Accelerating Rate Calorimeters

Advanced Solution for Chemical Process Safety,

Energetic Material, and Battery Development
Best-in-Class Adiabatic Calorimetry

ADIABATIC
CALORIMETRY

A Key Tool to Understand
Thermal Runaway

Adiabatic calorimetry has been the cornerstone

of chemical process safety for the last 30 years.
More recently, adiabatic calorimetry has been
widely used in measuring the potential of
thermal runaway of Li-ion cells. These cases are
similar in that they require measuring both the
amount of heat released (thermodynamics) and
the rate at which the heat is released (kinetics).
In both cases, there can be a significant increase
in sample pressure and the combination of the
temperature and pressure rise can lead to an
explosion. Therefore, adiabatic calorimeters are
generally designed to be much more robust
than many other types of calorimeters.

ARC® 244

2
When looking at a thermal runaway, whether it is
within a battery cell or part of a chemical process in
a reactor, the reaction produces heat which increases
the temperature of the reaction mixture and further
increases the rate of reaction. There can come a
point when the rate of heat release from the reaction
exceeds the rate at which the heat can be lost to the
surrounding environment – the point at which
thermal runaway starts. Obviously, the worst case is
when there is little or no ability for the heat to be lost
to the environment. Any heat, even small amounts
of heat, cause the temperature to rise and accel-
erates the reaction producing even more heat. This is
the adiabatic condition and it is this precise condition
that adiabatic calorimeters can safely measure in the
small scale. It is this same condition that can be
found inside large processing vessels as well as inside
a Li-ion pack running inside a laptop computer.

NETZSCH – a New Level of

Adiabatic Calorimetry
The adiabatic principle is realized in accelerating rate
calorimeters. The instruments described herein are
the best in their class. With the patented VariPhi®
system, not only can adiabatic test be done more
accurately but it also opens up new areas of
calorimetry not possible with the original ARC® units.
The systems have been enhanced to do more and
answer more questions.

ARC® 254

3
 Method

The energy release from chemical reactions (decomposition, etc.)

Sample Container is a point of focus in chemical research, battery research and other
industries. When energy is generated by a thermally induced
chemical reaction and the heat transfer to the outside is smaller
than the generated amount, runaway reactions can occur. In the
worst case, this can cause catastrophic effects (explosions). Adiabatic
calorimeters are ideal tools for analyzing such questions as they
simulate the worst case scenario with no heat exchange with the
surroundings. The behavior in real large scale chemical reactors can
therefore be simulated.

For decades accelerating rate calorimeters have been widely used by

researchers in this field, offering the capability to measure tempera-
tures, enthalpy changes and pressure changes quantitatively.

Adiabatic System: No heat in – no heat out

Top
Tube heater

Technique

A sample (several grams) is placed

in a spherical vessel. The vessel is
Gas-tight Top heater
surrounded by a sophisticated
ceramic insulation
heating system. Depending on the
working mode, the surroundings
of the vessel are controlled to the Sample vessel
same temperature as the sample. Control TC
If there is no temperature
difference between the heaters Safety TC
and the sample, then all the heat Bottom TC
Side TC
generated by the sample stays
Side bottom
within the sample. This is the heater
adiabatic condition.

Gas-tight
ceramic insulation

Magnetic Containment
stirring Bottom vessel

Schematic of the ARC® 254 Calorimeter Assembly

TC = Thermocouple

4
Understanding Adiabatic Reaction Calorimetry

Heat-Wait-Search mode (HWS) represents a careful approach to the reaction

temperature:

∙∙Heating the sample material to a certain temperature → Heat

∙∙Isothermal stabilization → Wait

∙∙Change to the adiabatic mode → Search (as soon the self-heating rate of the
sample extends a customer-defined threshold (usually 0.02 K/min))

Measurement Results

A thermal runaway reaction is

usually investigated with the
Heat‐Wait‐Search mode (HWS).
The temperature of reaction as
well as the temperature and
pressure increase are measured.
Additionally, the temperature and
pressure increase rates can be
determined. These are important
values in order to characterize the
worst case scenario of a
substance. Thermal runaway reaction of a 20% solution of di‐tert. butyl peroxide
(DTBP) in toluene.

