Characterization of Nuclear Materials Methods, Instrumentation, Applications

Analyzing & Testing

Leading Thermal Analysis Introduction

The world demand for electricity is In addition, the nuclear reactors of projected to double by mid-century. current design are safe and, save a Because of the ever-increasing price natural disaster such as the magnitude of fossil fuels and the associated 9 earthquake east of Japan and environmental concerns such as carbon resulting tsunami, accidents are highly dioxide emissions, nuclear power unlikely. In spite of the accident at the generation is regaining popularity. Fukushima nuclear power plant caused Nuclear fuel is clean and relatively by the earthquake/tsunami, the strong inexpensive compared to fossil fuels. resurgence – so-called renaissance – of It is in fact the only source of clean, nuclear power is expected to continue. sustainable and affordable energy which can meet current and near-term This renaissance has led to the demands for electricity generation, formation of a multi-national if sufficient numbers of reactors of cooperation called the Global Nuclear current and advanced design can be Energy Partnership (GNEP). Two of the brought on line in a timely manner. stated aims of GNEP are to:

2 develop a new generation of nuclear development and the GEN IV reactors power plants – the so-called Genera- under consideration are of unique design tion IV systems (GEN IV) in which with respect to safety, performance and six different reactor types are under economics. The GEN IV reactors include consideration (both thermal and fast the Very High Temperature Reactor reactors), and (VHTR), the Sodium-cooled Fast Reactor (SFR) and perhaps the most unique, the reduce waste by recycling used Molten-Salt Reactor (MSR). Many of nuclear fuel using new technologies. these reactors will contain unique fuel systems and reactor materials. The history of commercial nuclear power generation reaches back to the mid-60s. The Generation III+ reactors now under

Generation I Generation II Generation III Generation III+ Generation IV Early Prototype Commercial Power Advanced LWRs Evolutionary Highly Reactors Reactors Designs Offering Economical LWR-PWR, BWR Improved Enhanced Safety CANDU Economics Minimal Waste AGR for Near-Term Proliferation Deployment Resistant

I II III III+ IV

1950 1960 1970 1980 1990 2000 2010 2020 2030

Time line for reactor development

3 Introduction

Source: Idaho National Laboratory

The major concern with nuclear power Long-lived I and Tc generation today is the safe disposal of Minor 0.1% used fuels. Because of storage-related Actinides 0.1% Cs and Sr problems, recycling of used fuel is of Plutonium 0.3% paramount importance. Fuel recycling 0.9% is not a new concept. In fact, used fuel Other Long-lived from light-water reactors (LWR) has

Fission been reprocessed into (U,Pu)O2 – Products so-called MOX fuel – for some time by 0.1% Stable Fission various countries. This is economically Products 2.9% feasible because spent fuel contains not only fission products and minor actinides such as Americium, Neptunium and Curium, but a large percentage of U 95.6% (235U 0.5-1.0%) fissile Uranium and Plutonium isotopes Composition of used fuel as well.

4 Reactor/ Interim Fuel Fabrication UO2 Used Fuel Power Plant Fuel Storage

UO2 Aged Used Fuel (U,Pu,Np)O2

Reconversion (Am,Cm)O2 Fuel Recycle/ UO2 Target Fabrication/ UF6 Separation Enrichment Waste

UF6

UO2 Recycle Geological Conversion Repository

U3O8

Uranium Mining & Milling

F R O N T E N D B A C K E N D

Closed fuel cycle with front end processing of UO2 and back end recycling/target fabrication

It has been estimated that the effective reprocessed fuel or targets for capacity of geological repositories can transmutation/consumption. Several be increased greatly if the long-lived concepts have been proposed to realize minor actinides such as those this, some of which utilize fast reactors mentioned above plus Pu (transuranics) and others thermal reactors. are separated and fabricated into the

5 Introduction

In addition, studies have shown that Of course, a prerequisite for the significant reductions in repository heat successful design of any new reactor or and radiotoxicity loads can be realized by fuel system as well as modernization of placing used fuel in interim storage for the existing reactor fleet is the accurate a few years to allow short-lived fission knowledge of the thermophysical products such as Cs-137 and Sr-90 to properties for the materials of interest. partially decay prior to separation. This will necessitate the measurement of the thermophysical properties for Interim storage also reduces the fresh, reprocessed and used fuels as well problems associated with reprocessing as irradiated and unirradiated reactor fuel containing Cm, but also increases component materials. the content of high-vapor-pressure Am-241 due to the β-decay of Pu-241.

Assumptions Limited by 200°C Burnup: 50 GWd/MT 225.0 drift wall temp. Separation: 25 years at emplacement Emplacement: 25 years Closure: 100 years 175.0

94.0 Limited by 200°C drift 91.0 wall temp. at closure Limited by 96°C mid-drift temp. 54.0 >1600 yrs 44.0

5.7 10.5 10.3 5.5 10.0 0.001 1.0 4.4 1.0 0.01 1.0 1.0 Fraction Pu, 0.1 Am & Cm in 0.001 Waste 0.01 1 Fraction Cs & Sr in Waste 0.1 1

The calculated increase in repository capacity as a function of reduced Cs, Sr, Pu, Am and Cm content with separation after 25 years “Separations and Transmutation Criteria...“, Wigeland, et al., Nuc. Tech., 2006

6 Property measurements on fission of these properties on the materials use. All of these attributes are necessary products and/or their surrogates, glasses, mentioned above will necessarily be for instruments operating in harsh containment components and geological carried out in glovebox and hot cell environments such as gloveboxes and materials associated with long-term environments as well as in cold facilities. hot cells. Further, the modular design isolation in repositories are also of of our instruments makes them ideally paramount importance. The properties Over the past few years NETZSCH- suited for incorporation into these of interest include but are not limited Gerätebau GmbH has become the environments. Finally, the costs of to the thermal conductivity, thermal leading supplier of thermal analysis operating in hot cells and gloveboxes diffusivity, specific heat, transformation and thermophysical properties are extremely high, making downtime energetics, thermal expansion, bulk instrumentation to the nuclear industry. critical. Our exemplary global service density, solidus/liquidus temperatures This is because our instruments are is therefore one more reason for our and O/M ratio. Clearly, measurement reliable, robust, accurate and easy to success.

35 33000 MWd/MTIHM 75.5% 13% 95.3% 30 55000 MWd/MTIHM 242 (n,γ) 243 (n,γ) 244 (n,γ) 25 Cm Cm Cm 162.8 d (n,f) 29.1 y (n,f) 18.10 y (n,f) 20 24.5% 87% 4.7% 15

10 84% β (>83%) 5 (n,f) 242m Cm% in Am-Cm Fraction FPs Am 16% 0 141 y (n,γ) 0 20 40 60 80 100 9% Years after Removal from Reactor (n,β) 90% 34% 99.2% 20% α α α 241Am (n,γ) 242Am (n,γ) 243Am (n,γ) 244mAm 244Am (n,γ) 432.2 y (n,f) 16.02 h (n,f) 7370 y (n,f) 26 m 10.1 h (n,f) 1.0% 66% 0.8% 80%

92.6% 36.3% 99.8% 26% 98.7% 238Pu (n,γ) 239Pu (n,γ) 240Pu (n,γ) 241Pu (n,γ) 242Pu (n,γ) 243Pu (n,γ) 244Pu 87.7y (n,f) 2.41x104 y (n,f) 6563 y (n,f) 14.36 y (n,f) 3.733x105 y (n,f) 4.956 h 8.08x107 y 7.4% 66.7% 0.25% 74% 1.3%

α α α α α

17% 242Pu 241Am 242Am

242 238 239 83% Cm Pu Pu 241Pu 242Pu 243Am 244mAm 244Cm

“A G E D F U E L“ “Y O U N G F U E L“

Transmutation Benefits of Older Fuel “Closed Nuclear Fuel Cycle…”, Collins, et al., Atalante 2008 Int. Conf., 2008

7 Thermophysical Properties

Introduction

Thermophysical properties can be Thermodynamic properties include divided into two categories – transport specific heat, transition energetics and and thermodynamic. Transport thermal expansion (bulk density). properties include, but are not limited to, thermal conductivity, electrical resistivity and thermal diffusivity. Thermophysical Properties (Actually, thermal diffusivity is a hybrid transport/thermodynamic property.)

Thermodynamic Thermal Transport Properties Diffusivity Properties

Thermal Expansion Specific Heat Thermal Electrical (bulk density) and Enthalpy Conductivity Resistivity

Classification of some thermophysical properties

Thermal Conductivity ability of geological repositories and Specific Heat and Transition container material to dissipate heat Energetics The thermal conductivity is perhaps the heat transfer in multi-layer fuel single most important thermophysical systems, e.g. TRISO. The capacity of a material to store property and is paramount to the design energy is governed, in part, by the of any system operating at elevated or The complete list is quite long. The specific heat (sensible heat). It is made sub-ambient temperatures. It consists of thermal conductivity is greatly affected by up of lattice, electronic and defect a lattice and/or electronic component, corrosion, hydriding, fouling, O/M ratio, components, depending on the material. depending on the material (other fission product carry-over, irradiation This property is required for design of components are also possible). It is well damage, composition, porosity, etc. The any transient heat transfer process. It is known in the nuclear industry that the thermal conductivity/thermal diffusivity also used to quantify surface oxidation/ thermal conductivity controls: of almost all nuclear materials is most reduction and O/M ratio (defects) of efficiently measured by the laser flash fuels during processing. In some cases, temperature gradients in fuel technique (LFA). LFAs can readily be the specific heat can be used as an efficiency of cladding and heat incorporated into gloveboxes and hot indicator of the extent of damage in exchangers cells with the appropriate modifications. post irradiation examination (PIE), e.g.

