Heat Rate: 10˚C/min
80 TGA is a sensitive technique for analyzing and quantifying the 80
carbonate material with and without an added flame 460˚ ATM: Air
-28% filler content of polymeric composites. This figure contains a Method Log:
retardant. The flame-retarded material consistently decomposed at comparison of the TGA results for a virgin and filled PET 1: Ramp 20˚C/min to 650˚C
60

Weight (%)
460˚ 481˚ 2: Select Gas: 2

Weight (%)
a temperature about 20-25°C lower than that of the unmodified sample. The virgin material is first analyzed for comparison. By 60 3: Ramp 20˚C/min to 1000˚C 6.65% Carbon Black
-48% -48%
sample. The former material also lost a greater percentage quantifying the weight loss of the initial lower-temperature
of weight than the standard material (e.g., 48% vs. 28%) at a 40 40 78.64% 85.65%
decomposition, and comparing it to the oxidative decomposition
given temperature (e.g., 460°C) during the decomposition step. in the second weight loss, the filler content of the composite (11.26mg) (16.01mg)
This indicates that flame-retardant additives accelerate the 20 Flame Retardant material is accurately quantified. 20
polycarbonate decomposition. The purpose of the retardant Standard 20.64%
material is to inhibit flame propagation. 13.99% (2.957mg)
0 0 (2.614mg)
0 200 300 400 500 600 700 800 0 200 400 600 800 1000
Temperature (˚C) Temperature (˚C)

Verification of Thermal Events Moisture Content & Thermal Stability

2.0
5 100
TGA is very useful in conjunction with other thermal analysis 110 of a Pharmaceutical Material 150.00˚C 1.5
techniques such as DSC and is often critical to understanding
-5 80 98.04%

Deriv. Weight (%/min)

the true nature of thermal events. In this data, a pharmaceutical TGA is a useful technique for determining the absolute and
100

Heat Flow (mW)

material undergoes an endothermic transition above 125°C which relative thermal stability of pharmaceutical compounds, as well 400.00˚C
1.0

Weight (%)

Weight (%)
was previously thought to be melting. TGA analysis demonstrates -15 as the moisture content. In this example, an active pharmaceutical 60 0.7795 %/min.
125˚C 90
considerable weight loss below 125°C, which suggests that the ingredient (API) is analyzed by TGA at a heating rate of
90.00% 0.5
endotherm is actually decomposition. DSC analysis at multiple -25 10°C/min. The data show a small (~2%) weight loss below 40
80
rates exposes rate-dependence of this transition which confirms 150°C, which is typical for adsorbed water. The material is
decomposition. -35 relatively stable up to 200°C, after which a large, multi-step 0.0
70 20
weight loss is indicative of thermal decomposition.
-45 0 -0.5.2
40 60 80 100 120 140 160 180 0 100 200 300 400 500 600
Temperature (˚C) Temperature (˚C)

46 47
 Simultaneous TGA/DSC

Providing high-quality, truly differential simultaneous measurements

 SDT Q600 SPECIFICATIONS

System Design Horizontal Balance & Furnace

Balance Design Dual Beam (growth compensated)
Sample Capacity 200 mg (350 mg including sample holder)
Balance Sensitivity 0.1 µg
The Q600 provides simultaneous measurement Furnace Type Bifilar Wound
Temperature Range Ambient to 1 500°C
of weight change (TGA) and true differential heat
Heating Rate – Ambient to 1 000°C 0.1 to 100°C/min
flow (DSC) on the same sample from ambient
Heating Rate – Ambient to 1 500°C 0.1 to 25°C/min
to 1 500˚C. It features a field-proven horizontal Furnace Cooling Forced Air (1 500 to 50˚C in < 30 min,
dual beam design with automatic beam growth 1 000˚C in 50˚C in < 20 min)
compensation, and the ability to analyze two TGA Thermocouples Platinum/Platinum-Rhodium (Type R)
samples simultaneously. DSC heat flow data is Temperature Calibration Curie Point or Metal Standards (1 to 5 Points)
dynamically normalized using the instantaneous DTA Sensitivity 0.001°C
sample weight at any given temperature. Calorimetric Accuracy/Precision ± 2% (based on metal standards)
Mass Flow Controller with Automatic Gas Switching Included
Vacuum to 7 Pa (0.05 torr)
Reactive Gas Capability Included – separate gas tube
Dual Sample TGA Included
Auto-Stepwise TGA Included
Sample Pans Platinum: 40 µL, 110 µL
Alumina: 40 µL, 90 µL

50 51
 SDT Technology High Resolution SDT
If separation of closely related weight losses is required, the
Q600 offers an automated version of StepWise Isothermal
(SWI), the classical technique for improved TGA resolution.
The stepwise isothermal approach consists of heating at a
Thermobalance constant rate until a weight change begins (as determined by
an operator-chosen rate or amount of weight loss) and then
The Q600 features a highly reliable horizontal dual-balance mechanism that supports precise
holding isothermally until the weight change is complete. This
TGA and DSC measurements. It delivers superiority in weight signal measurements (sensitivity, sequence of heating and isothermal steps is repeated for each
accuracy and precision) over what is available from single beam devices, since the dual beam Sample Cup Photodiodes and Sensors weight change encountered. The result is optimum weight loss
design virtually eliminates beam growth and buoyancy contributions to the underlying signal. Dual-Balance Mechanism resolution.
It also uniquely permits independent TGA measurements on two samples simultaneously.
Sample Holder
Temperature Calibration and
Temperature Control and Measurement Furnace
Weight Loss Verification
A matched Platinum/Platinum-Rhodium thermocouple pair within the ceramic beams provides
TA Instruments offers the widest range of ICTAC certified and
direct sample, reference, and differential temperature measurements from ambient to 1 500ºC.
NIST traceable Curie Point reference materials that provide
This results in the best available sensitivity in detection of thermal events. Curie Point or pure metal SDT apparatus temperature calibration over the range from
standards can be used for single or multi-point temperature calibration. Calibration of the DSC 150 to 1 120°C. TA Instruments also offers certified Mass
signal with sapphire standards results in a differential heat flow (DSC) signal that is intrinsically Loss Reference Materials for validation of SDT instrument
superior to that from single beam devices. performance.
Reactive Gas Inlet

Furnace Balance/Thermocouple Beams Q600 Sample Pans

The Q600 features a rugged, reliable, horizontal furnace encased in a perforated stainless steel Platinum pans (40 and 110 µL) and ceramic cups (40 and
enclosure. The design ensures accurate and precise delivery of programmed and isothermal 90 µL) are available for use with the Q600. The platinum cups
operation over the full temperature range from ambient to 1 500ºC. The design also provides for are recommended for operation to 1 000°C, and for their
Sample/Reference Cups general inertness and ease of cleaning. The ceramic cups are
operator ease-of-use due to its automatic furnace opening/closing, easy sample loading, and
rapid post-experiment furnace cool-down. advised for operation to 1 500°C, and for samples that react
Thermocouple with platinum.
Horizontal Purge Gas flow
Purge Gas System Balance Arm
A horizontal purge gas system with digital mass flow control and integral gas switching capability
provides for precise metering of purge gas to the sample and reference pans. The design produces
better baselines, prevents back diffusion, and efficiently removes decomposition products from the
sample area. A separate Inconel® gas inlet tube efficiently delivers reactive gas to the sample. The
Q600 exhaust gas port can be readily connected to a MS or FTIR for component identification
purposes.
® Inconel is a registered trademark of Special Metals Corporation

52 53
 Applications

102 0.9
High Sensitivity
This figure shows a high sensitivity application of the Q600 96 Dehydration
Heat Flow (W/g) 7 0.6
in which a small (3 mg) sample of sodium tungstate is
90

Deriv. Weight (%/˚C)

2 analyzed at 10°C/min from ambient to 800°C. The TGA
Heat of Fusion using Weight at Start of Integration 4 0.3
and derivative TGA (DTG) signals quantitatively record the

Weight (%)
468.7J/g 459.1J/g 459.2J/g 464.4J/g 16 84
0 dehydration step. The DSC trace quantitatively shows the
14 loss of water plus higher temperature solid state phase and 78 1 0.0
-2 melting transitions respectively. The latter pair are thermal

Heat Flow (W/g)

13.27mg 12 72
Improved DSC Data events where no weight loss occurs.