5
 The Original DOW Design
for Basic ARC® Testing

Accelerating Rate Calorimeter

ARC® 244

The cost‐effective ARC® 244 is

designed to safely measure the
amount and rate of heat release
associated with the processing or
storage of chemicals with a sample
volume of 0.5 ml to 7 ml. This is the
only calorimeter which uses the
same design as the first ARC® system
developed by DOW for those
customers interested in keeping the
same platform.

The key features are high perfor-

mance, safety, usability, and flexi-
bility with data integrity and
robustness in a temperature range
from ambient to 500°C.

ARC® 244

6
 Operating Modes

∙∙Heat-Wait-Search test for thermal

∙∙
runaway reactions
Iso-Fixed/Iso-Track for studying
storage conditions/auto-catalytic

∙∙
reactions (iso-aging technique)
Ramp mode for fast screening of
unknown samples

Optionally with VariPhi®

Scanning and isothermal modes

allow detection of exothermic and
endothermic effects; similar to the
DSC method

ARC® 244 Calorimeter Assembly

Features Advantages Benefits

operator not required to lift

Easy for all operators to use
Motorized headlift calorimeter lid and can set working
safely and quickly
height based on personal preference
one safety thermocouple monitors
Over-temperature calorimeter temperatures and shuts Protects heaters and other
protection down the system independent of the instrument parts from runaways
software
Prevents refluxing and sample loss
heats the pressure transfer
which can cause great underestimation
Tube heater tube to the same temperature
of heats of reaction and temperature
as the sample
and pressure rates
allows the user to run isothermal aging
Iso-fixed mode More accurate and reliable data
tests for many days with minimized drift
the user can quickly set-up the
Automated anneal, anneal-adjustment-drift test sequence. No operator intervention
temp. The software will automatically go necessary, improved efficiency
from one test to the next

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 Advanced Technology
for Specialized Testing

Accelerating Rate Calorimeter

ARC® 254

The advanced Accelerating Rate

Calorimeter ARC® 254 helps
engineers and scientists identify
potential hazards and tackle key
elements of process optimization
and thermal stability. As a highly
versatile, miniature chemical reactor,
sample can be stirred, material
injected, and it can be used for vent
studies. The ARC® 254 has been
designed to use the traditional
10 ml ARC spherical vessel but can
also use the larger 130 ml vessel for
low Phi or vent testing.

ARC® 254

8
 Operating Modes

∙∙ Heat-Wait-Search test for thermal

runaway reactions of chemicals or

∙∙
battery samples
Iso-Fixed/Iso-Track for studying
storage/conditions/auto-catalytic

∙∙
reactions (iso-aging technique)
Ramp mode for screening
unknown samples

Optionally with VariPhi®

∙∙ Scanning and isothermal modes

allow detection of exothermic and
endothermic effects; similar to the

∙∙
DSC method
In‐situ battery cycling using
isothermal calorimeter mode

Features* Advantages Benefits

Temperature tracking fast reactions can be tracked without the More reliable data and wider
rate up to 200 K/min need to increase thermal inertia application range
Constant insulation properties
Machined gas-tight provides consistent insulation
provide for accurate test results,
ceramic insulation properties (i.e. density, geometry)
easy cleaning
with VariPhi® temperature
True temperature More accurate onset
measurements can be corrected
calibration temperature
to standards
Battery holder (D-cell, Testing of battery or
Easy testing of different batteries
18650, pouch cell) charging/discharging battery

* in addition to ARC® 244 features

9
 The basis of the VariPhi® is an additional controlled variable DC heater.
With this option, it is possible to define the thermal inertia in order to allow
real-world thermal environment by compensating for heat lost from the
sample to the vessel. By operating different modes such as isothermal or
scanning, endothermic and exothermic transitions can be quantified and
pressure data can be measured.