8 stored energy. It is also required to measurements, but care must be densification during sintering calculate the thermal conductivity from taken to avoid undercooling during thermal expansion coefficients thermal diffusivity data. solidification (especially critical for volume change during melting/ metal alloys). Sample time constants solidification Transition energetics (latent heat) are and temperature ramp rates must be bulk density required to characterize solid-solid carefully considered. Solidus/liquidus transitions, melting/solidification and temperatures of most metal alloys can and, as stated earlier, the data can be decomposition. Both specific heat and also be measured by the laser flash used to determine solidus and liquidus transition energetics are most accurately technique (by utilization of thermal temperatures. By far the most versatile, and efficiently measured by differential conductivity/thermal diffusivity data) and accurate and economical technique to scanning calorimetry (DSC). The specific dilatometry can be used for conductors measure thermal expansion is pushrod heat can also be measured by the laser and insulators alike. For materials that dilatometry. Dilatometers are well flash technique, albeit with reduced melt at ultra-high temperatures, thermal suited for glovebox/hot cell work. accuracy and only with a reduced number arrest is sometimes employed using of data points. (With DSC, generation of optical pyrometers for the temperature a quasi-continuous set of temperature- measurement. All things considered, Mass Change and Evolved Gases dependent specific heat data is standard.) DSC is the most versatile and accurate With the required expertise, DSCs can method. Temperature-dependent mass change readily be adapted for hot work. coupled with evolved gas analysis provides valuable information to help Thermal Expansion quantify: O/M ratio, out-gassing during Solidus and Liquidus Temperatures fuel processing, corrosion, reduction, Thermal expansion can be made up volatile fission products/actinides Solidus and liquidus temperature as of lattice, electronic, magnetic and during vitrification, impurities well as melting temperature data are vacancy/interstitial components, remaining from the separation process, necessary to establish safe reactor depending upon the material and etc. A thermogravimetric analyzer operating conditions and to model temperature. Thermal expansion (TGA) or simultaneous TGA-DSC (STA) accident scenarios such as loss of data are key to both reactor and fuel instrument coupled to a quadrupole coolant. These temperatures are design. For example, it is necessary for mass spectrometer (QMS), either greatly affected by impurities, radiation quantification of: directly or by a heated transfer line, damage, O/M ratios, burnup and, or a TGA or STA coupled to an FT-IR of course, composition. Surprisingly, fuel swelling during irradiation via a heated transfer line are widely solidus/liquidus temperatures are fuel/coating compatibility (e.g. UO2/ employed for these types of analysis. notoriously difficult to measure graphite/SiC or ZrC) As with the other techniques previously accurately. DSC is the technique abrasion and corrosion coating/ discussed, these instruments can easily most often employed for these substrate compatibility be modified for hot work.

9 Instrumentation

Flash Technique

The flash method is the fastest and most accurate way of measuring the thermal diffusivity ( thermal conductivity). It has been estimated that 80-85% of all e Clay

, Silicon Carbide thermal diffusivity/thermal conductivity ous Insulations ds, Oils

ds, Fiber Insulations,

opor measurements are carried out using this ene, PU Foams ete, Glass, Fir , Copper

ous Ceramics, Refractories technique. This is because of: , Micr ood, Polymers, Coal ater acuum Insulation on, Steel, Silicon V Air Polystyr Fiber Boar Building Boar W W Concr Por AlumonosilicatesSilicon Nitride Alumina, Carbon Bricks Ir Aluminum, GraphiteSilver Diamond easy sample preparation: coin-sized disk or square/rectangle Heat Flow Meter (-30°C to 100°C) (can be even smaller) flexibility: measurements on solids, Guarded Hot Plate (-160°C to 250°C) liquids, pastes, powder and laminate Hot Wire (RT to 1500°C) samples

small sample size: ideal for Flash (-125°C to 2800°C) fuels/irradiated materials fast measurement times: due to 0.001 0.010 0.100 1.00 10 100 1000 Thermal Conductivity at RT [W/(m.K)] small sample size

high accuracy: usually better than 5% Comparison of the flash method with other techniques utilized in NETZSCH instruments as well as wide thermal diffusivity/thermal approximate room temperature thermal conductivity ranges of several types of materials. conductivity range: approx. 0.01 to 1000 W/m·K wide temperature range: -125°C to 2800°C

As shown below, the front surface of a Using the measured thermal diffusivity The bulk density can be obtained from sample is heated by a short energy pulse values, the thermal conductivity is thermal expansion data, and the specific (xenon or laser) and the time-dependent calculated by: heat by either the LFA or a DSC. temperature rise on the rear surface is measured by an IR detector. From a plot λ(T) = a(T) · cp(T) · ρ(T) of T / Tmax (or V / Vmax) vs half-time, the thermal diffusivity of a perfectly insulated where sample at one half-time is given by: λ = thermal conductivity (W/m·K) ρ = bulk density (g/m3) 2 a = 0.1388 l /t½ Cp = specific heat (J/g·K) where

2 a = thermal diffusivity (mm /s) detector protective l = sample thickness (mm) 1.0 tube t½ = half-time (s) furnace max sample There are several sophisticated models thermo- sample 0.5 to correct for heat loss (non-adiabatic or V / couple conditions) and the finite pulse width of max T / the energy source. heating element power 1.0 half-time source Experimental data Flash technique

11 Instrumentation

Light/Laser Flash Analysis

LFA 457 MicroFlash®

The LFA 457 embodies the latest technology for modern laser flash systems. This bench-top instrument has a temperature range of -125°C to 1100°C using two user-exchangeable furnaces. The vacuum-tight design enables tests under well-defined atmospheres. Sample sizes of up to 25.4 mm Ø can be accommodated and the integrated sample changer allows simultaneous measurement of up to 3 samples. The innovative infrared sensor technology employed in the system enables measurement of the sample temperature increase, even at temperatures of -125°C.

The vertical arrangement of the sample holder, furnace and detector simplifies sample placement and, at the same time, guarantees an optimum signal-to-

noise ratio for the detector signal. The LFA 457 modified for small footprint of this instrument makes glovebox operation it ideal for modification for glovebox and hot cell applications. LFA 467 HyperFlash

The LFA 467 HyperFlash is a Xenon flash-based system with a compact design. It covers the temperature range from -100°C to 500°C. A variety of cooling options allow for measurements to be carried out across the full temperature range of the instrument without having to change either the furnace or the detector. The integrated automatic sample changer allows for unattended analyses on up to 16 samples. The very high sampling rate and the unmatched ZoomOptics make for a broad application range, even for thin samples.

12 The NETZSCH LFAs cover almost the entire range of temperatures and materials of interest to the nuclear industry. For convenience, some of the specifications are summarized in the table below.

Model Temperature Range Atmosphere Energy Detector

LFA 467 -100°C to 500°C inert, oxid. Xenon flash InSb LFA 457 -125°C to 1100°C inert, oxid., red., vac., corr. Laser InSb / MCT LFA 427 -120°C to 2800°C inert, oxid., red., vac., corr. Laser InSb / MCT

LFA 427

The 427 is the most powerful and versatile LFA system for research and development as well as all applications involving the characterization of standard and nuclear materials.

The LFA 427 guarantees high precision and reproducibility, short measurement times and defined atmospheres over a temperature range of -120°C to 2800°C. Special holders for liquid, fiber, paste, powder and laminate samples are available. Even fuel fragments can be tested.

The system is vacuum tight to 10-5 mbar. The variable laser power and pulse width functions make it easy to optimize test parameters.

LFA 427 modified for hot cell operation

13 Instrumentation

Differential Scanning Calorimetry (DSC)

Heat flux DSCs function by measuring where region of a phase transition the result is

the temperature difference (voltage Cp,s = sample specific heat [J/(g·K)] typically referred to as apparent specific C = standard specific heat [J/(g·K)] difference) between a sample and a p,std heat. The resulting peak in the specific ms = sample mass [g] reference while being heated or cooled mstd = standard mass [g] heat curve can then be integrated to μV = sample scan signal at a constant rate. The resulting signal s give the transition energy, Δh (J/g). μVstd = standard scan signal is proportional to the mass × specific μVBL = baseline scan signal Finally, the onset and end of the latent heat (sensible heat) plus the energy heat peaks can be used to define the associated with any phase change, etc. The resulting specific heat curve will also solidus and liquidus temperatures as (latent heat). This signal is converted to include any latent heat due to phase long as time constants and undercooling actual physical quantities through transitions, etc. In the temperature are given proper consideration. calibration using melting point standards having well-defined heats of fusion or specific heat standards with well-established and reproducible

temperature-dependent specific heat Difference

values. This is typically referred to as a ~ Mass · cp

TC Voltage [μV] Voltage TC (~ Temperature) T sensitivity calibration. The signal R Reference signal generated by a heat flux DSC is shown Sample signal T M T Transition temperature here. TS M

The temperature-dependent specific Time [s] t1 t2 heat is obtained by running a baseline

(empty crucibles), standard and sample S - T scan. Using these data the specific R Area A heat is calculated by the so-called ratio ~ Transition enthalpy ΔT = T method where the specific heat of the sample is given by: Difference (from 0) mstd μVs-μVBL ~ Mass · cp Cp,s = Cp,std ms μVstd-μVBL Signal generation in t t Time [s] 1 2 a heat flux DSC

The NETZSCH F Series DSCs cover most applications of interest to the nuclear industry. An overview of some of the specifications is given in this table.