Weight (mg)
-4 -2 -0.3
11.27mg 66
In SDT experiments, superior accuracy in DSC data is -6 10 Solid State and Melting Transitions
obtained when the instantaneous weight (rather than the 9.379mg 60 -0.6
7.628mg 8
initial sample weight) is used in heat flow calculations. This -8 0 200 400 600 800
figure shows data for sodium chloride (which loses weight on Temperature (˚C)
-10 Heat of Fusion using Original Weight (13.26mg) 6
heating) cycled through its melt four times, and the heat of
fusion (J/g) determined using the instantaneous weight. The 468.7J/g 384.1J/g 324.7J/g 266.9J/g
-12 4
accompanying table shows a comparison of this data versus 20 40 60 80 100
an identical experiment where the initial sample weight
Simultaneous DSC/TGA 100 Polymorphic Phase Transitions
Time (min)
was used for calculating the DSC data in each cycle. Melting
The differences in reproducibility are significant. This figure contains simultaneous DSC and TGA data to Transition -2
Dehydration
1 300°C for a soda ash sample. The TGA signal measures

Heat Flow (W/g)

Cycle 1 Cycle 2 Cycle 3 Cycle 4 the dehydration and the onset of a higher temperature 90

Weight (%)
Heat of Fusion decomposition. The DSC signal reveals transitions associated -4
468.7 384.1 324.7 266.9 with the dehydration, a polymorphic phase transition and
Initial Weight (J/g)
the high temperature melt. The inset shows details about the 80
Heat of Fusion phase transition. In the Q600, heat flow integrations are -6
468.7 459.1 459.2 464.4
Instantaneous Weight (J/g) automatically normalized using the dynamic weight at the
start of each transition. 300 400 500 600
70 -8
0 200 400 600 800 1000 1200 1400
Temperature (˚C)

54 55
 Vapor Sorption Analysis

Sensitive Measurements, Precise RH Control

 VTI-SA+
SPECIFICATIONS The VTI-SA+ Vapor Sorption Analyzer is a
continuous vapor flow sorption instrument for
Maximum Sample Weight 750 mg/5 g
Dynamic Range 100 mg/500 mg
obtaining precision water and organic vapor
Weighing Accuracy +/- 0.1%
isotherms at temperatures ranging from 5°C to Weighing Precision +/- 0.01%
150°C at ambient pressure. The VTI-SA+ combines Sensitivity 0.1 µg/0.5 µg
the features of VTI’s original SGA design with Signal Resolution 0.01 µg/0.05 µg
almost two decades of field-proven performance: Temperature Control Peltier Elements, Resistance Heaters
the isothermal aluminum block construction, Experimental Temperature Range 5 to 150°C
the three isolated thermal zones and chilled- Isothermal Stability +/- 0.1°C
Relative Humidity Control Range See Figure Below
mirror dew point analyzer for primary humidity
Accuracy +/- 1% RH
measurements with the field-proven TA Instruments
Humidity Control Closed Loop, Dew Point Analyzer
thermobalance technology… all to provide precise Organic Solvent Capability Optional
and accurate gravimetric measurements with Camera/2.5x Microscope Accessory Optional
excellent temperature and RH stability. Raman Probe Accessory Optional

100
98%

80 80%

Relative Humidity (%RH)

63%
60

41%
60
27%
20 Limit of Control 19%
13%
9%
0
5 25 45 65 85 105 125 145
Temperature (˚C)
*Performance may vary slightly, depending on laboratory conditions

58 59
 VTI-SA+ Technology

Symmetrical Microbalance Design

The VTI-SA+ Analyzer is a symmetrical vapor sorption instrument where both the sample and reference chambers are exposed to the same conditions of
temperature and humidity. In this symmetrical design, any water or organic vapor sorption onto the hangdown wires and sample holder is differentially
eliminated and the resultant data represents the uptake by the sample alone. This eliminates the need for background subtraction experiments and associated
uncertainty typical in competitive, asymmetrical systems.

Resolution and Stability of the Microbalance

The standard VTI-SA+ boasts a microbalance designed and manufactured by TA Instruments with 0.1 microgram sensitivity optimized for pharmaceutical
applications. A higher mass capacity version (5 g, 0.5 microgram sensitivity) is also available. To ensure effective work in pharmaceutical studies, the design
provides an enhanced stability by maintaining the balance compartment at a constant temperature, independent of the sample temperature. Because the
balance is maintained at constant temperature, the user has the option of drying the sample at temperatures other than the experimental temperature or to run
different temperature and RH profiles without removing the sample.

Precision Humidity Measurements

As part of our standard design, the VTI-SA+ employs a chilled mirror dew point analyzer (a NIST-traceable standard for humidity) to determine the absolute
relative humidity at the sample. In applications where RH control is critical (as in most pharmaceutical studies), chilled-mirror dew point analyzers are the
preferred method, because of the absence of drift and long term stability.

Sorption Testing Using an Organic Vapor

The VTI-SA+ can also be configured for organic vapor sorption. In the VTI-SA+, the concentration of the organic vapor in the gas stream reaching the sample is
determined by the fraction of gas going through the organic solvent evaporator and the fraction of dry gas.

In competitive systems, assumptions are made that the evaporator is 100% efficient and that the temperature of the evaporator is constant from low to high
concentrations. The VTI-SA+ system measures the temperature of the organic solvent in the evaporator and uses this information together with the Wagner
equation to control the organic vapor concentration in the gas phase. This method solves the issue of adiabatic cooling of the solvent, a major source of error
in competitive systems.

The solvent containers/evaporators are easily removed and exchanged so there is no need for decontamination or cleaning of the system when changing
organic solvents or reverting to water sorption experiments. For safety, the evaporator compartment is purged with dry nitrogen and fitted with a combustible
gas sensor with an audible alarm that, when triggered, shuts down the power to the analyzer.

60 61
 VTI-SA+ Technology

Simultaneous Microscope Camera or Raman Measurement

The VTI-SA+ is fully compatible with simultaneous optical measurements, including
a high-resolution CCD camera / 2.5x microscope or a dedicated Raman Probe.*
These optional accessories are field installable, providing the highest level of
flexibility for your measurements.

Sample Chamber Design

In the VTI-SA+ Analyzer, the sample and reference chambers are located within an
aluminum block maintained at constant temperature (within ±0.1°C) by precise Peltier
control elements. Our unique aluminum block design has two distinct advantages.
First, due to the high thermal conductivity of the aluminum, thermal gradients within
the chambers are minimal. Second, because the chamber is a metal block, errors
associated with static electricity are eliminated. This feature is especially useful
when analyzing finely divided powders, as is often the case with pharmaceuticals.
The sample temperature is measured with a highly accurate, calibrated platinum
resistance thermometer. When higher temperatures are required, the block can be
heated to 150 °C using installed resistance cartridge heaters.

*Raman Spectrometer Required

62 63
 Q5000 SA
SPECIFICATIONS

Temperature Controlled Thermobalance Included

Dynamic Range 100 mg
Weighing Accuracy +/- 0.1%
Weighing Precision +/- 0.01%
The patented Q5000 SA delivers the performance Sensitivity < 0.1 µg
and reliability required in a leading sorption analyzer Baseline Drift* < 5 µg
in a compact, user-friendly design. The Q5000 Signal Resolution 0.01 µg
SA is designed for manual or automated sorption Temperature Control Peltier Elements
Temperature Range 5 to 85°C
analysis of materials under controlled conditions of
Isothermal Stability +/- 0.1°C
temperature and relative humidity (RH). Its design
Relative Humidity Control Range 0 to 98% RH
integrates our latest high-sensitivity, temperature-
Accuracy +/- 1% RH
controlled thermobalance with an innovative humidity Autosampler – 10 samples** Included
generation system, multi-position autosampler, Platinum™ Software Included
and powerful Advantage™ software with technique- Sample Pans Quartz or Metal-Coated Quartz 180 µL
specific programs and Platinum™ features. Platinum 50, 100 µL
Aluminum Sealed Pan 20 µL

* Over 24 hours at 25˚C and 20 % RH with empty metal coated quartz pans
** Optional tray accommodates 25 samples for use with platinum and sealed aluminum pans

64 65
 Q5000 SA Technology

The Q5000 SA is a compact, benchtop instrument that delivers the performance and reliability required in a leading sorption analyzer designed for the study
Balance
of materials under controlled conditions of temperature and relative humidity. Its modern, user-friendly design features a high sensitivity, temperature-controlled
thermobalance, an innovative humidity generation system, a 10-position autosampler, and our latest Advantage™ software with Platinum™ features.