VariPhi®
A Patented Solution for
Low Phi Operation and
Reduced Testing Time

Theory

Thermocouples Sample containers absorb some of the energy from the reaction. How
much heat is absorbed depends upon the mass and heat capacity of the
sample container. The ratio between the product of the system (sample +
vessel) and heat capacity to the product of the container mass and heat
capacity is what is known as thermal inertia.

Sample When the sample mass is large compared to the container mass, the
heater
Guard
thermal inertia approaches one. These tests are often called “low phi” tests.
heater They are important because most industrial scale processing or storage
conditions are low thermal inertia conditions. The mass of a large storage
container is very small compared to the mass of the stored material. Since
this is not always true, it is important to be able to run multiple tests at
varying thermal inertia. The VariPhi® gets its name because the user can
quickly and easily run low and high thermal inertia (˝Phi˝) tests in the same
calorimeter using a small and inherently safer sample size.
Diagram of VariPhi®
Formula for thermal inertia (Φ-factor) according to ASTM E1981:

mc = mass of the container

(ms · Cp,s + mc · Cp,c) mc · Cp,c Cp,c = heat capacity of the container
Φ = –––––––––––––––––– Φ = 1+ ––––––– ms = mass of the sample
ms · Cp,s ms · Cp,s
Cp,s = heat capacity of the sample

10
Standard Modes such as Heat-Wait-Search, Iso-Fixed or Iso-Track

∙∙∙∙
Compensation for heat lost to the sample container during test

∙∙
Thermal inertia or Phi (Φ) factor can be defined
Low Phi testing with small samples

Scanning Mode

∙∙∙∙
Reduces test time by 75% or more without loss of sensitivity
Endothermic transition can be accurately measured

Fire-Exposure Mode
Simulation of additional heat to the sample during external fire scenario

Isothermal Mode

∙∙ True isothermal calorimeter mode is possible on chemical samples and

∙∙
battery cells
3D battery sensors are available based on the VariPhi® concept. They
allow the study of charge/discharge of batteries inside the calorimeter

Testing Vessels for the Accelerating Rate Calorimeters

A broad variety of testing vessels are available to meet different test requirements. Tube-type vessels are available
for running energetic materials and for use with solids and pastes in the VariPhi® mode. For battery testing,
specific holders are designed for common commercial sizes. Custom vessels can also be designed.

Materials

∙∙ Spherical vessels with a wall thickness between 0.4 mm and 5.1 mm

∙∙
are made of glass, Hastelloy, Inconel, stainless steel, tantalum and titanium
Tube-type vessels with a wall thickness of 0.4 mm and 0.7 mm are
made of stainless steel and titanium

Volume

∙∙∙∙
1 ml to 130 ml for spherical vessels
0.1 ml to 9 ml for tube-type vessels

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 ARC® 244 ARC® 254

Temperature range RT to 500°C RT to 500°C

Pressure range (Standard) 0 bar to 200 bar 0 bar to 200 bar
Lift mechanism motorized motorized
Typical sample volume* 0.5 ml to 7 ml 0.5 ml to 8.5 ml
Max. tracking rate 20 K/min 200 K/min
Temperature reproducibility 0.1 K 0.1 K
VariPhi® Optional Optional

∙∙∙∙
Heat‐Wait‐Search ∙∙∙∙ Heat‐Wait‐Search

∙∙ ∙∙
Operating mode Constant heating rate Constant heating rate
Isothermal Isothermal
Stirring Optional Optional
Injection Optional Optional
Venting Optional Optional

∙∙∙∙ Thermal runaway

∙∙
Accessory for battery test – Isothermal
Cycling
Low Φ factor Yes, pressure-dependent** Yes, pressure-dependent**
Kinetics software Optional Optional

∙∙∙∙
Process Safety ∙∙∙∙ Process Safety

∙∙
Applications Comparison to Battery
legacy data Energetic Materials

* Sample volumes shown are typical and not limits. The choice of sample vessels can influence test results.
See product manual or spare parts list for more details.
** Dependent on sample pressure built-up

Technical Specifications
12
 Configurable Options to
Match Testing Needs
ARC®244 options
P
Thermocouple VariPhi® heater