Model Temperature Range Atmosphere Vacuum Sensor Types

DSC 404 F1 -150°C to 2000°C inert, oxid., red., vac., corr., humid 10-4 mbar E, K, S, B, W-Re DSC 404 F3 -150°C to 2000°C inert, oxid., red., vac., corr., humid 10-2 mbar E, K, S, B, W-Re

14 NETZSCH DSC 404 F Pegasus® Series

The F Series DSCs (F1 and F3) have These units are widely used in the a temperature range of -150°C to nuclear industry in both cold and hot 2000°C and are vacuum tight down applications. The glovebox/hot cell to 10-4 mbar. Eight different furnaces versions are equipped with special are available and, when equipped sample loading mechanisms and sample with a double hoist, 2 furnaces can be carrier adjustment systems to facilitate mounted simultaneously. There are 13 operation. These special configurations different user-exchangeable fast-fix have reduced footprints with separate plug-in sensors which allow optimization electronics and MFCs located outside of sensitivity and time constants. the glovebox or hot cell.

The F Series was designed specifically for high-temperature specific heat measurements. Accuracies in the range of ±2.5% can be obtained for most materials over the temperature range of -150°C to 1400°C for specific heat and better than 2.0% for latent heat over the temperature range of -150°C to 1650°C.

Evolved gases can also be identified and quantified (with optionalPulse TA® unit) by coupling the DSC to an MS, GC-MS and/or an FT-IR via a heated furnace adapter head and heated transfer line. Special options for corrosive gases are also available.

Automatic sample changers are available for the F Series, but are not generally recommended for glovebox/ hot cell operation.

DSC 404 F1 Pegasus® with automatic sample changer

15 Instrumentation

Dilatometry (DIL)

Pushrod dilatometers measure, via The volumetric expansion for an an LVDT, the thermal expansion of a isotropic material is then calculated by: sample while it is being heated at a ΔV constant rate or held isothermally (with ≈ 3αΔT V the exception of non-linear rates in 0 rate-controlled sintering studies). The where voltage signal is proportional to the V = volume (cm3) V = initial volume (cm3) expansion of the sample. This raw signal 0 is converted to the length change by calibrating the instrument using a Thus, the instantaneous temperature- standard with a well-defined and dependent bulk density, ρ, for an reproducible thermal expansion. isotropic material can be calculated using:

The temperature-dependent length m m change is used to calculate the ρ = ≈ V V0 (1+ 3αΔT) coefficient of linear expansion,α , i.e.: where m = instantaneous mass (g). 1 ΔL 1 (L -L ) α = = 2 1 L0 ΔT L0 (T2-T1) where L = length (mm)

L0 = initial length (mm) T = temperature (°C)

Four modified DIL 402 C dilatometers operating in a hot cell

Rolf, this is an extremely powerful picture, but it needs some editing. We have permission to use it.

Four modified DIL 402 C dilatometers operating in a hot cell 16

16 NETZSCH DIL 402 Series

NETZSCH manufactures 5 unique horizontal dilatometer models which operate over a temperature range of -260°C to 2800°C. The LVDT housings are thermostatted and have Invar LVDT mounting systems. This ensures that the length signal is not disturbed by the furnace or fluctuations in the room, glovebox or hot cell temperature. All of these dilatometers (except the ED) can be equipped with at least 2 Dilatometer model 402 C user-exchangeable furnaces and some up to 4. All models except the PC are vacuum-tight down to 10-4 mbar Software options such as c-DTA®, and sintering, respectively. Using or better. The accuracy is better than RCS, density and thermokinetics special sample holders, the solidus

1% for most materials. Graphite, Al2O3 allow calculation of phase and liquidus temperatures can also be and fused silica sample carriers and transitions, measurement of determined. pushrods with sample thermocouple densification under variable heating types E, S, B and W-Re are available. rate conditions, calculation of bulk The small footprint and horizontal Special holders for liquid metals, pastes, density from linear expansion data design of the NETZSCH dilatometers powders, fibers and thin films are also for isotropic samples and kinetic make them ideal for incorporation into available. evaluation during phase transitions gloveboxes/hot cells.

The NETZSCH dilatometers cover almost all conceivable nuclear applications. For convenience, some of the specifications are summarized in this table.

Model Temperature Range Atmosphere ∆l Resolution Type

DIL 402 PC RT to 1600°C inert, oxid. 8 nm single pushrod

DIL 402 C -180°C to 2000°C inert, oxid., red., vac., corr., humid 0.125 / 1.25 nm single pushrod DIL 402 E -180°C to 2800°C inert, oxid., red., vac., corr., humid 1.25 nm single pushrod

DIL 402 CD -180°C to 2000°C inert, oxid., red., vac., corr., humid 0.125 / 1.25 nm dual sample/differential

DIL 402 ED -260°C to 30°C inert, oxid., red., vac., corr., humid 0.125 / 1.25 nm dual sample/differential

17 Instrumentation

Thermomechanical Analysis (TMA)

Thermomechanical Analysis (TMA) inductive displacement transducer determines dimensional changes of (LVDT) via a push rod and transformed solids, liquids or pasty materials as a into a digital signal. function of temperature and/or time under a defined mechanical force (DIN The force imparted to the sample is 51 005, ASTM E831, ASTM D696, generated electromagnetically. This ASTM D3386, ISO 11359 – Parts 1 to guarantees a quick response time for 3). It is closely related to Dilatometry, experiments with a changing load, which determines the length change of e.g. tests on creep behavior. A highly samples under negligible load (DIN sensitive force sensor (digital resolution 51 045). < 0.01 mN) continuously measures the force exerted via the push rod and Irrespective of the selected type of readjusts it automatically. The force deformation (expansion, compression, can be applied as a single pulse or as penetration, tension or bending), every continuous modulation at frequencies change of length in the sample is up to 1 Hz. The force and displacement communicated to a highly sensitive signals are measured simultaneously.

furnace

sample

push rod

force sensor sample carrier

F height setting

displacement actuator transducer (static or modulating)

Thermomechanical Analysis (TMA)

Standard TMA 402 F1 Hyperion® with double furnace hoist

18 NETZSCH TMA 402 F Hyperion® Series

The NETZSCH TMA is a vertical system and thermokinetics allow calculation and is available as the F1 or F3. of phase transitions, densification, Both models are vacuum tight with calculation of bulk density, etc. thermostatted LVDT housings and Further, determination of visco-elastic Invar mounting systems, making them properties from measurements using ideal for the measurement of low CTE variable force is possible. materials because the measurement signal is not disturbed by fluctuations in the room, glovebox or hot cell temperature. Both the F1 and F3 are The NETZSCH TMAs are suitable for most nuclear applications. available with a double furnace hoist For convenience, some specifications are shown here. which allows two furnaces to be mounted simultaneously (the -150°C to 1000°C steel furnace and the RT to 1550°C SiC furnace). These furnaces Technical Data TMA 402 F1 TMA 402 F3 are interchangeable with the NETZSCH Max. sample length 30 mm 30 mm STA 449 and DSC 404 F Series. Integrated software-controlled MFCs Temperature range -150°C to 1550°C (2 furnaces) mean that sample purge gases can be Atmosphere inert, oxid., red., vac., corr., humid switched or mixed (to control e.g. PO ) 2 Measuring range ± 2.5 mm ± 2.5 mm as many times as necessary during the measurement. Dig. resolution (length) 0.125 nm 0.125 nm 0.001 N to 3 N in steps of 0.2 mN Force range Sample holders for expansion, (tension or pressure) penetration, tension and 3-point Dig. resolution (force) < 0.01 mN < 0.01 mN bending are available in Al2O3 or fused silica and are easily exchangeable. Modulated force Up to 1 Hz - Further sample containers for Final vacuum < 10-4 mbar < 10-2 mbar powders, liquids, pastes and molten Protective gas, Protective gas, metals are available in several different Gas connections 2 purge gases 2 purge gases materials. Mass flow controller (MFC) Standard Optional The vertical design of the TMA 402 makes it ideal for coupling to an MS, GC-MS and/or FT-IR (chimney effect) and for glovebox/hot cell operation after, of course, the appropriate modifications such as separation of electronics, MFCs, etc.