Humidity Control Chamber

The patented design features a pair of mass flow controllers that accurately meter and proportion gas to a symmetrical, well-insulated, aluminum block. The block
contains a humidifier, gas transmission and mixing lines, plus easily accessible, identically arranged, sample and reference measurement chambers. Temperature
regulation of the block interior from 5°C to 85°C is performed by four thermoelectric (Peltier) devices in conjunction with a thermistor in a closed-loop system.
The mass flow controllers adjust the amounts of wet (saturated) and dry gas to obtain humidities from 0 to 98 %RH. Identical sensors are located adjacent to the
N2 MFC
sample and reference crucibles, and provide a continuous indication of humidity. Benefits of the design include precise temperature control and highly consistent
atmosphere within the sample and reference chambers.

Sample Chamber

RH Sensor
Reference Chamber

RH Sensor

Humidity Chamber

Humidifier

MFC MFC

N2 N2

66 67
 Q5000 SA Technology

Thermobalance
The heart of the Q5000 SA is our latest high performance thermobalance maintained at a constant temperature (±0.01˚C) by three
symmetrically arranged heaters in a well-insulated, gas-purged chamber. Isolated from the furnace by a water-cooled plate, the sensitive
null-balance design features the latest in precision weighing technology. A key feature of the design for sorption analysis operation is the
perfect symmetry of the balance assembly. Customer benefits of the patented design include sensitive, reliable operation with superior
baseline flatness and exceptional accuracy and precision in weight-change detection. These factors are critical for proper gravimetric
sorption-analysis performance and results that are totally free from error caused by vapor condensation or electrostatic forces.

Autosampler
The integral Q5000 SA Autosampler features a programmable multi-position sample carousel that permits automated analysis of up
to 10 samples using semispherical quartz (or metal-coated quartz) crucibles, and 25 samples using the optional Discovery TGA tray
and platinum or sealed aluminum pans. The design provides smooth and efficient loading and unloading of the sample pan without
disturbing the balance. All aspects of sample testing are automated and software controlled including pan taring and loading, sample
weighing, autosampler movement, furnace movement, pan unloading, and furnace cooling. Autosampler productivity is maximized by our
Advantage™ software which provides pre-programmed analysis, comparison, and presentation of results.

Sample Crucibles
Semispherical quartz, metal-coated quartz (180 µL) and optional platinum (50 and 100 µL) TGA pans are available for use with the
Q5000 SA. The former are commonly used in sorption analysis because of their anti-static capabilities, chemical inertness and ease of
cleaning, while Platinum pans are generic for TGA analysis of most materials. Sealed aluminum pans are also an option for ensuring the
integrity of materials which readily adsorb moisture or lose volatiles.

68 69
 Gravimetric Vapor Sorption Analysis
General Practice
Vapor Sorption analysis is an established technique for determining the effect on materials of exposure to controlled conditions of
temperature and humidity. Isotherm and Isohume™ experiments are the most commonly performed analyses.

All TA Instruments sorption analyzers perform a range of essential sorption experiments such as time-courses, isotherms (constant
temperature, variable RH), and isohumidity (Isohume™) experiments (constant RH, variable temperature). Complex protocols with step
changes in temperature and RH can be defined and saved for later use. Also, multiple experiments can be run sequentially without
further operator assistance.

In isothermal experiments, a weighed sample is “dried” externally, or preferably in the instrument, and exposed to a series of humidity
step changes at constant temperature. The sample is staged at each humidity level until no further weight change is detected or a set
time has elapsed. A data point is recorded, the humidity is changed in 5 or 10% controlled RH steps, and the process repeated in an
increasing or decreasing procedure. Isohume experiments involve a series of temperature step changes at constant humidity and result
in similar plots. They are used to determine how sample exposure to a given humidity results in a physiochemical change, such as a
change in the sample’s hydration state. The curve shape provides useful information to this end.

TA Instruments analysis software offers Sorption Analysis, BET Analysis, and GAB programs. In addition, the full power and flexibility
of our renowned Universal Analysis software provides for easy data manipulation, advanced reporting, plotting, and file exporting
capabilities. In addition, advanced data reduction of VTI-SA+ data can be performed using custom-designed data analysis packages.
Analysis options include:

• Kinetic analysis for the determination of rate constant of adsorption

• Isosteric heat of adsorption using the Clausius-Clapeyron equation

• Surface area calculation using the BET equation for either water or organic vapors

70 71
 Applications

5 5.0
Evaluation of Amorphous Structure Hydrate Formation
Amorphous Anhydrous
Pharmaceutical scientists are often interested in determining 4 The figure to the right contains the experimental results demonstrating 4.0
the amount of amorphous material in a drug formulation. the formation of a hydrate. The hydrate formation is characterized by

Weight Change (%)

Weight (% change)
As the amorphous and crystalline forms are chemically a plateau in the desorption branch of the isotherm. In this example 3.0
identical, classical analysis techniques are often insensitive 3
the hydrate is formed at around 45% RH. The sample adsorbs about
to amorphous content. The figure below shows the moisture 4.5% by weight water and does not lose the water of hydration until 2.0
sorption analysis of a generic drug in its amorphous and 2 the RH is lowered below 25%. This hydrate would be considered as Adsorption
crystalline forms. As the amorphous form absorbs significantly Crystalline Desorption
Monohydrate a labile or unstable hydrate. 1.0
more water, the Q5000 SA can be used to quantify relative
1
amorphous content in drug mixtures. 0.0
10 20 30 40 50 60 70 80 90 100
0 -1.0 Relative Humidity (%)
0 20 40 60 80 100
Relative Humidity (%)
Analyzing Small Amounts
of Pharmaceuticals
0.08 Characterization of Morphological Stability 112
When evaluating pharmaceuticals it is common for only small 55.68%
amounts of material to be available for conducting multiple Size: 13.8100 mg Exposure to elevated humidity can initiate morphological changes 110 Bulk & Surface Adsorption Crystallization
analytical tests. Hence, the ability to work with small samples in some pharmaceutical materials, particularly in amorphous
is critical. The low baseline drift of the Q5000 SA means that 0.06 108
sugars. As the humidity is increased, the adsorbed water plasticizes

Weight Change (%)

good results can be obtained on even 10-20 milligrams of a the material and lowers the glass transition. When the glass

Weight (%)
106
crystalline drug, such as prednisone, which adsorbs <0.1% transition temperature decreases to the experimental temperature, Glass Transition
moisture over a broad humidity range. The sorption results 0.04 crystallization will typically occur. The data in the figure below 104
shown below represent about 15 micrograms of weight show the behavior of amorphous lactose at 25°C under a constant Desorption
Adsorption
change full-scale. The reversibility (lack of hysteresis) in the Desorption increase in humidity. Note how the character in the measured 102
sorption/desorption profile for prednisone (as well as the low 0.02 Adsorption weight signal is indicative of a variety of morphological changes 41.16%
100
level of moisture adsorbed) indicates that the moisture picked including the glass transition and subsequent crystallization of the
up by the material is adsorbed on the surface of the material Surface Adsorption
amorphous phase. 98
rather than being absorbed into its structure. 0.00
0 20 40 60 80 100 0 20 40 60 80 100
Relative Humidity (%) Relative Humidity (%)

72 73
 Applications

1.0 
Organic Vapor Sorption (VTI-SA+) Packaging Film Analysis
35
With the organic vapor sorption capability, the VTI-SA+ can 0.80 In addition to evaluation of the actual pharmaceutical formulations, 
obtain not only water sorption isotherms, but can also be sorption analysis can also be valuable in comparing the polymeric

Weight Change (%)

used to measure organic vapor isotherms. The use of organic 25 films which are being considered for packaging the drugs and

Rel Press (req)



:HLJKW
0.60 other materials. The figure to the right shows comparative profiles )LOP$
vapor increases the sensitivity of the sorption measurement
for many pharmaceutical and polymer materials, and for two different packaging materials undergoing temperature and
15
provides information on the specificity of solvent adsorption 0.40 relative humidity cycling. Film A adsorbs and desorbs moisture at  5+DWÛ&
for many materials. In the first figure, the time course data a more rapid rate than the other film evaluated which suggests it )LOP%
for the adsorption of ethanol on activated carbon is shown. -5 may not be suitable for packaging moisture sensitive compounds. 
0.20
The sample is initially dried at 0% RH, then the relative
'U\LQJDWÛ&5+ 'U\LQJDWÛ&5+
pressure of the ethanol is stepped in 0.10 increments.
-5 0.00 
0 200 400 600 800          
Temperature (˚C) 7LPHPLQ