Sample
vessel Syringe
injection

Stir bar
Vent
Guard
Stirring heaters
magnet

Stirring

ARC®254 options

P2
Syringe
Sample pump
VariPhi® heater P1

Thermocouple Sample Vent vessel

vessel

Vacuum Magnadrive
stirrer
Vent

Selecting the Best Calorimetry for Your Applications

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 Intelligent Software Solutions
Measurement Task
The measurement software for the Accelerating Rate Calorimeters offers easy setup
of a measurement, selection of the measurement mode and follow-up of the test
progress. All raw data signals are accessible on the screen, switches can be set with
one mouse click and simple plots of the running measurements can be generated.
The software stores data in binary and ASCII formats, making it easy to load results
into other software packages for advanced analysis.

∙∙Software automatically customizes itself to the instrument and application

∙∙Intuitive Windows set-up of testing methods with input checks to reduce typos

∙∙Methods can be saved and recalled for later use

∙∙Online help, comprehensive and easy to understand, available throughout the

software

∙∙Data is automatically saved to hard-drive throughout the run

∙∙Intelligent firmware monitors the status and health of key operating sensors and
active components

∙∙Safety integrated with hardware and firmware controls

∙∙Seamless integration of data files to Proteus®

∙∙Analysis, NETZSCH Advanced Software Tools

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 Evaluation Software
Pressure /bar
Temp. /°C
35
Analysis of the measurements is
30
done using the well-known
200
Horizontal Step (115.77 °C - 201.10 °C):
Proteus® Thermal Analysis
Thermal Inertia: 1.489
delta T: 85.3 K 25 software. Presentation of measu-
delta T ideal:
react. spec. heat:
127.1 K
266.838 J/g
rement results such as various
150
react. total heat: 1531.651 J
20
temperatures, heat generation
15
rates or the pressure development
can be done in one plot. Direct
100
10 evaluation of decomposition
Horizontal Step: 29.3 bar
enthalpies and standard kinetic
5
analysis is possible.
50
0
0 100 200 300 400 500 600 700 800
Time /min

Screenshot of the Proteus® evaluation software

Advanced Thermokinetic
and Thermal Simulation

Most decomposition reactions

cannot be explained by simple
kinetic approaches. In such cases,
the nature of a reaction is based
on various steps (consecutive,
parallel or competitive reactions).
Multiple step reactions with more
than 15 different reaction types
can be used in NETZSCH Thermo-
kinetics for the analysis of the
results. This is the ideal tool for
understanding the real chemistry
and kinetics behind a reaction.

Comparison of measured and calculated data for different phi-factors

15
 Typical Applications
Accelerating Rate Calorimeters by NETZSCH can be used for the Thermal Analysis of solid or liquid
chemicals or for gas/liquid, liquid/liquid, gas/solid, and liquid/solid mixtures. They can also be used for
process simulation of batch and semibatch reactions, fire exposures, emergency relief venting, and physical
properties measurement.

Energetic Materials
Ammonium nitrate is a base
material for various applications,
such as fertilizers. Measured here
are solid-state phase transitions
and melting (at 166°C) as well as
the decomposition behavior,
starting at 221°C. Such tests are
crucial for safety studies on such
highly energetic materials.

Analysis of the phase changes and decomposition behavior of

ammonium nitrate using the VariPhi® option

Autocatalytic Behavior
3-methyl-4-nitrophenol displays autocatalytic
behavior when heated to decomposition
temperatures. This may be studied using the
Iso-Track or Iso-Fixed feature of the
calorimeter control software. Using the
VariPhi® option allows measurement of the
sample under true isothermal conditions. The
plot shows the autocatalytic nature of the
material where the sample heat flux initially
increases and then decreases due to
consumption of reactant. The total heat
release during decomposition is simply
obtained by integration of the heat flux signal.
Autocatalytic behavior of 3 g 3-methyl-4-nitrophenol
at 180°C (isothermal)

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Vented Tests
All ARC®s may be operated in vented or open
vessel mode. For vented tests, a computer-
controlled valve is opened which allows material
to flow to a 500 ml dropout pot. If the pressure in
the reaction vessel ceases to rise and the sample
temperature remains flat or is tempered, then the
reaction may be classified as a vapor system. The
pressure in the reaction vessel may continue to
rise, but at a reduced rate because of the increase
in the head space of the reaction vessel. At the
end of the test, the contents of the drop-out pot
are available for analysis.