As with the dilatometers, software options for c-DTA®, RCS, density

19 Instrumentation

Thermogravimetric Analysis (TGA)/Evolved Gas Analysis (EGA)

TGAs measure the mass change of a If the STA is coupled to a QMS, GC-MS sample during heating/cooling or in and/or an FT-IR, the mass change, an isothermal phase via a sensitive energetics and evolved gases are microbalance. In systems in which the measured simultaneously. Of course, balance is located on top, the sample this is ideal because the TGA and DSC crucible is suspended in the furnace by tell us how much, while the evolved a wire or rod. Instruments with such an gases tell us what and, generally, why. arrangement are generally referred to as “hang-down” systems. If the balance is STAs can also be run in the so-called located below the furnace, the sample rate controlled mass change mode. In crucible sits on a sensor at the terminal this case, the sample is not heated at end of a ceramic rod. These systems are a constant rate, but in such a fashion commonly referred to as “top-loading”. as to produce a constant rate of mass Some instruments make use of a change. This is ideal for cases where horizontal design. high rates of mass loss can cause sample damage and/or skew the results, e.g., When TGA is coupled with DSC, binder burnout during sintering of simultaneous measurement of mass technical ceramics or powder metals. change and energetics (simultaneous thermal analysis – STA) with one instrument is possible. The advantage of this is that both the mass change and energetics are measured simultaneously on one sample so that the test conditions, e.g. gas flow rate, gas partial pressure, heating rate, temperature, etc. are identical. The rate of mass change is calculated from the mass signal.

exo STA 449 F1 Jupiter® coupled to a 300 amu ® Δm1 QMS 403 D Aëolos prepared for glovebox DSC TG Δm DTG T1 T2

Δm2 mW Δm (%)

T3 Δm/t (%/min)

Temperature

Measured and calculated STA curves

20 NETZSCH STA/EGA Systems

NETZSCH produces 3 different STA is ideal for EGA work (chimney effect). systems which cover a temperature The balances have high capacities and range of -150°C to 2400°C. There are digital resolutions (see below). The units 9 unique furnaces available and 16 are all vacuum tight, making them well different user-exchangeable fast-fix suited for work requiring controlled plug-in sensors which allow sensitivity/ atmospheres. The STAs have excellent time constant optimization. The long-term stability (low drift) because balances are all top-loading and purge the balance chambers are thermostatted gases flow from the bottom and exit to isolate the balance from fluctuations at the top of the furnace along with in glovebox/hot cell temperatures. The the evolved gases. This arrangement vacuum-tight design and long-term stability make the NETZSCH STAs ideal for corrosion and O/M studies. An optional water vapor furnace and generation system is an additional advantage for corrosion studies.

The NETZSCH STAs can be coupled to EGA systems (e.g., MS, GC-MS, FT-IR) via a heated adaptor head and heated transfer line or, in the case of the MS, directly via SKIMMER® technology. A well-defined quantity of gas can be injected into the STA via a PulseTA® unit. This permits calibration of the EGA system so that the gases released from the sample can not only be identified, but quantified as well.

The NETZSCH STA/EGA systems handle almost all nuclear applications. For convenience, some system specifications are summarized below.

Model Temperature Range Atmosphere Digital Resolution

STA 449 F1 -150°C to 2400°C inert, oxid., red., vac., corr., humid 0.025 μg STA 449 F3 -150°C to 2400°C inert, oxid., red., vac., corr., humid 1.0 μg STA 409 CD -150°C to 2400°C inert, oxid., red., vac., corr., humid < 2.0 μg

21 Instrumentation

NETZSCH STA/EGA Systems

The STA 409 CD can be directly coupled the barrel-shaped jet expansion behind The nozzle and SKIMMER® are precisely to an MS via SKIMMER® technology the divergent nozzle. The pressure machined from either alumina or which utilizes a unique supersonic jet reduction of the purge gas flow at amorphous carbon (glassy carbon), gas transfer system. The SKIMMER® atmospheric pressure down to the high allowing application temperatures of coupling yields the shortest possible vacuum behind the SKIMMER® orifice is 1450°C or 2000°C in the corresponding path for the gas transfer from the achieved in two steps along a distance furnaces. The molecular beams are sample to the MS. An intense, highly of less than 20 mm. All components analyzed by a quadrupole mass parallel molecular beam is collimated by are heated to at least the sample spectrometer up to high mass numbers the aerodynamic beam SKIMMER® from temperature and therefore there is little of 512 amu or optionally 1024 amu. chance for condensation; even metal vapors are detected by this unrivaled coupling system.

Standard STA 409 CD SKIMMER®

22 Gas chromatography (GC) is a method Some of the GC-MS specifications are summarized below. for separation of volatile and semi-volatile compounds with high resolution. Gas mixtures are separated Technical Data based on the differences in component Mode/Ionization Non-coated inert source, electron impact ionization (EI) distribution between a stationary phase (e.g., inner coating of a capillary) and Transfer line temperature 100°C to 300°C a mobile phase (purge gas, e.g., He, N, Furnace adapter max. 300°C head temperature Ar, H2). Mass filter Monolithic hyperbolic quadrupole Gas components with low affinity Mass range 1.6 amu to 1050 amu for the stationary phase but higher affinity for the mobile phase will be Mass resolution Unit mass, adjustable rapidly carried away by the purge gas, Valve box Heatable up to 300°C, Sampling loop 250 μl whereas gases with a high affinity for the stationary phase will follow with a relatively significant time delay provide detailed structural information The GC-MS can be coupled to any of the (“retention time”). on most compounds and thus allow for NETZSCH STAs via a heated transfer line. their precise identification. The mobile phase in GC is a gas, therefore all analytes must be evaporated and introduced into the column in gas form.

The stationary phase in the GC is for universal applications. In current technology, this is usually a polymeric coating inside a long and narrow fused silica capillary.

MS is applied as a detection system at the outlet of the GC separation column and will register the time distribution of the separated gas components in the purge gas flow. This pre-separation of gases by the GC, along with the sensitivity and resolution of the MS,

Standard STA 449 F1 Jupiter® coupled with the GC-MS via the heated transfer line

23 Applications

Thermal ConductivityApplications

Thermal Conductivity of Four Stoichiometric Oxide Ceramics Thermal Conductivity Thermal Conductivity 40 Depicted here is the thermal conductivity 40 Thermal Conductivity of of four stoichiometric oxide ceramics 35 Thermalsome Oxide Conductivity Ceramics of 35 AlO, some98% TD Oxide Ceramics with 95% to 98% theoretical density. 2 3 UAlOO2 ,3 ,95% 98% TD, TD O/M=2.0, 0% BU 30 2 U(UO2P, u95%)O ,TD, 95% O/M=2.0, TD, O/M=2.0, 0% BU 0% BU The materials showFigure the 13 depictsclassical the thermaltrends 30 95 5 2 (ThU9O5P,u 98%5)O2, 95%TD TD, O/M=2.0, 0% BU Figureconductivity 13 depicts of four the stoichiometric thermal 2 for non (or low) electrical conductors. 25 ThO2, 98% TD conductivityoxide ceramics of four with stoichiometric 95-98% 25 That is, exponentialoxidetheoretical andceramics densit1/T with decayy. The 95-98% materials with theoretical density. The materials 20 show the classical trends for non 20 increasing temperatureshow(or low) the electrical classicaldue to conductors. trends defect for non andThat phonon-phonon(oris, scattering, exponentiallow) electrical and respectively. conductors. 1/T decay Thatwith 15 is,increasing exponential temperature and 1/T decaydue to with 15 Further, decreasingincreasingdefect thermal and temperaturephonon-phonon conductivity due to 10 defectscattering, and phonon-phononrespectively. Furthe r, Thermal Conductivit y/ W/(m ∙ K) 10 Thermal Conductivit y/ W/(m ∙ K) with increasing differencescattering,decreasing respectivel thermal in ion conductivity ymass. Furthe isr, decreasing thermal conductivity 5 with increasing difference in ion 5 typical, that is: withmass increasing is typical, dithatfference is: in ion mass is typical, that is: 0 l UO2 < l ThO2 < l Al2O3 < l BeO. λ < λ < λ < λ . 0 0 400 800 1200 1600 2000 2400 2800 UO2 ThO l 2UO2 < All 2ThOO32 < l BeOAl2O3 < l BeO. 0 400 800 T120emperatur0 e/160°C0 2000 2400 2800 Temperature/°C

Fig. 13. Thermal Conductivity of some Oxide Ceramics Fig. 13. Thermal Conductivity of some Oxide Ceramics

Thermal Conductivity of Some Actinide Nitrides

Increasing thermal conductivity with 30 temperature indicates a significant 30 Thermal Conductivity of Thermalsome Actinide Conductivity Nitrides of electronic component and decreasing 25 somecorrected Actinide to 100% Nitrides TD 25 correctedUN to 100%PuN TD electrical resistivity. Decreasing thermal UNNpN PuNAmN NpN AmN

conductivity withShown increasing in Figure ion14 is massthe thermal W/(m ∙ K) 20

Shownconductivity in Figure of a 14few is actinide the thermal W/(m ∙ K) 20 difference suggestsconductivitynitrides. increased Increasing of a few phonon- thermal actinide nitrides.conductivity Increasing with temperature thermal 15 electron scattering,conductivityindicates i.e., a shortersignificant with temperature meanelectronic 15 free path. indicatescomponent a significantand decreasing electronic componentelectrical resistivit and decreasingy. Decreasing 10 electricalthermal conductivity resistivity. Decreasing with increasing 10

thermalion mass conductivity difference suggestswith increasing Thermal Conductivit y/

ionincreased mass di phonon-electronfference suggests Thermal Conductivit y/ 5 increased phonon-electron scattering, i.e. shorter mean free 5 Moore, et al., J. Amer. Ceram. Soc., 1970 scattering,path. i.e. shorter mean free Moore,Arai, et al.,et al., J. Ame 10thr .IEMP Ceram.T, 2008 Soc., 1970 path. 0 Arai, et al., 10th IEMPT, 2008 0 0 250 500 750 1000 1250 1500 0 250 500 Temperatur750 e/°C 1000 1250 1500 Temperature/°C

Fig. 14. Thermal Conductivity of some Nitride Ceramics Fig. 14. Thermal Conductivity of some Nitride Ceramics

