Adaptation of standard thermal analyzers and calorimeters

It may occur that standard instruments are limited in terms of application because of temperature, pressure ranges available, because of the lack of chemical compatibility of some materials against the atmospheres to be tested, or because they cannot achieve very specific functions.
Coupling analytical methods can be a way to draw more information from a single sample to understand more into depth its chemical / physical behavior, or to obtain simultaneous data under the exact same conditions. But it requires the evolution of standard analyzers so that they can physically fit and that they are not disturbed by their simultaneous operation.
For such reasons the SETARAM standard thermal analyzers can be customized

…for specific sample and process conditions

SETSYS Evolution schematics

Thermogravimetry is a common technique for the characterization of the thermal stability of materials, to understand their degradation process or to analyze their composition. Some materials like fluorides or oxyfluorides – which have interesting optical properties – release significant amounts of corrosive gases during their thermal stability testing. To fit to a customer request, our standard SETSYS Evolution TGA was modified in order to stand the release of fluorine and hydrofluoric acid (up to 20% of initial sample mass). A further challenge was that the users wanted to test the material mass uptake under a flow of a gas containing up to 10% in mass of fluorine.

For more information on the SETARAM achievements in that field, click here and download technical note TN701 in our application library

…for multiple simultaneous measurements

 Schematics of the setup after microbalance integration,
reproduced from P. Bazin and al, Dalton Trans., 2010, 39, 8432–8436

A good way to determine the adsorbed species on the surface of a catalyst is infrared spectroscopy, while thermogravimetry is a good tool for the quantification of those adsorbed species. The Laboratory of Catalysis and Spectrochemistry of Caen (France) approached us to modify a standard microbalance in order to fit it with operando IR spectroscopy. The goal was to develop a TG-IR coupling with an IR beam directly oriented to the surface of the catalyst being weighed by the balance.

HIGH TEMPERATURE OXIDATION AND CORROSION

Metallic alloys are frequently used under high thermal, chemical and mechanical stress. Numerous energy productions applications favor their oxidation, leading to a degradation of their properties. An extreme case is the nuclear power production, where zirconium based alloys are employed in nuclear reactors, at high temperature, under high humidity, and irradiation levels.  The aeronautics industry is also concerned by the corrosion phenomena of alloys used in aircraft gas turbines that decrease their service life and/or their efficiency.

Thermogravimetric analysis (TGA) is a well-established experimental method to study the growth of oxide layers on metallic alloys and can be employed to study corrosion processes providing that the thermobalance used:

  • Is sensitive enough to detect and quantify the mass uptake linked with the growth of a thin oxide layer at the surface of the test specimen
  • Can accurately and repeatedly simulate severe atmospheric conditions close or identical to those met in real applications (temperature, oxygen level, humidity…)
  • Has a stable signal over the duration of corrosion tests (up to more than 100 hours)
  • Is not significantly affected by buoyancy effect linked with atmosphere change during testing, or at least can easily and accurately be corrected by a blank experiment

This is the case of several TGA designed and manufactured by SETARAM Instrument, more specifically SETSYS Evolution TGA and the symmetrical high temperature thermobalance TAG.

METHODS

Isothermal

A typical isothermal TGA data set is depicted in Figure 1, where the resistance to corrosion of an alloy plate was tested at 1100°C. The observed mass uptake (279,5 µg.cm-2) is due to the surface oxidation of the sample. After a fast mass increase, the diffusion of more oxygen through the already formed oxide layer becomes more and more difficult, leading to a deceleration of the oxidation reaction. Several other processes may have an effect on the TGA signal like breakaway, corresponding to mechanically driven rupture in the oxide layer and a subsequent fast increase of the oxidation rate.


Figure 1 – mass uptake vs. time of an alloy plate tested at 1100°C
under a flow of oxygen (30 mL/min) during 100 hours with a SETSYS Evolution TGA

Cyclic oxidation

When testing the resistance to oxidation at high-temperature, the cyclic-oxidation may be preferred to replicate conditions close to the actual conditions of use. Indeed, it integrates isothermal oxidation kinetics, oxide-scale adherence, mechanical stresses, oxide creep and the evolution of these properties with time.