Vented tests showing increasing tempering as the

vent set pressure is reduced

Temp. /°C
Time-to-Maximum-Rate
220 (TMR)
200
In order to identify potential
180 hazards of chemicals during
measured data (PHI = 1,489) processing and storage often the
160
extrapolated data (PHI = 1,489) Time-to-Maximum-Rate (TMR) is
extrapolated data (PHI = 1,0) measured under adiabatic condi-
140
tions. This information is used for
predicting the temperatures for
120
safe storage of chemicals. TMR is
8.21e+001, the time between the start of a
90.0 °C
100
thermal runaway reaction and the
maximum reaction rate (maximum
80 5.50e+001, 90.0 °C self-heating rate). In case a
chemical reactor faces the
10 2 10 1 10 0 10 -1 10 -2
hazardous event of a runaway
Time-to-Maximum-Rate /h reaction, the maximum reaction
rate is equivalent to an explosion.
Temperature plotted versus Time-to-Maximum-Rate (logarithmic scaling) for a As the experimentally observed
measurement performed with 5.74 g of DTBP in toluene in a titanium sample vessel TMR value using the ARC is
(Phi factor 1.489)
If the substance/mixture is stored in a vessel which exhibits heat loss in the order influenced by the Phi factor of the
of Phi = 1.489, then the maximum self-heating rate will be reached after 82 hours. reaction vessel usually a correction
However, if there is no heat loss during storage (Phi = 1), the maximum self-heating to Phi = 1 is done which in fact
rate will be already achieved after 55 hours. predicts the worst case scenario.

17
 Typical Battery Applications

Battery Thermal Runaway

Adiabatic calorimeters allow the researcher to test full cells
in an adiabatic environment to determine how well they
perform in real and exaggerated conditions. Cells can be
charged and discharged while inside the calorimeter so
many use scenarios can be tested. With the VariPhi® option,
cells can be held isothermally during the charge and
discharge process in order to get important data on heat
energy management.

Effect of state-of-charge on the thermal stability of

a prototype 18650 lithium ion batteries

Lithium-ion battery

Battery Cycling – isothermal

Battery cycling inside a calorimeter
can provide insight into the
underlying phenomena occurring
in the cell. Furthermore, the
necessary data to design thermal
management systems for battery
packs can be determined at
Cell heater power and cell current versus time for an isothermal battery normal and exaggerated
cycling test on ARC® 254 operating conditions.

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VariPhi® Heaters for Various Battery Sizes

18650 cell and its VariPhi® 3-D sensor

D cell and its VariPhi® 3-D sensor

Expertise in
SERVICE
All over the world, the name NETZSCH stands for comprehensive support and expert, reliable service, both before
and after sale. Our qualified personnel from the technical service and application departments are always
available for consultation. In special training programs tailored for you and your employees, you will learn to tap
the full potential of your instrument.

To maintain and protect your investment, you will be accompanied by our experienced service team over the
entire life span of your instrument.

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

The three Business Units – Analyzing & Testing, Grinding & Dispersing and
Pumps & Systems – provide tailored solutions for highest-level needs. Over
3,400 employees at 210 sales and production centers in 35 countries across
the globe guarantee that expert service is never far from our customers.

When it comes to Thermal Analysis, Calorimetry (adiabatic & reaction) and

the determination of Thermophysical Properties, NETZSCH has it covered.
Our 50 years of applications experience, broad state-of-the-art product line
and comprehensive service offerings ensure that our solutions will not only
meet your every requirement but also exceed your every expectation.

NGB · Adiabatic & Reaction Calorimetry · EN · 0318 · NWS · Technical specifications are subject to change.

NETZSCH-Gerätebau GmbH
Wittelsbacherstraße 42
95100 Selb
Germany
Tel.: +49 9287 881-0
Fax: +49 9287 881 505
[email protected]