20 20

24 21

Moore, et al., Shown in Figure 15 is the thermal J. Amer. Ceram. Soc., 1970 conductivity of UN separated into 18 the lattice and electronic components. Here the typical lattice

conductivity and electrical resistivity Thermal Conductivit y/ measurements using a fitting 6 routine. The Wiedemann-Franz- Lorenz (WFL) law, which can lead to significant errors in regions of 3 non-elastic scattering, was not 0 250 500 750 1000 applied directly. Temperature/°C

Thermal Conductivity of Three Carbide Ceramics

Even though a conductor, SiC follows 120 the classical lattice thermal conductivity Thermal Conductivity of trend, while ZrC displays more of a 100 some Carbide Ceramics SiC ZrC UC dominant electronicFigure 16 trend. shows UCthe thermal shows conductivity of three carbide

only a slight decreaseceramics. inEven thermal though a conductor, W/(m ∙ K) 80 SiC follows the classical lattice conductivity withthermal increasing conductivity temperature. trend, while This is due to theZrC displaysfact that more the of aelectronic dominant 60 electronic trend. UC shows only a and lattice componentslight decrease trends in thermal almost conductivity with increasing 40 nullify each othertemperature. even though This is due the to the fact electronic componentthat the electronic is dominant. and lattice Thermal Conductivit y/ component trends almost nullify 20 each other even though the electronic component is dominant. 0 0 400 800 1200 1600 2000 Temperature/°C

Thermal Conductivity of Uranium Nitride 21 In this example, the thermal conductivity the lattice and electronic components of UN has been separated into the of thermal conductivity were calculated lattice and electronic components. Here from thermal conductivity and electrical the typical lattice 1/T and increasing resistivity measurements using a fitting electronic behavior is displayed. Note the routine. The Wiedemann-Franz-Lorenz noncoincidental agreement between the (WFL) law, which can lead to significant lattice thermal conductivities of UN and errors in regions of non-elastic

UO2. It must be pointed out here that scattering, was not applied directly.

Moore, et al., Shown in Figure 15 is the thermal J. Amer. Ceram. Soc., 1970 conductivity of UN separated into 18 the lattice and electronic components. Here the typical lattice

1/T and increasing electronic W/(m ∙ K) 15 behavior is displayed. Note the noncoincidental agreement between the lattice thermal conductivities of 12 Thermal Conductivity of Uranium Nitride UN and UO2. It must be pointed out here that the lattice and electronic Lattice Contribution components of thermal conductivity 9 Electronic Contribution were calculated from thermal Total UO2 - Lattice conductivity and electrical resistivity Thermal Conductivit y/ measurements using a fitting 6 routine. The Wiedemann-Franz- Lorenz (WFL) law, which can lead to significant errors in regions of 3 non-elastic scattering, was not 0 250 500 750 1000 applied directly. Temperature/°C

120

Thermal Conductivity of 100 some Carbide Ceramics SiC ZrC UC Figure 16 shows the thermal conductivity of three carbide ceramics. Even though a conductor, W/(m ∙ K) 80 SiC follows the classical lattice thermal conductivity trend, while ZrC displays more of a dominant 60 electronic trend. UC shows only a slight decrease in thermal conductivity with increasing 40 temperature. This is due to the fact that the electronic and lattice Thermal Conductivit y/ component trends almost nullify 20 each other even though the electronic component is dominant. 0 0 400 800 1200 1600 2000 Temperature/°C

21 Applications

Specific Heat and Transition Energetics

Specific Heat of IN-718

The specific heat and heat of fusion of IN-718 up to ≈1450°C during heating and cooling are presented here. Integration of the melting peak yields ΔH≈185 J/g ±5.0%. The solidus and liquidus temperatures were also determined from these data. It should be noted however that care must be taken not to lose sight of possible undercooling, which is not atypical for metals. The solidus and liquidus temperatures are 1252°C and 1347°C, respectively.

Specific Heat of Zr-40wt%U 1.4 Metal Fuel

1.2 Specific Heat of Zr-40wt%U Metallic Fuel The specific heat of Zr-40wt%U fuel Measured Calculated using Neumann-Kopp was measured between 25°C and 1.0 1000°C. Other than the endothermic peak between approximately 550°C 0.8 and 620°C, which is due to the phase 0.6 transition, the measured specific Specific Hea t/ J/(g ∙ K) B. H. Lee, et al., heat values are in reasonably good J. Nuc. Mat., 2007 0.4 agreement with those calculated by the Neumann-Kopp rule. 0.2 0 200 400 600 800 1000 Temperature/°C

26 Thermal Expansion

Thermal Expansion of Some Thermal Temperature/°C 0 400 800 1200 1600 2000 2400 Neutron Absorbers 2.0 Linear Thermal Expansion of some Neutron Absorbers

B4C Gd2O3 The thermal expansionThermal Expansionof some ceramic Dy O 1.5 HfB2 2 3 ZrB Eu2O3 and elemental neutron absorbers is 2 3.0 presented here. In general, these 1000°C 1500°C 2000°C 2500°C 2800°C, 2.6257% 1.0 1.0 materials expand somewhere between 2.5 Thermal Expansion - Heat (%) 0.7869 1.2472 1.7406 2.2940 1.0% and 3.0% between 25°C and Thermal Expansion - Cool (%) - - 1.7535 2.2956 Literature (%) 0.7871 1.2509 1.7536 2.2941 0.8 the melting temperature. This is the 2.0 Maximum Deviation (%) (rel.) 0.03 0.30 0.74 0.07 The thermal expansion of high- 0.5 Linear Thermal Expansio n/ % expected behavior.purity POCO graphite over the 0.6 temperature range of 500 to 1.5 2800°C is given in Figure 19. Clearly the reproducibility is 0.0 excellent and, as shown, the 1.0 0.4 deviation from literature values is Thermal Expansion of Linear Thermal Expansio n/ % Linear Thermal Expansion significantly less than 1.0%. POCO Graphite of some Elemental

Neutron Absorbers Linear Thermal Expansio n/ % 0.5 Heat 0.2 Cool B Dy Literature Hf Er Gd Cd 0.0 0.0 500 1000 1500 0 2000200 2500400 6003000 800 1000 Temperature/°C Temperature/°C

Thermal Expansion of Some 3

Nitride Ceramics Linear Thermal Expansion of some Nitride Ceramics Figure 20 shows the thermal BN ZrN AlN UN In comparing theexpansion thermal of several expansion nitride of AmN several nitride ceramics,ceramics. It is it interesting is interesting to note 2 that the thermal expansion to note that theincreases thermal with expansion ion mass difference. This increasing asymmetric increases with behaviorion mass is also difference. responsible This for increasing asymmetricincreased phononbehavior and phonon-is also electron scattering, resulting in 1 responsible forshorter increased mean freephonon paths and and

therefore inverse behavior between Linear Thermal Expansio n/ % phonon-electronthermal scattering, expansion resultingand thermal in shorter mean freeconductivity paths in and many therefore ceramics. inverse behavior between thermal 0 expansion and thermal conductivity in 0 500 1000 1500 2000 2500 Temperature/°C many ceramics.

27 Applications Courtesy of SEPM

Urania

Mass Change of Hyperstoichiometric UO2 Urania

Plotted are the mass change and rate 100.0 0 of mass change in inert and reducing Plotted in Figure 21 are the mass

atmospheres.change Clearly and the rate curvesof mass changeoverlay of -2 hyperstoichiometric UO2 in inert until ≈325°C.and The reducing first atmospheres.mass loss stepClearly -5 below 325°Cthe is curvesdue to overlay the evolutionuntil » 325°C. of 99.5 The first mass loss step below moisture and325 impurities.°C is due to Abovethe evolution 325°C of Mass Change and Rate of Mass Change of UO moisture and impurities. Above 2 -10 the curves deviate325°C thebecause curves deviate of the because greater Inert oxygen loss inof the greater reducing oxygen atmosphere. loss in the Reducing

reducing atmosphere. By 700°C the Mass Chang e/ % 99.0 By 700°C theurania urania is stoichiometric is stoichiometric in the in reducing atmosphere, while in the -15 the reducing inertatmosphere, atmosphere thewhile material in the inert atmosphereremains the over-stoichiometric. material remains This Rate of Mass Change/(%/min ) x 10 has far-reaching consequences over-stoichiometric.with regard This to the has sinterabilit far-reachingy. 98.5 -20 consequences with regard to the 0 200 400 600 800 1000 1200 1400 1600 Temperature/°C sinterability. Fig. 21. Mass Change of Hyperstoichiometric UO 2

Oxidation of Stoichiometric UO2 in an Air Atmosphere

10 100 1.6 The conversion from UO2 to U3O7 to

U3O8 is of course accompanied by 10 100 50 1.6 UO2 U307 U308 mass increases of 1.14% and 1.72%. 7 1.2 Presented here is the oxidation of 50 0 The exothermal energetics of the UO2 U307 U308 stoichiometric UO2 in an air 7 1.2 -50 transitions areatmosphere. clearly shown The conversion by the from 4 0 0.8 UO2 to UO3 7 to U3O8 is of course 189.3°C DSC curve. It is interesting to note + 1.72% accompanied by mass increases of -100 -50 1.14 and 1.72%. The exothermal 4 0.8 the excellent correlation between the 189.3°C 1 + 1.14% Oxidation of UO2 0.4

energetics of the transitions are Energetic s/ µV + 1.72% -150 clearly shown by the DSC curve. It Mass Chang e/ % Mass Change -100 mass change, rate of mass change Energetics is interesting to note the excellent Rate of Mass Change -200 1 + 1.14% Oxidation of UO2 0.4 Rate of Mass Chang e/ mg/min and energeticcorrelation curves. betweenThis plot the clearlymass - 2 -150 Energetic s/ µV 0.0 Mass Chang e/ % Mass Change shows the advantagechange, rate of of simultaneousmass change and 371.9°C Energetics -250 energetic curves. This plot clearly Rate of Mass Change -200 TG-DSC (STA)shows measurements the advantage usingof one Rate of Mass Chang e/ mg/min -- 25 -300 -0.40.0

simultaneous TG-DSC (STA) 371.9°C instrument. 0 100 200 300 400 500 600 700 -250 measurements using one Temperature/°C instrument. - 5 -300 -0.4 0 100 200 300 400 500 600 700 Temperature/°C 28 Fig. 22. Oxidation of UO 2