Complex temperature profiles such as the one depicted by the red curve on Figure 2 can be easily programmed. The result is a stepwise mass increase due to the successive oxidation rate increases during heating and decreases during cooling. A chart showing the mass variation per step as a function of the cycle number can then be derived from the mass uptake signal.


Figure 2 – mass uptake vs. time of a steel plate cycled between
500 and 1100°C under a flow of air (30 mL/min) with a TAG symmetrical TGA.

Wet atmosphere

In most cases, humidity promotes corrosion, and experiments under dry conditions may not describe accurately the oxidation processes as they occur in wet atmospheres. This is why it is important to mention that SETARAM thermogravimetric analyzers can be connected to the WETSYS humid gas generator.

WETSYS is designed for any application in which controlling the relative humidity rate of a chamber is necessary. It is a compact and automated wet gas generator based on a simple principle: the mixing of a dry gas and a water-saturated gas so as to maintain the relative humidity of the generated outlet gas at a given temperature.

Both isothermal and cycling temperature profiles can be operated under wet conditions as the TGA temperature control is independent of the WETSYS.

Figure 3 Wetsys humid gas generator

APPLICATIONS

Isothermal, dry conditions

Nb-silicide composites are potentially interesting materials for applications in gas-turbine engines for aircraft, where they may face high-temperature (1150°C) hostile environments (oxygen, water vapor, etc). The team of Michel Vilasi from the Institut Jean Lamour in Nancy, France used their TAG symmetrical thermobalance in order to conduct isothermal oxidation tests at 1100°C under an industrial air flow of 1.5 L.h-1 [1]. The parabolic rate constant that is used in oxidation models could be deduced from these tests.

Temperature cycling, dry conditions

The team of Daniel Monceau, from Institut Carnot CIRIMAT in Toulouse, France, has developed a methodology based on temperature cycles meant to determine the Net Mass Gain, the Gross Mass Gain, the total mass of spalled oxide, the rate of metal consumption and the average oxide scale thickness as a function of the number of cycles.
The instruments involved were a standard TAG symmetrical thermobalance and a home designed 6 samples thermobalance system with a six halogen-lamps-furnace and 6 independent alumina sample holders and 6 balances.

They validated their method on slow and fast oxidation kinetics alloy samples, respectively single-crystal beta-NiAl (168 cycles between 150 and 1150°C) at and P91 steel (13 cycles between at 140 and 800°C) [2].

Later on, a custom designed 5 samples thermobalance developed by SETARAM was adapted to a lamps furnace by CIRIMAT and the same method was also applied other materials like Thermal Barrier Coating [3].

 

Isothermal, wet conditions

Chromium-bearing steels are used as piping or heat exchanger materials in oxyfuel processes for coal combustion, where they are exposed to hot CO2–H2O gas mixtures. The team of Daniel Monceau, from Institut Carnot CIRIMAT in Toulouse, France, has worked on model Fe–Cr and Fe–Cr–Ni alloys, reacted in Ar–CO2 and Ar–CO2–H2O gas mixtures at 650 °C in a Setsys Evolution TGA equipped with a WETSYS [4]. Oxidation isotherms as long as 300 hours, showing mass uptakes as low as 3mg.cm-2 were collected and showed that during reaction in Ar–CO2 and Ar–CO2–H2O at 650 °C, breakaway occurred via nucleation and growth of Fe-rich oxide nodules.