Rate of Diffusion
This second figure shows the sorption isotherm plot for the 50 The VTI-SA+ can be equipped with a diffusion cell which allows for 10 100
carbon/ethanol experiment, excluding the initial drying step. the direct measurement of the permeability of a film or membrane
The sample exhibits a significant adsorption at low solvent for a particular solvent vapor. The cell consists of a cavity that
40 8 80
concentrations. This is typical of the particle and internal is filled either with a desiccant or absorber, a gasketed lid for

Weight Change (%)

Relative Humidity (%)

Weight Change (%)
pore-size distribution of activated carbon which is designed attaching the film to be tested, and a wire stirrup to hang the
to allow for rapid gas-phase adsorption with low pressure 30 assembled cell on the hang-down wire of the balance. Any vapor 6 60
drop. permeating through the film gets absorbed immediately and the
20 weight of the cell will increase until steady-state conditions are 4 40
reached. The normalized rate of permeation is obtained from
Film Permeability
the slope of this line (weight per unit time) and the diameter of the FP = (Slope)/(Cell Area)
10 permeating film. 2 Slope = 3.00E-04 20
Diameter = 1.5 cm
FP = 1.70E-04 g/(min* cm2)
0 -2 0
0.0 0.20 0.40 0.60 0.80 1.00 0 50 100 150 200
Rel Pressure (req) Time

74 75
Dynamic Mechanical ANALYSIS

Accurate, Precise,
Versatile DMA
Measurements
 DMA Q800
SPECIFICATIONS

Maximum Force 18 N
Minimum Force 0.0001 N
Force Resolution 0.00001 N
Strain Resolution 1 nanometer
Modulus Range 103 to 3x1012 Pa
Modulus Precision ± 1%
The Q800 is the world’s best-selling DMA, for very Tan δ Sensitivity 0.0001
good reason. It utilizes state-of-the-art, non-contact, Tan δ Resolution 0.00001
linear drive technology to provide precise control Frequency Range 0.01 to 200 Hz
of stress, and air bearings for low friction support. Dynamic Sample Deformation Range ± 0.5 to 10 000 µm
Strain is measured using optical encoder technology Temperature Range -150 to 600°C
Heating Rate 0.1 to 20°C/min
that provides unmatched sensitivity and resolution.
Cooling Rate 0.1 to 10°C/min
With its unique design, the Q800 easily outperforms
Isothermal Stability ± 0.1°C
competitive instruments and is ideal for high-stiffness Time/Temperature Superposition Yes
applications, including composites. RH Control Optional

Output Values
Storage Modulus Complex/Dynamic Viscosity Time
Loss Modulus Creep Compliance Stress/Strain
Storage/Loss Compliance Relaxation Modulus Frequency
Tan Delta (δ) Static/Dynamic Force Sample Stiffness
Complex Modulus Temperature Displacement
Relative Humidity (Optional)

78 79
 DMA Deformation Modes & Sample Size Subambient Operation

Gas Cooling Accessory

Dual/Single Cantilever
The Gas Cooling Accessory (GCA) extends the operating range of the Q800
8/4* mm (L), Up to 15 mm (W) and 5 mm (T)
to -150°C. The GCA uses cold nitrogen gas generated from controlled
20/10* mm (L), Up to 15 mm (W) and 5 mm (T) evaporation of liquid nitrogen. Automated filling of the GCA tank can be
35/17.5* mm (L), Up to 15 mm (W) and 5 mm (T) programmed to occur after the scan is complete.

The GCA will provide ballistic or controlled cooling rates over the entire
3-Point Bend
operating range of the Q800 DMA (-150 to 600°C). In general, the maximum
5, 10, or 15 mm (L), Up to 15 mm (W) and 7 mm (T) cooling rate is a function of the installed clamp and the thermal characteristics
20 mm (L), Up to 15 mm (W) and 7 mm (T) of the sample. The figure below shows the typical range* of controlled cooling
50 mm (L), Up to 15 mm (W) and 7 mm (T) rates available as a function of temperature.

Tension
Film/Fiber 5 to 30 mm (L), Up to 8 mm (W) and 2 mm (T) 0
Fiber 5 to 30 mm (L), 5 denier (0.57 tex) to 0.8 mm diameter 10
20

Cooling Rate (˚C/min)

Shear 10 mm square, Up to 4 mm (T)
30

Compression 15 and 40 mm diameter, Up to 10 mm (T) 40

50
Submersion 60
Tension Fixed at 15 mm (L), Up to 8 mm (W) and 2 mm (T) 70
Compression 25 mm diameter, Up to 10 mm (T)
80
3-Point Bend 5, 10, or 15 mm (L), Up to 15 mm (W) and 7 mm (T) -150˚C -50˚C 50˚C 150˚C 250˚C 350˚C 450˚C 550˚C
Temperature (˚C)
*Lengths are for dual/single cantilever
*Actual performance may vary slightly depending on laboratory conditions and
the clamping system installed.

80 81
 Q800 Technology

Drive Motor Optical Encoder Furnace

The Q800 uses a non-contact, direct drive motor to provide the oscillatory A high-resolution linear optical encoder is used to measure displacement
or static force required. The motor is constructed of high performance on the Q800 DMA. Based on diffraction patterns of light through gratings
composites that ensure low compliance and is thermostated to eliminate (one moveable and one stationary), optical encoders provide exceptional
heat build-up even when using large oscillation amplitudes and high resolution compared to typical LVDT technology. Due to the excellent
deformation forces. Sophisticated electronics enable the motor current to 1 nanometer resolution of the optical encoder, very small amplitudes can
be rapidly adjusted in small increments. The motor can deliver reproducible be measured precisely. This, combined with the non-contact drive motor
forces over a wide range and the force can be changed rapidly, enabling and air bearing technology, provides excellent modulus precision and high
a broad spectrum of material properties to be measured. tan δ sensitivity allowing the Q800 DMA to characterize a broad range of
materials.
Air Bearings Low Mass, High Stiffness Sample Clamps Air Bearings
Low Mass, High Stiffness Sample Clamps
The non-contact drive motor transmits force directly to a rectangular
air bearing slide. The slide is guided by eight porous carbon air The Q800 features a variety of sample clamps that provide for multiple
bearings grouped into two sets of four near the top and bottom of the Rigid Aluminum Casting
modes of deformation. The clamps are optimized using finite element
slide. Pressurized air or nitrogen flows to the bearings forming a frictionless analysis to provide high stiffness, with low mass, and attach to the drive
surface that permits the slide to “float.” The slide, which connects to shaft with a simple dovetail connection. The clamps are easy to use and
the drive shaft and sample clamp, can move vertically 25 mm and its adjust, and each is individually calibrated to ensure data accuracy. A broad
rectangular shape eliminates any twisting of the sample. Very weak range of samples can be analyzed. The high stiffness minimizes clamp
materials like films and fibers can be characterized with ease. compliance, and the low mass ensures rapid temperature equilibration.
These simple, yet elegant designs reduce the time necessary to change
Furnace clamps and load samples.

The Q800 features a bifilar wound furnace with automated movement.

The furnace design, combined with the Gas Cooling Accessory, provides Rigid Aluminum Casting
for efficient and precise temperature control over the entire temperature The Q800 drive motor, air bearing slide assembly with optical encoder
range, both in heating, cooling, and isothermal operation. The automatic and air bearings are all mounted within a rigid aluminum casting that is
furnace movement simplifies experimental setup. temperature controlled. The rigid aluminum housing minimizes system
compliance and the temperature-controlled housing ensures precise data. Drive motor Optical Encoder

82 83
 Modes of Deformation

Dual/Single Cantilever Compression

In this mode, the sample is clamped at both ends and either flexed in the middle (dual In this mode, the sample is placed on a fixed flat surface and an oscillating plate
cantilever) or at one end (single cantilever). Cantilever bending is a good general-purpose applies force. Compression is suitable for low to moderate modulus materials
mode for evaluating thermoplastics and highly damped materials (e.g., elastomers). Dual (e.g., foams and elastomers). This mode can also be used to make measurements of
cantilever mode is ideal for studying the cure of supported thermosets. A powder clamp is expansion or contraction, and tack testing for adhesives.
also available for characterizing transitions in powder materials.