24 Specific Heat of UO2 0.40 Matzke, et al. J. Nuc. Mat., 1997 The specific heat of stoichiometric and overstoichiometric UO are shown 2 0.35 here. The stoichiometric UO2 follows the classical temperature-dependent specific heat trend, while that for UO2.04 and UO2.084 display an endothermic 0.30 Specific Hea t/ J/(g ∙ K) Specific Heat of peak between approximately 600 and UO2+x at 0% BU x 950K. This is due to energy required 0 0.04 0.04 0.084 to dissolve the U4O9 phase. Notice that the peak area for UO is larger than 0.25 2.084 300 500 700 900 1100 1300 1500 1700 that for UO2.04 because of the greater Temperature/K quantity of the U4O9 phase.

Thermal Diffusivity of UO2 0.020

Thermal Diffusivity of 0.018 95% Dense Stoichiometric UO2 The thermal diffusivity of 95% dense 1 ms pulse width 0.016 10 ms pulse width stoichiometric UO2 follows the expected 1/T behavior for lattice-driven transport 0.014 at these temperatures. It should be 0.012 fusivit y/ cm²/s noted that the thermal conductivity 0.010 does not display this trend at 0.008 temperatures above ≈2000K, because Thermal Dif the specific heat does not follow the 0.006 0.004 Ronchi, et al. Debye theory. J. of App. Phy., 1999 0.002 500 1000 1500 2000 2500 3000 Temperature/K

29 Applications

Urania

Thermal Diffusivity of (U,Ce)O2-X 3.5

Thermal Diffusivity of (U,Ce)O2-x 3.0 Ceria Content (%) The thermal diffusivity of (U,Ce)O2-X 0 20 follows the expected 1/T trend for lattice

/s 25

2 2.5 30 transport. Also, the impact of increased

y/ mm lattice strain ( defect-phonon 2.0 scattering) with increasing Ce content 1.5 on thermal diffusivity is obvious.

1.0 Thermal Diffusivit

0.5 Courtesy of A. T. Nelson Los Alamos National Lab Private communication 0.0 0 200 400 600 800 1000 1200 1400 1600 Temperature/°C

3.0 Inverse Thermal Diffusivity of Inv. Thermal Diffusivity of (U,Ce)O 2-x (U,Ce)O2-X Ceria Content (%): 0 20 25 30 2 2.5 Here, the inverse thermal diffusivity y/ s/mm 2.0 a-1 = A + B.T (A and B represent defect-phonon and phonon-phonon 1.5 scattering, respectively) is plotted against temperature and Ce content. 1.0 Ceria A B As anticipated, this yields a series of Cont. (%) (s/mm2) (s/mm2-°C) Inverse Thermal Diffusivit 0 0.2504 8.50 ´ 10-4 curves with a relatively constant slope, 0.5 -4 20 0.7067 9.20 ´ 10 -1 -4 B. The effect of solutionized Ce ions on a = A + B · T 25 1.0373 8.84 ´ 10 30 1.5248 8.33 ´ 10-4 defect-phonon scattering can be further 0.0 0 200 400 600 800 1000 1200 1400 1600 quantified by plotting A against the Ce Temperature/°C content.

30 Gadolinia

Sintering of Gadolinia

2 0.2 0.0 Shown here are the densification and -0.2 0 rate of densification of GdO1.5. The -0.4 densification follows the expected -0.6 heating rate and temperature -2 -0.8 -1.0 dependence up to ≈1250°C. At

Linear Thermal Expansion of Gd O -1.2 ≈1250°C the heating rate dependence -4 2 3 » Thermal Expansio n/ % during Sintering @ PO2 1.0 -1.4 disappears and the rate of densification b(K/min) Expansion Rate 20 -1.6 Rate of Length Chang e/ %/min Linear increases dramatically. This is due to the -6 10 5 -1.8 2.5 cubic to monoclinic phase transition, -2.0 which significantly complicates the -8 -2.2 0 200 400 600 800 1000 1200 1400 1600 interpretation of the sintering data. Temperature/°C

0.75 Specific Heat of Gadolinia

0.70 Specific Heat of Gd2O3 @ b = 20 K/min and P » 1.0 0.65 O2 This plot depicts the specific heat of 1st Heat (green) 0.60 2nd Heat (sintered) GdO1.5 during the first (sintering) and DH » 14.6 J/g second heatings. Clearly the phase 0.55 transition, with a ΔH of ≈14.6 J/g, is 0.50 irreversible. This has been verified by 0.45 XRD data. The low temperature Specific Hea t/ J/(g ∙ K) 0.40 endothermic and exothermic trends in 0.35 the first heating data are due to the 0.30 release of moisture and other impurities.

0.25 0 200 400 600 800 1000 1200 1400 1600 Temperature/°C

31 Applications

Ceria

Densification of CeO2

The shrinkage and rate of shrinkage

2 0.1 of ceria at five different heating rates during sintering are plotted here. The 0 0.0 samples were pressed to 51-53% -2 theoretical density at 355 MPa. No -0.1 -4 e/ %/min binders or mold lubricants were employed. The onset of densification -6 -0.2 occurs at ≈800°C and sintering is not Linear Thermal Expansion of -8 Thermal Expansio n/ % CeO during Sintering @ P »0.2 2 O2 -0.3 complete by 1660°C. Typical heating rate Expansion Rate -10 20 K/min dependence due to rate-limited metal Linear 10 K/min Rate of Length Chang 5 K/min -0.4 -12 2.5 K/min atom diffusion is displayed. The curves 1 K/min show a two-step densification process -14 -0.5 0 200 400 600 800 1000 1200 1400 1600 1800 which is somewhat atypical. Final density Temperature/°C was 81-85% of theoretical.

O/M Ratio of CeO2 During Sintering

This figure shows the O/M ratio during 2.000 heating. These values were calculated

O/M Ratio of CeO2 as a Function of from TGA data measured under multiple Temperature and PO2 at 10 K/min 1.995 partial pressures of oxygen (P ). O2 Sample preparation was identical to that

Increasing PO2 1.990 above. During heating the O/M starts to decrease at ≈1000°C and there are

O/M Ratio 1.985 clearly different reduction rates resulting from the variable P over the sample. O2

1.980 The process is reversible. The resulting deviation from stoichiometry has a profound effect on the sinterability. 1.975 200 400 600 800 1000 1200 1400 1600 Temperature/°C

32 Specific Heat of CeO2 During Sintering

Depicted here is the specific heat of 0.70 ceria with and without reduction. Specific Heat of CeO 0.65 2 Sample preparation remained during Sintering @ PO2» 0.2 With Reduction unchanged. In the absence of reduction 0.60 Without Reduction Extrapolated the specific heat follows the Debye 0.55 theory and is in good agreement with published values. With reduction 0.50 the specific heat (actually apparent 0.45 specific heat) increases non-linearly Specific Hea t/ J/(g ∙ K) with temperature. This is a result of the 0.40 energy required for the increased rate of 0.35 defect formation. The reduction becomes 0.30 obvious at ≈950°C. The difference 0 200 400 600 800 1000 1200 1400 1600 1800 between the two curves is often referred Temperature/°C to as the excess specific heat.

Property Evolution of CeO2 During Sintering

In this figure the thermal diffusivity, specific heat, bulk density, rate of 8 6.0 1.0 0.70 Properties of CeO2 during Sintering @ P » 0.2 change of bulk density and O/M are 7 O2 0.65 Thermal Diffusivity - 5.5 superimposed. First, the correlation 3 Sample Avg. 0.8 -3 6 Bulk Density 0.60

10 Rate of Bulk Density Change ∙ between the specific heat and O/M is Specific Heat with Reduction 3

/s) 5.0 2 5 Specific Heat w/o Reduction 0.55 obvious. Next, the thermal diffusivity Specific Heat Extrapolated 0.6 O/M - Heat y/ g/cm increases between ≈400°C and 4 4.5 0.50

850°C due to surface diffusion (no 3 0.4 0.45

4.0 Bulk Densit densification). The increase in thermal Specific Hea t/ J/(g ∙ K) 2 Inverse Normalized O/M 0.40 diffusivity above ≈850°C is a result of Thermal Diffusivity/(cm 0.2 3.5 1 0.35 O/M=1.9995 O/M=1.9840 decreasing porosity (densification), but O/M=1.9895 is partially attenuated by the decreasing 0 3.0 0.0 0.30 0 200 400 600 800 1000 1200 1400 1600 1800 O/M (increased defect scattering). The Temperature/°C densification (diffusion) rate between O/M=1.9995 and 1.9840 (1165°C and 1620°C) is controlled, in part, above ≈1600°C coarsening occurs at by the O/M-created defects. Likely the expense of densification, which controlling mechanisms are VM→Mi / manifests itself as a drop in the cluster. XRD measurements show that sintering rate.