Figure 5 – Setsys Evolution TGA

 

 

Innovating approaches

At the Saint Etienne School of Mines, in the SPIN lab, an innovative setup involving the coupling between a TAG symmetrical thermogravimetric analyzer and acoustic emission was used to study the Zircaloy-4 corrosion mechanism [5].
The system, in which piezoelectric sensors were placed in the balance head and specific wave guides were employed to hold the samples in the TGA furnace, allowed simultaneous measurements of the sample mass variation and AE burst.  Combined with post mortem characterization of oxidized samples, it provided additional information on the Zircaloy-4 corrosion mechanism:

  • Kinetic transition is detected under air oxidation tests at 900°C by a change in the rate of mass gain and by the AE activity
  • AE allowed distinguishing the cracks which occur during oxidation from the cracks linked with the cooling of the samples

Viscosity of inkjet inks with m-VROC® and microVISC™:

Viscosity of inkjet inks with m-VROC® and microVISC™:

Digital printing technology has motivated a rapid growth of the inks industry. The increasing demand for inkjet inks has resulted in faster production and more stringent quality control requirements. To meet the market demands, efficient, fast, and highly accurate and fast characterization methods are required.

Two main physical properties determine print quality – surface tension and viscosity. These two factors play a key role in droplet formation as well as the uniformity of the resulting printout. Ink viscosity depends on the ink formulation (pigments, resins, binders…), temperature, and in some cases, the shear rate specific of the inkjetting process.

At the same time, inks often present low viscosity values (<10 cP). This results in flow instabilities when trying to achieve high shear rate measurements of viscosity with conventional rheometers and viscometers.

VROC® powered instruments, m-VROC® and microVISC™, provide a solution to the challenges of conventional viscometer technologies. By utilizing the combination of a capillary and MEMS device, VROC®’s superior technology enables fast and accurate characterization of inkjet inks, ceramic inks, water based inks and biopolymer based inks. The high accuracy and repeatability over a wide range of shear rates make our systems Simply Precise™ with ease!

View Ink Application Notes
High Temperature, High Shear hts-VROC Viscometer
Target Keywords
Inks Viscosity
Inkjet Inks
Non-Newtonian Inks
Shear Thinning Inks
Accurate Low Viscosity Measurements
Viscosity Fingerprinting
Industries:
Inkjet Inks
Ceramic Inks
Water Based Inks
Biopolymer and Protein Inkjet
Formulations
Current Customers
Hewlett PackardHewlett-Packard Company (HP) is a global company headquartered in Palo Alto, California, United States. It is one of the first developers and leading manufacturers of inkjet printers since the late 1970s.

Viscosity is one of the key factors determining the quality of inks. Utilizing m-VROC at various locations, researchers study the rheological behaviors of inks during jetting.

FerroHeadquartered in Cleveland, Ohio, Ferro operates in 26 countries globally.

One of Ferros’s innovative product lines focus on inks for digital print decorations for ceramic tiles. With the help of m-VROC, Ferro is able to build the fluid profile for their samples and correlate viscosity with different formulation parameters.
​​
Potential Customer

INX International Ink Co.

A part of Sakata INX, a $1.3 billion company, INX International has 15 plants in the U.S. and Canada along with more than 50 locations worldwide.

Among North America’s top three ink providers, only INX focuses on print formluations, starting from developing the chemical and into the finished product.

Combining Rheometry with FTIR and Microscopy: Benefits and Applications in Polymer Research

Thermo Scientific
Webinar Banner
Join us for our webinar:Combining Rheometry with FTIR and Microscopy: Benefits and Applications in Polymer Research
Register
Date:
Tuesday, October 20, 2015Times:
Session 1:
8:00 a.m. (EDT) /
12:00 (GMT) /
2:00  p.m.(CEST)
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Session 2:
11:00 a.m. (EDT) /
15:00 (GMT) /
5:00 p.m. (CEST)
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Webinar Duration:
45 minutes with
15 minutes for QA

Presenter:
Jan Plog
Senior Applications Specialist
Thermo Fisher Scientific

Register today!

Simultaneous rheological and optical measurements are becoming increasingly popular – particularly for product development in the polymer area. Here, changes in the rheological profile can be correlated with information on either the microstructure (microscopy) or molecular structure (FTIR).