Tension
3-Point Bend In this mode, the sample is placed in tension between a fixed and moveable clamp.
In this mode, the sample is supported at both ends and force is applied in the middle. In oscillation experiments, the instruments use a variety of methods for applying a
3-point bend is considered a “pure” mode of deformation since clamping effects are static load to prevent buckling and unnecessary creep. The clamps are suitable for
eliminated. The 50 and 20 mm clamps on the Q800 utilize unique low-friction, roller both films and fibers.
bearing supports that improve accuracy.

Submersible Clamps
Shear Sandwich Film tension, compression, and 3-point bend clamps are available in submersible
In this mode, two equal-size pieces of the same material are sheared between a fixed and configurations for the Q800. These clamps allow samples to be analyzed in a fluid
moveable plate. This mode is ideal for gels, adhesives, high viscosity resins, and other environment up to 80°C.
highly damped materials.

84 85
 DMA Accessories
1
DMA-RH
The new DMA-RH Accessory allows mechanical properties of a sample to be analyzed under controlled and/or varying conditions of both relative humidity and
temperature. It is designed for use with the Q800 Dynamic Mechanical Analyzer.

The DMA-RH Accessory is a fully integrated unit and includes the following hardware components:

1. The sample chamber mounts to the DMA in place of the standard furnace. Peltier elements in the chamber precisely control the temperature to +/-0.1°C.
The sample chamber accommodates standard DMA clamps (tension, cantilever, and 3-point bending). It is quickly removed for conversion back to the standard
DMA furnace.

2. A heated vapor-transfer line is maintained at a temperature above the dew point temperature of the humidified gas in order to avoid condensation and
provide accurate results.
2
3. The DMA-RH Accessory contains the humidifier and electronics which continuously monitor and control temperature and humidity of the sample chamber.

100
The DMA-RH accessory offers the
widest range of temperature and relative humidity. 90
80

Relative Humidity (%)

Temperature Range 5 to 120°C 70
Temperature Accuracy ±0.5°C 60
Heating/Cooling Rate Maximum ±1°C/min 50
Humidity Range See humidity range chart.
40
Humidity Accuracy 5-90% RH: ±3% RH
30
>90% RH: ±5% RH
Humidity Ramp Rate 2% RH/min (fixed)
20 3
10
(both increasing and decreasing)
0
0 10 20 30 40 50 60 70 80 90 100 110 120
Temperature (˚C)

86 87
 DMA-RH Applications

4000 0.28 1000

Effect of Relative Humidity on the Glass 80% RH Stress Relaxation of Nafion® 112 Under 0.5% Strain
Transition of Nylon 6 50% RH 0.24 Varying Temperature/RH Conditions

Relaxation Modulus (MPa)

2000 20% RH 25˚C/50% RH

Storage Mdulus (MPa)

0.20

[ – – – –] Tan Delta
Nylon 6 is strongly plasticized by water; as such the mechanical 50% RH Recent research has focused on alternative fuel technologies
properties will be dependent on the surrounding relative humidity.  including Proton Exchange Membrane Fuel Cells (PEMFC) which
0.16
The data in this figure demonstrate the effect of relative humidity contain polymeric membranes such as Nafion* 112.  PEM 100
0 61.08˚C 67.49˚C
on the glass transition of Nylon 6 as measured on the Q800 DMA 49.44˚C 0.12 properties can significantly change as functions of time and
31.99˚C 85˚C/85% RH
equipped with the DMA-RH accessory. The sample was analyzed exposure to elevated temperatures and humidity, as water is the
in single cantilever mode at a frequency of 1 Hz at a variety of -2000
0.08 primary by-product of the electrochemical reaction of the fuel
constant RH conditions. Note how the mechanical properties and cell.  The Q800 DMA equipped with the DMA-RH accessory is
glass transition are significantly influenced by the imposed relative 0.04 the ideal platform to study the effect of temperature and humidity
humidity. -4000 0.00 on the time-dependent processes of the PEM. In this example, the
0
0 20 40 60 80 100 stress relaxation behavior of a Nafion 112 membrane is analyzed 1 10 100 1000 10000
Temperature (˚C) in tension mode under two discrete conditions; 25°C/50% RH Decay Time (sec)
(controlled ambient) and under elevated temperature and RH
conditions of 85°C/85% RH.
Measurement of the Coefficient of *Nafion is a registered trademark of DuPont Co.
Hygroscopic Expansion (CHE)
1500 Analysis of a Pharmaceutical Gelatin Capsule 10000 0.5
Hygroscopy is defined as the ability of a substance to attract water
molecules from the surrounding environment through either absorption 83.46% 93.63%
Gelatin capsules are widely used in the pharmaceutical and 0.4
or adsorption. The effect of moisture sorption on the mechanical

Storage Modulus (MPa)

1000 dietary supplement market. When stored in an ambient, low- 1000
characteristics of a material can be quantified by the Coefficient 0.25% RH/min

[ – – – –] Tan Delta
humidity environment gelatin is remarkably stable. However, when
of Hygroscopic Expansion (CHE), the constant which relates the 0.3
combined with water, gelatin forms a semi-solid colloid gel which
dimensional change of a material to a change in the surrounding
can profoundly affect its mechanical properties. The data in this 100
relative humidity. The data in this figure show the effect of imposed 500 example illustrate the effect of increasing relative humidity on a 0.2
relative humidity on the Nylon 6 sample as measured by the
gelatin sample cut from the side wall of a two-piece capsule at
Q800 DMA with the DMA-RH Accessory. As the relative humidity 25˚C
25°C and 40°C. As the relative humidity is increased, the material 10
is increased the sample expands. The resulting slope of the line 0.1
0 undergoes a multi-step transition resulting in a significant decrease
is equivalent to the CHE for the material.
in modulus near 80% RH.  The transition is resolved in both the 40˚C
storage modulus and tan d signals. 1 0.0
0 20 40 60 80 100 0 20 40 60 80 100
Relative Humidity (%) Relative Humidity (%)

88 89
 DMA Theory Multi-Frequency
Modes of Operation

% Strain/Stress
Range of Material Behavior
Dynamic Mechanical Analysis (DMA) is a technique used to measure the
mechanical properties of a wide range of materials. Many materials, including Solid Like Liquid Like
polymers, behave both like an elastic solid and a viscous fluid, thus the term Time
Multi-Frequency
viscoelastic. DMA differs from other mechanical testing devices in two important Ideal Solid Most Materials Ideal Fluid Multi-Stress/Strain The multi-frequency mode can assess viscoelastic properties as a function of frequency,
ways. First, typical tensile test devices focus only on the elastic component. In
many applications, the inelastic, or viscous component, is critical. It is the viscous Purely Elastic Viscoelastic Purely Viscous while oscillation amplitude is held constant. These tests can be run at single or

% Strain/Stress
multiple frequencies, in time sweep, temperature ramp, or temperature step/hold
component that determines properties such as impact resistance. Second, tensile
Viscoelasticity: Having both viscous and elastic properties experiments.
test devices work primarily outside the linear viscoelastic range. DMA works
primarily in the linear viscoelastic range and is therefore more sensitive to structure.
Multi-Stress/Strain
DMA measures the viscoelastic properties using either transient or dynamic
oscillatory tests. The most common test is the dynamic oscillatory test, where a Figure 1 Creep/Stress Relaxation In this mode, frequency and temperature are held constant, and the viscoelastic
properties are monitored as strain or stress is varied. This mode is primarily used to
sinusoidal stress (or strain) is applied to the material and a resultant sinusoidal δ = 0˚ δ = 90˚ identify the Linear Viscoelastic Range (LVR).
strain (or stress) is measured. Also measured is the phase difference, δ, between

Strain/Stress
the two sine waves. The phase lag will be 0° for purely elastic materials and
90° for purely viscous materials (Figure 1). However, viscoelastic materials Stress Creep/Stress Relaxation
(e.g. polymers) will exhibit an intermediate phase difference (Figure 2a).
With creep, the stress is held constant and deformation is monitored as a function of
T1 T1 time. In stress relaxation, the strain is held constant and the stress is monitored vs. time.
Since modulus equals stress/strain, the complex modulus, E*, can be calculated. Strain Time
From E* and the measurement of δ, the storage modulus, E’, and loss modulus, Controlled Force/Strain Rate
E’’, can be calculated as illustrated in Figure 2b. The storage modulus (E’) is the Controlled Force/Strain Rate
elastic component and related to the sample’s stiffness. The loss modulus (E’’) 100% Elastic Behavior 100% Viscous Behavior