33 Applications

Graphite

Speci c Heat and Transition Energetics

Specific Heat of Graphite 2.5

The specific heat of graphite was 2.0 Depicted in Figure 17 is the specific measured overheat the of temperaturegraphite over the rangetempera- of -100°C to 1300°C.ture range ofAs -100 expected, to 1300°C. As expected, the trend follows the 1.5 the trend followsDebye the theory Debye (electronic theory specific heat is negligible at these Graphite (electronic specifictemperatures). heat is The negligible measured and Sample 1 - Run 1 (LT) at these temperatures).published values The deviate measured by a 1.0 Sample 1 - Run 2 (LT) maximum of » 5.0% and are Sample 2 - Run 1 (LT) Specific Hea t/ J/(g ∙ K) Sample 2 - Run 2 (LT) and published generallyvalues withindeviate »2.0%. by Note a the Sample 1 - Run 1 (HT) reproducibility of the measurements 0.5 Sample 1 - Run 2 (HT) maximum of ≈5.0%over both and the low-temperature are generally (LT) Sample 2 - Run 1 (HT) Sample 2 - Run 2 (HT) within ≈2.0%.and Note high-temperature the reproduc (HT)- ranges. ibility of the measurements over 0.0 -200 0 200 400 600 800 1000 1200 1400 both the low-temperature (LT) and Temperature/°C high-temperature (HT) ranges.

0.10

Zirconium Alloy Thermal Expansion (Zr-Nb-Fe) 858.5°C + The heat flow during heating and Heat +889.3°C Cool cooling for a Zr-Nb alloy over the 3.0 0.05 Thermal Expansion of POCO 47.37 J/g temperature range of 400 to + Graphite »1050°C is presented in Figure 18. 1000°C 1500°C 2000°C 2500°C 2800°C, 2.6257% ++ Thermal Expansion - Heat (%) 0.7869 1.2472 1.7406 2.2940 + Of interest here is the solid-solid 2.5 814.2°C endothermal phase transition Thermal Expansion - Cool (%) - - 1.7535 2.2956 0.00 The thermal expansionbetween »815 of and high-purity 990°C on Literature (%) 0.7871 1.2509 1.7536 2.2941 heating. Upon cooling, the exo- 2.0 Maximum Deviation (%) (rel.) 0.03 0.30 0.74 0.07 Thethermal thermal phase expansion transition of ishigh- shifted

POCO graphite was measured over the DS C/ mW/mg purityto lower POCO temperatures, graphite over i.e. thebetween + temperature temperaturerange»985 and of 750 500°Crange°C. Noticeof 500to 2800°C. thatto the -47.46 J/g 1.5 -0.05 983.9°C 2800transition°C is given energetics in Figure are relatively19. ++ ++ Clearly the reproducibilityequal at 47.4 and is 47.5 excellent J/g on + + Clearly the reproducibility is 779.3°C 948.8°C and, as shown,excellentheating the deviationand,and cooling, as shown, respectivelfrom the y. + This is not atypical for metal alloys. 1.0 867.0°C deviation from literature values is Thermal Expansion of Linear Thermal Expansio n/ % -0.10 literature valuessignificantly is significantly less than 1.0%. less 400 500 600 700 800 900POCO Graphite1000 1100 than 1.0%. 0.5 Temperature/°C Heat Cool Fig. 18. Heat Flow in a Zirconium Alloy Literature 0.0 500 1000 1500 2000 2500 3000 Temperature/°C 22

Linear Thermal Expansion of some Nitride Ceramics Figure 20 shows the thermal BN ZrN AlN UN expansion of several nitride AmN ceramics. It is interesting to note 2 that the thermal expansion increases with ion mass difference. 34 This increasing asymmetric behavior is also responsible for increased phonon and phonon- electron scattering, resulting in 1 shorter mean free paths and

therefore inverse behavior between Linear Thermal Expansio n/ % thermal expansion and thermal conductivity in many ceramics.

0 0 500 1000 1500 2000 2500 Temperature/°C

23 2.50

Stored Energy in Graphite 2.50 Specific Heat and Stored 2.00 Energy in Irradiated 20 2 SpecificGraphite Heat @ 5×1and0 Storedn/cm Here the apparent specific heat curves 2.00 Energy in Irradiated ∙ K) Graphite @ 5×1020n/cm2 for irradiated graphite are superimposed 1.50 Non-irradiated ∙ K) on those for the true specific heat of Tirr=250°C 1.50 Non-irradiated unirradiated graphite. As expected, the 1.00 Tirr=250°C lower irradiation temperature, T , results Specific Hea t/ J/(g irr =200°C 1.00 Tirr in more stored energy because fewer 0.50 Specific Hea t/ J/(g defects are annealed out. Of course, Tirr=200°C Tirr=150°C 0.50 once Tirr is exceeded stored energy is 0.00 0 50 100 150 200 250 300 350 400 450 500 released, resulting in a decrease in the Temperature/°C Tirr=150°C apparent specific heat. 0.00 0 50 100 150 200 250 300 350 400 450 500 Temperature/°C

Thermal Diffusivity and Thermal 1.2 140

Conductivity of Graphite Thermal Diffusivity and Thermal Conductivity 120 1.0 of Graphite

Thermal Diffusivity K) 1.2 140∙ The thermal diffusivity of graphite was Thermal Conductivity 100

0.8 W/(m measured over the temperature range Thermal Diffusivity and Thermal Conductivity 120 of 25°C to about 2800°C. The thermal 1.0 of Graphite 80 K)

fusivit y/ cm²/s 0.6 Thermal Diffusivity conductivity was calculated using the ∙ Thermal Conductivity 60 100

measured specific heat, bulk density and 0.8 W/(m 0.4 thermal diffusivity data. The calculated 40 Thermal Di f 80 Thermal Conductivity/

thermal conductivity follows the fusivit y/ cm²/s 0.6 0.2 20 expected 1/T behavior for graphite. 60

0.40.0 0 0 500 1000 1500 2000 2500 3000 40 Thermal Di f

Temperature/°C Thermal Conductivity/ 0.2 20

0.0 0 0 500 1000 1500 2000 2500 3000 Temperature/°C

35 Applications

Cladding

Oxidation of Zircaloy-4

Presented here are the mass gain and 115 2.5 detected H during oxidation of 2 Oxidation of Zircaloy-4 Cladding Zircaloy-4 cladding in a steam in a Water Vapor Atmosphere 2.0 b(K/m) Mass Detected H atmosphere. The oxidation is due, of 2 10 110 5

course, to the highly exothermic reaction -9 1.5 Zr + 2H2O → ZrO2 + 2H2 + ΔH.

The heating rate dependence of the 1.0 Mass Chang e/ % 105 Ion Current/A ∙ 10 oxidation and therefore the H2 production is obvious.Speci c Heat At the and 5 T ransitionK/min Energetics 0.5 heating rate the rate of mass gain and 2.5

H2 production reach steady-state at 100 0.0 400 500 600 700 800 900 1000 1100 2.0 approximately Depicted950°C, in which Figure 17 is is not the specific the Temperature/°C case for the fasterheat of 10 graphite K/min over rate. the temperature range of -100 to 1300°C. As expected, the trend follows the 1.5 Debye theory (electronic specific heat is negligible at these Graphite temperatures). The measured and Sample 1 - Run 1 (LT) published values deviate by a 1.0 Sample 1 - Run 2 (LT) maximum of »5.0% and are Sample 2 - Run 1 (LT) HeatSpecific Hea t/ J/(g ∙ K) Flow in a Zirconium Alloy Sample 2 - Run 2 (LT) generally within »2.0%. Note the Sample 1 - Run 1 (HT) reproducibility of the measurements 0.5 Sample 1 - Run 2 (HT) over both the low-temperature (LT) Sample 2 - Run 1 (HT) and high-temperature (HT) ranges. The heat flow during heating and Sampleexothermal 2 - Run 2 (HT) phase transition is shifted cooling in a Zr-Nb alloy over the to lower temperatures, i.e. between 0.0 temperature-200 range0 of200 400°C400 to 600 800 ≈985°C1000 1200 and 1400750°C. Notice that the Temperature/°C ≈1050°C has been analyzed. Of interest transition energetics are relatively equal here is the solid-solid endothermal at 47.4 J/g and 47.5 J/g on heating and phase transition between ≈815°C and cooling, respectively. This is not atypical 990°C on heating. Upon cooling, the for stable metal alloys.