Join us for this webinar and learn more about:

  • Simultaneous Rheology and FTIR spectroscopy measurements
  • Simultaneous Rheology and Optical Microscopy measurements
  • Viscoelasticity
  • Thermal and UV curing
  • Pharmaceutical polymers and Hot Melt Extrusion

Who may be interested in attending?
Scientists, engineers and laboratory staff members, involved with development and formulation of polymer related products using rheology and/or optical analytical methods.

Register
Know you’re already busy this day? Register anyway, we’ll send the recording and slides after the webinar to watch on your time!

Upcoming WITec Webinar: Correlative Microscopy/Low dimensional Materials – 15. October

FREE TO REGISTER

Thursday 15th October, 4pm (CEST), 11am (EDT)

The aim of this webinar is to highlight the benefits of correlative microscopy for studies of graphene and related two-dimensional transition metal dichalogenides (TMDs) such as MoS2 and WS2. Raman Imaging is used to characterize the optoelectronic properties of 2D materials. In combination with AFM and SEM the precise geometric dimensions of these materials is determined. Photonic properties can be gained using SNOM.

Key learning objectives are:

Gain insight as to how unrivalled spectral and spatial resolution, ultra-fast acquisition times, and exceptional signal sensitivity in Raman Imaging can be combined with AFM, SNOM and SEM.

Learn which properties of low dimensional materials can be characterized with Raman and how complementary techniques lead to a more comprehensive understanding of the sample.

Learn how to configure a Raman microscope in order to perform high-sensitivity and high-resolution 3D spectral imaging routinely.

New Rheometer Provides Fast, Insightful Analysis

Get easy, fast Material Characterization with our new Rheometer

The new Thermo Scientific™ HAAKE™ MARS™ rheometer helps reduce measuring errors and optimize your workflow with easy access for sample preparation. Plus it has automatic recognition of measuring geometries and temperature modules that quickly snap into place.

Flexible Design. The rheometer’s modular design offers maximum flexibility for application-specific or advanced testing needs in polymers, petrochemicals, coatings, food, cosmetics, and pharmaceuticals. For example, easy-to-use FT-IR or microscopy modules connect quickly to the rheometer for hybrid analyses to match macroscopic analysis with microscopic information to understand changes in your sample.

Seamless Method Transfer. Advance research in the lab, and get the results to your production line faster. Established methods easily transfer to the Thermo Scientific™ HAAKE™ Viscotester™ iQ rheometer for routine QA/QC testing.

Find out how the new HAAKE MARS can advance your rheological measurements today.
Download the Brochure

Benefits of Combining Rheometry with FTIR and Microscopy for Polymer Research

Webinar Banner
Join us for our webinar:Combining Rheometry with FTIR and Microscopy: Benefits and Applications in Polymer Research
Register
Date:
Tuesday, October 20, 2015

Times:
Session 1:
8:00 a.m. (EDT) /
12:00 (GMT) /
2:00  p.m.(CEST)
What time is this for me?

Session 2:
11:00 a.m. (EDT) /
15:00 (GMT) /
5:00 p.m. (CEST)
What time is this for me?

Webinar Duration:
45 minutes with
15 minutes for QA

Presenter:
Jan Plog
Senior Applications Specialist
Thermo Fisher Scientific

Register today!

Simultaneous rheological and optical measurements are becoming increasingly popular – particularly for product development in the polymer area. Here, changes in the rheological profile can be correlated with information on either the microstructure (microscopy) or molecular structure (FTIR).

Join us for this webinar and learn more about:

  • Simultaneous Rheology and FTIR spectroscopy measurements
  • Simultaneous Rheology and Optical Microscopy measurements
  • Viscoelasticity
  • Thermal and UV curing
  • Pharmaceutical polymers and Hot Melt Extrusion

Who may be interested in attending?
Scientists, engineers and laboratory staff members, involved with development and formulation of polymer related products using rheology and/or optical analytical methods.

Register
Know you’re already busy this day? Register anyway, we’ll send the recording and slides after the webinar to watch on your time!