Strain/Stress
In this mode, the temperature is held constant while stress or strain is ramped at a
is the viscous component and is related to the sample’s ability to dissipate
constant rate. This mode is used to generate stress/strain plots to obtain Young’s
mechanical energy through molecular motion. The tangent of phase difference, or
tan δ, is another common parameter that provides information on the relationship Figure 2a Figure 2b Modulus. Alternatively, stress can be held constant with a temperature ramp while
strain is monitored.
between the elastic and inelastic components. 0˚ < δ < 90˚
E* Time
Transient tests include creep and stress relaxation. In creep, a stress is applied to Ell Isostrain Isostrain
the sample and held constant while deformation is measured vs. time. After some
δ In isostrain mode, available on the Q800, strain is held constant during a temperature
time, the stress is removed and the recovery is measured. In stress relaxation,
ramp. Isostrain can be used to assess shrinkage force in films and fibers.
a deformation is applied to the sample and held constant, and the degradation of El

Strain
the stress required to maintain the deformation is measured versus time. E* = stress/strain
El = E*cosδ
Ell = E*sinδ
Viscoelastic Behavior tan δ = Ell/El Temperature

90 91
 Applications

10000 10000 100000

Tg by E’ Onset
Tg by Tan Delta Peak
-30.60˚C Tg 0.09
1000 -2.04˚C 1000
2.0 200.72˚C

Storage Modulus (MPa)

0.08
Measurement of Tg of Polymeric Materials The Measurement of Secondary Transitions

Storage Modulus (MPa)

Loss Modulus (MPa)

100 100 10000
0.07
1.5 in Vinyl Ester

Tan Delta
A common measurement on polymers is the glass transition

Tan Delta
Tg by E’’ Peak β Relaxation 0.06
temperature, Tg. It can be measured with various techniques, but 10 10
-28.58˚C DMA is one of the few techniques sensitive to β and γ second- 101.27˚C
DMA is by far the most sensitive. The figure to the right shows a 1.0 0.05
ary transitions. Secondary transitions arise from side group motion
scan of a pressure sensitive adhesive run in the tension clamps at a 1 1 1000 γ Relaxation
with some cooperative vibrations from the main chain as well as 0.04
frequency of 1 Hz. Tg can be measured by the E’ onset point, -89.55˚C
0.5 internal rotation within a side group. The transitions are below the
by the E’’ peak, or the peak of Tan δ. In addition to the Tg, the 0.1 0.1 0.03
Tg and typically subambient. They are very important as they af-
absolute value of the various viscoelastic parameters is also useful.
fect impact resistance and other end-use properties. This data was
0.01 0.01 100
generated using 3-point bending and also illustrates the ability to -150 -100 -50 0 50 100 150 200 250 300
-100 -75 -50 -25 0 25 50 75 100 125
run stiff composites.
Temperature (˚C) Temperature (˚C)

5000 0.20 1010 102

E’ at 10 HZ Tg at 0.1 HZ 103.00˚C
Frequency Effect on Modulus and Glass 4000 Tg at 10 HZ 113.25˚C Measuring Effect of Adhesive Coatings 109 E' 101
0.15

Storage Modulus (MPa)

Transition of Polyethylene Terephthalate (PET) Frequency = 6.28 1 Hz

E' Storage Modulus (Pa)

on Films
Because the Tg has a kinetic component, it is strongly influenced 3000 E’ at 0.1 HZ 108 100

Tan Delta
This figure shows a comparison among three PET samples in tension

Tan Delta
by the frequency (rate) of deformation. As the frequency of the test 0.10 Uncoated
on the DMA; one with a uniform adhesive layer that performs well, Good Coating Tan Delta
increases, the molecular relaxations can only occur at higher 2000 Tan Delta at 0.1 HZ one with a non-uniform layer that performs poorly, and one that is 107 Poor Coating 10-1
temperatures and, as a consequence, the Tg will increase with uncoated. A transition peak due to the adhesive is seen in Tan δ
increasing frequency as illustrated to the right. In addition, the shape 0.05 around 40°C in the “good” sample, whereas the “poor” sample
and intensity of the Tan δ peak as well as the slope of the storage 1000 106 10-2
shows a much smaller peak. Knowing the characteristics of good
modulus in the transition region will be affected. Based on end- Tan Delta at 10 Hz and poor samples enables quality control of the coating process
use conditions, it is important to understand the temperature and 0 0.00 and the finished product. 105 10-3
frequency dependence of transitions. 20 40 60 80 100 120 140 160 -90 -60 -30 0 30 60 90 120 150 180 210
Temperature (˚C) Temperature (˚C)

92 93
 Applications

12000 2000 10
10401 MPa 142.70˚C 8.944% Good (PTFE/PP)
10000 Poor (PTFE/PP)
8 Excellent (PTFE/PP/PE)
Characterizing Printed Circuit Boards 141.84˚C 15000 Characterizing Packaging Films

Storage Modulus (MPa)

9589 MPa

Loss Modulus (MPa)

8000 Jer=2.89 E-8 Pa-1
Printed Circuit Boards (PCB) are typically comprised of fiberglass Using Creep 6 5.520%

Strain (%)
braid impregnated with a thermosetting resin. Characterizing 1000
6000 PCB “As Received” In a thermoforming process, a film is pulled down into a heated mold
the Tg of PCB’s is often difficult due to the very low amount of
PCB “Post Baked” to form a desired shape. The ability to produce a stable product 4 3.466%
resin used. This figure shows a typical PCB run in single cantilever Jer=2.43 E-8 Pa-1
4000 can be predicted by using a creep-recovery experiment. This figure
bending. The Tg is clearly discernible and the difference between
500 illustrates data on a packaging film using the tension mode. In the
the sample “as received” and “post baked” clearly shows the effect 2
2000 recovery phase, the equilibrium recoverable compliance, (Jer) can Jer=8.86 E-9 Pa-1
that further crosslinking has on both the Tg and the absolute value
be calculated. If the sample compliance is too high, as observed by
of modulus. 0
0 a high Jer, then the elasticity may be too low at the forming 0
40 60 80 100 120 140 160 180 200 temperature to maintain the desired shape. 0 5 10 15 20 25 30 35
Temperature (˚C) Time (min)

1010 10 Predicting Material Performance Using Time/ 1010

Effect of Carbon Black in Elastomers
Temperature Superpositioning (TTS)
Another very common application is the effect of fillers and 109
additives on viscoelastic properties. The figure to the right illustrates 1 The TTS technique, well-grounded in theory, is used to predict
the effect on storage modulus (E’) and Tan δ when adding carbon material performance at frequencies or time scales outside the range

Modulus E' (Pa)

108 of the instrument. Data is usually generated by scanning multiple
E' Master Curve

Tan Delta
black to an SBR rubber. This test, performed in dual cantilever on

E' (Pa)
Tr=75˚C
the DMA, shows that adding carbon black increases the absolute 0.1 frequencies during a series of isothermal step-hold experiments 109
value of the storage modulus and significantly increases the Tg 107 over a temperature range. A reference temperature is selected and
temperature. Understanding how fillers and additives affect the data shifted. A shift factor plot is generated and fit to either a
material properties is crucial in many industrial applications. 0.01 Williams-Landel-Ferry (WLF) or Arrhenius model. Finally, a master
106 SBR curve at a specific temperature is generated as illustrated to the right
SBR + Carbon Black
for a PET film sample. Using this technique, properties at very high
105 0.001 frequencies (short time scales) or very low frequencies (long time 108
-80 -65 -50 -35 -20 scales) can be assessed. 10-15 10-8 10-1 106 1013 1020
Temperature (˚C)
Frequency (Hz)

94 95
 Thermomechanical Analysis

Sensitive Measurement, Unmatched Versatility

 TMA Q400EM/Q400
SPECIFICATIONS

Q400EM Q400
Temperature Range (max) -150 to 1 000°C -150 to 1 000°C
Temperature Precision ± 1°C ± 1°C
Furnace Cool Down Time (air cooling) <10 min from 600°C to 50°C <10 min from 600°C to 50°C
Maximum Sample Size - solid 26 mm (L) x 10 mm (D) 26 mm (L) x 10 mm (D)
The Q400EM is the industry’s leading Maximum Sample Size - film/fiber
research-grade thermomechanical analyzer Static Operation 26 mm (L) x 1.0 mm (T) x 4.7 mm (W) 26 mm (L) x 1.0 mm (T) x 4.7 mm (W)
with unmatched flexibility in operating Dynamic Operation 26 mm (L) x .35 mm (T) x 4.7 mm (W) —
modes, test probes, and available signals. Measurement Precision ± 0.1% ± 0.1%
The Enhanced Mode (EM) allows for Sensitivity 15 nm 15 nm
additional transient (stress/strain), dynamic Displacement Resolution <0.5 nm <0.5 nm
Dynamic Baseline Drift <1 µm (-100 to 500°C) <1 µm (-100 to 500°C)
and Modulated TMA™ experiments that
Force Range 0.001 to 2 N 0.001 to 2 N
provide for more complete viscoelastic
Force Resolution 0.001 N 0.001 N
materials characterization plus a way Frequency Range 0.01 to 2 Hz —
to resolve overlapping thermal events Mass Flow Control Included Included
(MTMA). The Q400 delivers the same Atmosphere (static or controlled flow) Inert, Oxidizing, or Reactive Gases Inert, Oxidizing, or Reactive Gases
basic performance and reliability as the
Operational Modes
Q400EM but without the latter’s advanced
Standard Included Included
features. It is ideal for research, quality
Stress/Strain Included —
control, and teaching applications. Creep Included —
Stress Relaxation Included —
Dynamic TMA (DTMA) Included —
Modulated TMA™ (MTMA™) Included —

98 99
 Q400 Technology
Furnace

A thermomechanical analyzer measures sample dimensional changes under conditions of controlled temperature, time, force, and atmosphere.
Our engineering experience in design and integration of critical furnace, temperature, dimension measurement, and atmosphere-control components meld
with powerful, flexible software to optimize the numerous tests available which the Q Series™ TMA can perform.

Linear Variable Differential Transducer

Furnace Linear Variable Differential Transducer
The Q400 vertical furnace is designed for high performance, The heart of the Q400 TMA sample measurement system is the Sample Stage
reliability and long life in a wide variety of applications. Customized precision, moveable-core, linear variable differential transducer (LVDT),
electronics provide the temperature control and response required which generates an accurate output signal that is directly proportional
for superior baselines, enhanced sensitivity and Modulated TMA™ to a sample dimension change. Its precise and reliable response over a
operation. Software control of the furnace movement ensures wide temperature range (-150 to 1 000˚C) ensures reproducible TMA
operational convenience and simplified sample loading/unloading. results. Its location below the furnace protects it from temperature effects
The Inconel® 718 Dewar atop the furnace allows continuous operation and ensures stable baseline performance.
in cyclic heating/cooling studies using the new optional mechanical
cooling accessory (MCA 70).

Sample Stage Force Motor

The easily accessible stage simplifies installation of the available probes A non-contact motor provides a controlled, friction-free, calibrated force
(see Modes of Deformation), sample mounting, and thermocouple to the sample via a probe or fixture. The force is digitally programmed
placement. An integral digital mass flow controller meters the flow of from 0.001 to 1N, and can be increased manually to 2 N by addition
purge gas to the sample area. Precise and responsive temperature of weights. The motor precisely generates the static, ramped or oscillatory
control and the well-regulated purge gas result in optimized dynamic forces necessary for quality measurements in all deformation
performance in the standard and MTMA modes of operation. modes. Ten individual frequencies are available for optimizing data
The design benefits also include flexibility in operation and ease of use. quality in dynamic TMA experiments in compression, 3-point bending,
or tension modes of deformation. Force Motor

100 101
 Modes of Deformation
The Q400 offers all the major TMA deformation modes necessary to characterize Compression
a wide range of materials such as solids, foams, films, and fibers. These include
expansion, penetration, compression, tension, and 3-point bending. 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
Expansion experiments and used to measure intrinsic material properties, or by dynamic Expansion Macro-Expansion Penetration
Expansion measurements determine a material’s coefficient of thermal expansion tests and used to determine viscoelastic parameters, detect thermal events, and
(CTE), glass transition temperature (Tg), and compression modulus. A flat-tipped separate overlapping transitions (MTMA).
standard expansion probe is placed on the sample (a small static force may
be applied), and the sample is subjected to a temperature program. Probe 3-Point Bending
movement records sample expansion or contraction. This mode is used with
most solid samples. The larger surface area of the macro-expansion probe In this bending deformation (also known as flexure), the sample is supported
facilitates analysis of soft or irregular samples, powders, and films. at both ends on a two-point, quartz anvil atop the stage. A fixed static force is
applied vertically to the sample at its center, via a wedge-shaped, quartz probe.
This mode is considered to represent “pure” deformation, since clamping effects
Penetration are eliminated. It is primarily used to determine bending properties of stiff
Penetration measurements use an extended tip probe to focus the drive force on materials (e.g., composites), and for distortion temperature measurements.
a small area of the sample surface. This provides precise measurement of glass Dynamic measurements are also available with the Q400EM, where a special,
transition (Tg), softening, and melting behavior. It is valuable for characterizing low-friction, metallic anvil replaces the quartz version. Tension
coatings without their removal from a substrate. The probe operates like the
expansion probe, but under a larger applied stress. The hemispherical probe Dilatometer Probe Kit
is an alternate penetration probe for softening point measurements in solids.
A specialty dilatometer probe kit is also available for the Q400 and Q400EM.
This kit includes a special dilatometer probe, small quartz vial to enclose
Tension the sample and a filling medium. Whereas TMA generally measures the linear
Tensile studies of the stress/strain properties of films and fibers are performed Coefficient of Thermal Expansion (CTE), the dilatometer kit is designed to
using a film/fiber probe assembly. An alignment fixture permits secure and determine the Coefficient of Volume Expansion, or CVE, of a material.
reproducible sample positioning in the clamps. Application of a fixed force
is used to generate stress/strain and modulus information. Additional The expansion, macro-expansion, and penetration probes are supplied with 3-Point Bending
measurements include shrinkage force, Tg, softening temperatures, cure, and the Q400. These probes, plus the flexure probe, and the low-friction bending Hemispherical
cross-link density. Dynamic tests (e.g. DTMA, MTMA™) in tension can be fixture, are included with the Q400EM module. Data analysis programs
performed to determine viscoelastic parameters (e.g., E’, E”, tan δ), and to relevant to each of the measurements described are provided in our
separate overlapping transitions. Advantage™ software.

102 103
 TMA Theory/Modes of Operation
Creep and Stress Relaxation (Q400EM)
Standard Mode Creep and Stress Relaxation (Q400EM) Dynamic TMA Mode (Q400EM)
TMA can also measure viscoelastic properties using transient
TMA measures material deformation changes under controlled conditions of force, atmosphere, time T (creep or stress relaxation) tests. These require the Q400EM T
and temperature. Force can be applied in compression, flexure, or tensile modes of deformation using module. In a creep experiment, input stress is held constant,
E*
specially designed probes described in pages 102-103. TMA measures intrinsic material properties and resulting strain is monitored as a function of time. In a Ell

Strain / Stress
Strain (Force)
(e.g., expansion coefficient, glass transition, Young’s modulus), plus processing/product performance stress relaxation experiment, input strain is held constant, and

% Strain
parameters (e.g., softening points). These measurements have wide applicability, and can be performed Force stress decay is measured as a function of time. The δ data can S
by either the Q400 or the Q400EM. The Q400 and Q400EM operating modes permit multiple material Strain also be displayed in units of compliance (creep mode) E and
l

property measurements. The Q400 features the Standard mode, while the Q400EM additionally offers stress relaxation modulus (stress relaxation mode).E* = stress/strain
Stress/Strain, Creep, Stress Relaxation, Dynamic TMA, and Modulated™ TMA modes as described El = E*cosδ
below. Temperature (Time)
Modulated TMA™ (MTMA™; Q400EM) Ell = E*sinδ T
1 Time T
2 Figure A
Temperature (time)

tan δ = Ell/El
In Modulated TMA (MTMA), the sample experiences the Modulated TMA (MTMA; Q400EM)
Standard Mode combined effects of a linear temperature ramp and a 0˚ < δ < 90˚
F sinusoidal temperature of selected amplitude and period. The T

Standard Mode (Q400/Q400EM) output signals (after Fourier transformation of the raw data)

Modulated Temperature
are total displacement and the change in thermal expansion

Modulated Length
Temperature Ramp: Force is held constant and displacement is monitored under a linear temperature coefficient. Both can be resolved into their reversing and

Strain
ramp to provide intrinsic property measurements. Isostrain (shrinkage force): Strain is held constant T non-reversing component signals. The reversing signal
and the force required to maintain the strain is monitored under a temperature ramp. This permits contains events attributable to dimension changes and is
assessment of shrinkage forces in materials such as films/fibers. Force Ramp: Force is ramped and useful in detecting related events (e.g.,Tg). The non-reversing
resulting strain is measured at constant temperature to generate force/displacement plots and modulus signal contains events that relate to time-dependent kinetic
assessment. Force (Time) processes (e.g., stress relaxation). This technique is unique Temperature
Figure B Viscoelastic Behavior
to the Q400EM.