NEW PRODUCT RELEASE: Automatic Viscometer, VROC initium September 30, 2015 | 11:00 am (PST)

This webinar will introduce RheoSense’s automatic, high throughput viscometer, VROC® initium. Attendees will get the first sneak peek of the instrument and data.
Key Features Include:
  • 10 microliters
  • 40 Vial Rack/96 Well Plate
  • Unattended Measurements
Major Applications of VROC® initium Include: 

  • High Throughput Screening with Viscosity
  • Protein Therapeutics — Stability & Injectability
  • Kinetics of Chemical Reaction and Degradation
  • Intrinsic Viscosity — Protein & Polymer Size
  • Solubility
Attend Webinar

Monitoring oil viscosity as a function of temperature

Webinar :
Oil Viscosity — ​ ​
September 23, 2015
11:00 am (PST)

Monitoring oil viscosity as a function of temperature and shear rate is essential for many reasons including:

– Ensuring Oil Quality
– Oil Characterization Under Different Conditions
– Detecting Oxidation (Decay)
– Improving performance of engines & preventing mechanical failure
– Reducing wear, inhibiting corrosion, improving sealing and cooling
​This webinar will cover the analysis and characterization of oils across temperature and shear rate ranges, along with the importance of such characterization. In addition, it will cover the estimation of high-temperature viscosity values utilizing room-temperature viscosity measurement and ASTM D341.

Viscosity Fingerprint of Conductive Inks with m-VROC

Application Corner is an outlet to help specify target markets and provide guidance to exploring applications and potential customers. Application information, target keywords related to the application, and customers will be provided.
Viscosity Fingerprint of Conductive Inks with m-VROC:

Printed electronics, touch screens, optoelectronics and PV devices are just some application examples for conductive inks. To enhance electric conductivity these fluids often contain silver, copper or carbon-like materials. The rheological properties of these formulations are determined by the size, shape, concentration, and structures formed by the conductive materials.

The viscosity fingerprint (i.e. viscosity dependence on shear rate) of these conductive fluids will determine performance and flow during manufacturing processes. Conventional methods to measure viscosity often suffer from flow instabilities at high shear rates, which can result in erroneous estimates of viscosity at the shear rates that are relevant for inkjet (104-5 1/s) and roll coating (104) processes.

m-VROC™ viscometer has the widest dynamic range for the measurement of viscosity. The high accuracy, high shear rate capabilities, and high speed of measurement make our systems Simply Precise™

Download Graphene Inks Application Note
Download Silver Inks Application Note
High Temperature, High Shear hts-VROC Viscometer
Target Keywords
m-VROC™ high shear viscometer
Conductive inks
Silver nanoparticles inks
Silver nanowires inks
Graphene inks
Conductive pastes
Inkjet printing
Roll coating
Ink formulation
High-Shear Viscosity
High-Accuracy Viscosity
Industries:
Printed electronics
Flexible Electronics
Touch screens
Optoelectronic
Photovoltaic devices
Current Customers
Electroninks
Electroninks Incorporated is a printed electronics company based on high-performance, low-cost printed electronics via novel materials development. Currently, the company offers two product lines; Circuit Scribe, a rollerball conductive pen for the STEM education and maker communities and Reactive Silver Inks, novel silver inks for the printed electronics industry that achieve conductivities of up to 90% of bulk silver with annealing temperatures under 100C.

Potential Customers

C3nano
C3nano is the developer of the solution-based, transparent conductive inks and films as direct replacements for indium tin oxide (ITO). C3nano’s advancements in silver nanowire (AgNW) based technology enable 30 to 50 Ohms per square for a new generation of smart flexible devices with enhanced sensing functions.

Cambrios Technologies
Cambrios is the leader in silver nanowire solutions to enable the development of electronic devices with transparent conductors. Our proprietary nanostructured materials can be deposited using existing production equipment to achieve enhanced performance of display devices and components at lower manufacturing cost.
ClearOhm®, their first product, is a directly patternable, wet-processable transparent conductive film made from silver nanowires that is poised to replace the industry standard sputtered indium tin oxide (ITO). Subsequent products will leverage this technology to produce other functional films for display and thin film applications for multiple consumer electronic device markets.