Stress/Strain Mode (Q400EM)

Dynamic TMA Mode (Q400EM)
Stress/Strain Mode (Q400EM) Strain
Stress In Dynamic TMA (DTMA), a sinusoidal force and linear
Stress or strain is ramped, and the resulting strain or stress is measured at constant temperature. temperature ramp are applied to the sample (Figure A), and

Stress (Strain)
Using customer-entered sample geometry factors, the data provides both stress/strain plots and related the resulting sinusoidal strain, and sine wave phase difference
modulus information. In addition, calculated modulus can be displayed as a function of stress, strain, T (δ) are measured (Figure B). From this data, storage modulus
(E’), loss modulus (E”), and tan δ (E”/E’) are calculated as Figure C
temperature, or time.
functions of temperature, time, or stress (Figure C). This
technique can be useful in the analysis of thin polymer films.
Strain (Stress)

104 105
 Mechanical Cooling
Accessory (MCA70)

Û&


&RROLQJ5DWHƒ&PLQ





Û&
The MCA70 is a high performance accessory for the Q400 and 
Q400EM Thermomechanical Analyzer that permits controlled           
cooling within the temperature range of 400 to –70ºC. The 7HPSHUDWXUHÛ&
MCA 70 is ideal for use in cyclic heating/cooling experiments
that are increasingly being used by manufacturers to test materials
under conditions of actual use and verify their performance. The figure above/below details the operating envelope of the
MCA70. Controlled rates are detailed in the table below:

MCA70 Controlled Cooling Rates, from 400°C (upper limit)*

Controlled Rate To Lower Temperature

50°C/min 70°C
20°C/min -15°C
10°C/min -40°C
5°C/min -55°C
2°C/min -65°C

*Performance may vary slightly, depending on laboratory conditions

106 107
 Applications


Intrinsic and Product Property Material Performance and Selection
Measurements The figure to the right is an example of a 3-point bending
This figure shows expansion and penetration probe Ts 40˚C mode (flexure probe) experiment on a polyvinyl chloride
Penetration Tg -44˚C

Displacement
measurements of the Tg and the softening point of a synthetic (PVC) sample using the ASTM International Test Method
rubber using a temperature ramp at constant applied force. Loading: 5g E2092 to determine the distortion temperature or “deflection
Ts 39˚C 
The large CTE changes in the expansion plot indicate the temperature under load” (DTUL). This test specifies the
transition temperatures. In penetration, the transitions are temperature at which a sample of defined dimensions
Expansion
detected by the sharp deflection of the probe into the sample. produces a certain deflection under a given force. It has long
Loading: None
been used for predicting material performance.
Tg -43˚C

-120 -80 -40 0 40 80       
Temperature (˚C) 7HPSHUDWXUHÛ&

0 
Û&
Accurate Coefficient of 50 230˚C 
Multilayer Film Analysis
Thermal Expansion Measurements 40 
This figure shows a compression mode analysis, using a
This example demonstrates the use of the expansion probe 30 penetration probe, of a double layer PE/PET film sample 
to accurately measure small CTE changes in an aluminum supported on a metal substrate. The sample temperature was
sample over a 200°C temperature range. Advantage™ 20 
ramped from ambient to 275°C at 5°C/min. The plot shows
software permits analysis of the curve slope using a variety probe penetrations of the PE layer (93.2 µm) at 103°C, and 
10 45˚C Û&
of methods to compute the CTE at a selected temperature, or the PET layer (14.8 µm) at 258°C, respectively.
over a range. 
0

-10

40 80 120 10 200 240         
˚C 7HPSHUDWXUHÛ&

108 109
 Applications

2030 0.3 3
Shrinkage Force Testing Fiber Stress/Strain Measurements
75
This figure illustrates a classic shrinkage force (isostrain) 2025 Stress/strain measurements are widely used to assess and
experiment in the tensile mode on a food wrapping film. The compare materials. The figure shows the different regions

Temperature (˚C)
film was strained to 20% at room temperature for 5 minutes, 0.2 2 Yield Region
of stress/strain behavior in a 25 µm polyamide fiber in
2020 25

Force (N)
cooled to -50°C and held for 5 more minutes, then heated tension, subjected to a force ramp at a constant temperature.
at 5°C/min to 75°C. The plot shows the force variation The fiber undergoes instantaneous deformation, retardation,
(shrinkage force) required to maintain a set strain in the film. 2015 linear stress/strain response, and yield elongation. Other
This test simulates film use from the freezer to the microwave. 0.1 1
-25 parameters (e.g., yield stress, Young’s modulus) can be
2010 determined.
Elastic Region
2005 0.0 0
0 10 20 30 40 50 0 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40
Time (min)
Force (N)

0.020 0.6
Film Tensile Testing As Received
The figure to the right displays a strain ramp experiment, Thermal Stress Analysis of Fibers
0.015
at a constant temperature, on a polymeric film in tension. This figure displays a tensile mode experiment, using a
The plot shows an extensive region where stress and strain 0.4
temperature ramp at a constant strain (1%), to perform a

Stress (MPa)

Force (N)
are linearly related, and over which a tensile modulus can stress analysis on a polyolefin fiber, as received, and after
be directly determined. Quantitative modulus data can also 0.010 Cold Drawn
cold drawing. The plot shows the forces needed to maintain
be plotted as a function of stress, strain, time, or temperature. the set strain as a function of temperature. The data has been
Slope = Modulus 0.2
The results show the ability of the Q400EM to function as a correlated with key fiber industry processing parameters,
mini tensile tester for films and fibers. 0.005 such as shrink force, draw temperature, draw ratio,
elongation at break, and knot strength.
0.000 0.0
0 5 10 15 20 20 40 60 80 100 120 140 160 180 200
Strain (%) Temperature (˚C)

110 111
 Applications

1.2 3000 200

Creep Analysis Creep Viscoelastic Property Determination -
Creep tests are valuable in materials selection for applications 1.0 Dynamic TMA 2500 0.10

Tan Delta
where stress changes are anticipated. This example illustrates 150

Storage Modulus (MPa)

This figure illustrates a dynamic test in which a semi-crystalline

Loss Modulus (MPa)

an ambient temperature creep study on a polyethylene film in 0.8 2000 0.08
polyethylene terephthate (PET) film in tension is subjected to

Strain (%)
tension. It reveals the instantaneous deformation, retardation,
0.6 a fixed sinusoidal force during a linear temperature ramp. 1500 0.06 100
and linear regions of strain response to the set stress, plus
The resulting strain and phase data are used to calculate the
its recovery with time, at zero stress. The data can also be
0.4 material’s viscoelastic properties (e.g., E’, E”, and tan δ). The 1000 0.04
plotted as compliance, and recoverable compliance, versus
plotted data shows dramatic modulus changes as the film is 50
time. Recovery
0.2 heated through its glass transition temperature. 500 0.02

0.0 0 0
0 2 4 6 8 10 12 40 60 80 100 120 140 160
Time (min) Temperature (˚C)

150 40 40
Stress Relaxation Analysis
This figure shows a stress relaxation test in tension on Separating Overlapping Transitions -

Relaxation Modulus (MPa)

the same polyolefin film used for the creep study in the 145
previous example. A known strain is applied to the film, and
Modulated TMA™
20 20 20
maintained, while its change in stress is monitored. The plot The figure to the right shows a MTMA™ study to determine
shows a typical decay in the stress relaxation modulus. Such 131.68 ˚C
140 the Tg of a printed circuit board (PCB). The signals plotted
tests also help engineers design materials for end uses where are the total dimension change, plus its reversing and
changes in deformation can be expected. non-reversing components. The total signal is identical to that 0 0 0
135 from standard TMA, but does not uniquely define the Tg.
The component signals, however, clearly separate the actual
Tg from the stress relaxation event induced by non-optimum
130 processing of the PCB. -20 -20
0.001 0.01 0.1 1 10 60 80 100 120 140 160 180 200
Time (min) Temperature (˚C)

112 113
 NOTES
 tainstruments.com

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