0.10

Zirconium Alloy (Zr-Nb-Fe) 858.5°C + The heat flow during heating and Heat +889.3°C Cool cooling for a Zr-Nb alloy over the 0.05 47.37 J/g temperature range of 400 to + »1050°C is presented in Figure 18. ++ + Of interest here is the solid-solid 814.2°C endothermal phase transition between »815 and 990°C on 0.00 heating. Upon cooling, the exothermal phase transition is shifted to lower temperatures, i.e. between DS C/ mW/mg + »985 and 750°C. Notice that the -47.46 J/g -0.05 983.9°C transition energetics are relatively ++ ++ equal at 47.4 and 47.5 J/g on + + 779.3°C 948.8°C heating and cooling, respectively. + This is not atypical for metal alloys. 867.0°C -0.10 400 500 600 700 800 900 1000 1100 Temperature/°C

Fig. 18. Heat Flow in a Zirconium Alloy 36

22 Waste Surrogates

Thermal Diffusivity and Specific Heat of a Waste Glass

The thermal diffusivity and specific heat the glass transition. The correlation of a waste glassW asteconsisting Glass of oxides between the two data sets is excellent. ranging from alumina to neodymia are The thermal diffusivity and specific 0.0050 2.00 plotted here. Theheat specificof a waste glassheat consisting data of show the glassoxides transition ranging (endothermal)from alumina to Waste Glass neodymia are plotted in Figure 23. Specific Heat 1.75 in the range ofThe 500°C specific followed heat data show by cold the 0.0045 Thermal Diffusivity glass transition (endothermal) in the 2 crystallization (exothermal)range of 500°C followed between by cold 1.50 crystallization (exothermal) between 0.0040 600°C and 750°C,600 and indicating 750°C, indicating that thatthe the sample was cooled fast enough to sample was cooled fast enough to fusivit y/ cm /s 1.25 produce a significant amorphous produce a significantphase. Also, amorphous the large excess phase. 0.0035 enthalpy peak superimposed on the Also, the large excess enthalpy peak 1.00 Specific Hea t/ J/(g ∙ K) glass transition may indicate superimposed significanton the glassaging timetransition below the Thermal Di f 0.0030 transition. The diffusivity displays 0.75 may indicate significantthe classical 1/ agingT behavior time followed below the transition.by a significant The diffusivitydrop across the glass transition. The correlation 0.0025 0.50 displays the classicalbetween 1/the T two behavior data sets is 0 200 400 600 800 excellent. followed by a significant drop across Temperature (°C) Fig. 23. Thermal Di usivity and Specic Heat of a Waste Glass

Evolved Gas Measurement on Surrogate Waste Material

Waste material can contain silicates like shows maximum intensity at 668°C. carbonates. Even during storage in an clays contaminated with radioactive The amount of CO2 is very small. Most air atmosphere some carbonates could inorganic salts (hydrates, sulphates, probably there are some impurities be formed due to the small grain size of nitrates etc.). The processing of these of organic material, hydrocarbons or the material. waste materials E.is Postoften paragraph done by a heat treatment. TG-MS measurements allow Need plot and paragraph from Dr. Post on TG/MS measurements 3.5 the determination, identification and 100 done-9.8% on one of the PNNL surrogate quantification of the evolved gases 3.0 90 during heating of these materials. The waste compositions.-9.4% 2.5 surrogate material for this investigation 80 -12.1% contained vermiculite and alkali and 2.0 -10 70 159.6°C 10 496.4°C ∙ earth alkali nitrates. During linear -10.8% 60 1.5 t/ A heating at 10 K/min in a He atmosphere, H2O NO2 -7.8% water, nitrogen oxide, nitrogen dioxide 50 1.0 Mass Chang e/ % Fig. 24. Title and carbon dioxide were detected. 658.1°C Ion Curren 40 0.5 214.7°C The water came off between RT CO2 30 NO and about 400°C, nitrogen dioxide 0.0 25 shows two intensity maxima at about 20 -0.5 0 200 400 600 800 1000 1200 1400 180°C and 497°C. The nitrogen oxide Temperature/°C emission starts at around 300°C and

37 Thermophysical Properties of Some Important Nuclear Materials at Room Temperature

The properties given in this table are Fuels intended to be used as estimates only. Some are quite accurate while Property Material 3 others are less certain. Of course it λ (W/m·K) Cp (J/g·K) ρ (g/cm ) is well known that small changes in Pu 6.7 0.145 19.816 stoichiometry, porosity, microstructure, PuC 6.9 0.176 - etc. can have a profound effect on the thermophysical properties. As a result, PuN 9.6 - 14.400

NETZSCH does not guarantee the PuO2 6.3 0.240 11.460 th. accuracy of these values. Th 54.0 0.118 11.700

ThO2 13.0 0.235 9.110 th. U 27.6 0.116 19.070 U-14%Zr 18.5 - - U-91%Zr 7.4 - -

(U0.8 Pu0.2)O2 8.9 @ th. 0.240 11.660 th. UC 25.3 0.200 13.630 th. UN 13.0 0.190 14.300 th.

UO2 8.7 @ th. 0.235 10.960 th.

Miscellaneous

Property Material 3 λ (W/m·K) Cp (J/g·K) ρ (g/cm )

Al2O3 36.0 0.765 3.970 MgO 60.0 0.929 3.770

Si3N4 16.0 0.691 2.700 SiC 120.0 0.675 3.160 ZrC 26.3 0.378 6.730 ZrN 10.5 (80-90%th.) 0.386 7.090

ZrO2 (Y-stab.) 1.9 0.455 5.680

Structural

Property Material 3 λ (W/m·K) Cp (J/g·K) ρ (g/cm ) InX-750 11.7 0.439 8.510 Low Cr Steel 42.3 0.442 7.858 Nichrome 12.0 0.420 8.400 SS-304 14.9 0.477 7.900 SS-316 13.4 0.468 8.238 Zirc2 17.0 0.290 6.550 Zirc4 14.1 0.293 6.580 Zr-2.5%Nb 19.0 0.315 6.570

38 Additional elements

Property Material 3 λ (W/m·K) Cp (J/g·K) ρ (g/cm ) Ag 429.0 0.235 10.500 Al 237.0 0.903 2.702 Cd 96.6 0.231 8.650 Ce 11.3 0.192 6.770 Cr 93.7 0.449 7.160 Fe 80.2 0.447 7.870 In 81.8 0.267 7.310 Mg 156.0 1.024 1.740 Mo 138.0 0.251 10.240 Nb 53.7 0.265 8.570 Ni 90.7 0.444 8.900 V 30.7 0.489 6.100 W 174.0 0.132 19.300 Zr 22.7 0.278 6.570

Moderators

Property Material 3 λ (W/m·K) Cp (J/g·K) ρ (g/cm )

Be 200.0 1.825 1.850 BeO 270.0 1.030 3.000

D2O 0.560 4.230 1.100 Graphite 100.0 0.710 1.700

H2O 0.561 4.217 1.000

ZrH1.8 34.0 0.410 5.620

Absorbers

Property Material 3 λ (W/m·K) Cp (J/g·K) ρ (g/cm ) AgInCd 60.0 0.230 10.170 B 27.0 1.107 2.500

B4C 92.0 0.960 2.520 BN 28.7 0.848 2.250 Hf 22.3 0.363 13.090

HfB2 22.6 0.396 11.200 Ta 57.5 0.140 16.600 ZrB 23.0 0.230 6.090 sources: diverse sources: 2

39 Our Expertise

Service Summary of Our Services

All over the world, the name NETZSCH Installation and commissioning stands for comprehensive support and Hotline service expert, reliable service, before and Preventive maintenance after sale. Our qualified personnel from Calibration service the technical service and application IQ / OQ / PQ departments are always available for On-site repairs with emergency consultation. service for NETZSCH components Moving / exchange service In special training programs tailored Technical information service for you and your employees, you will Spare parts assistance 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.

40 R&D and Engineering

Our R&D and Engineering teams are our instruments can be serviced and regarded as some of the world’s finest. operated efficiently in these rigorous NETZSCH employs the largest number of environments. Further, we access PhD engineers, physicists, material mock-up hot cell facilities to give us the scientists and chemists in the industry. experience required to produce instru- Our philosophy is to continuously ments which are robust enough to be expand the boundaries of technology, handled efficiently in the even more ensuring that our instruments lead demanding hot cell environments. the world in performance, quality and robustness. This is proven by the We invite you to join us at our head- longevity of our instruments as well quarters in Selb, Germany to work as the many patented and proprietary together on an instrument solution for features incorporated into them. your specific application and hot environment. For your convenience, our For the nuclear industry, we engineer nuclear applications specialists and special instruments for glovebox and engineers are also available to work hot cell applications in addition to our with you on site at your facility. standard products. We utilize mock-up gloveboxes throughout the design and At NETZSCH, we convert the impossible construction processes to ensure that to reality – challenge us.

41 Our Expertise

Applications Laboratories

The NETZSCH Thermal Analysis Measurements can be carried out on Applications Laboratories are a samples of the most varied of geome- proficient partner for nearly any thermal tries and configurations. You will receive analysis issue. Our involvement in your high-precision measurement results and projects begins with proper sample valuable interpretations from us in the preparation and continues through shortest possible time. This will enable meticulous examination and you to precisely characterize new interpretation of the measurement materials and components before actual results. Our diverse methods and over deployment, minimize risks of failure, 30 different state-of-the-art measuring and gain decisive advantages over your stations will provide ready-made competitors. solutions for all your thermal needs. For production problems, we can work Within the realm of thermal analysis with you to analyze concerns and and the measurement of thermophysical develop solutions. The minimal properties, we offer you a comprehen- investment in our testing and services sive line of the most diverse analysis will reward you with reduced down time techniques for materials character- and reject rates, helping you optimize ization (solids, powders and liquids). your processes across the board.

42 Notes

43 the globeguarantee thatexpertserviceisneverfar from ourcustomers. 3,000 employeesat163salesandproduction centersin28countriesacross Pumps &Systems–provide tailored solutionsfor highest-levelneeds.Over The three Business Units–Analyzing&Testing, Grinding&Dispersingand sales, andservicebranches. the manufacture ofmachineryandinstrumentationwithworldwideproduction, The NETZSCHGroup isamid-sized, family-owned Germancompanyengagingin Fax: Tel.: Germany 95100 Selb Wittelsbacherstraße 42 NETZSCH-Gerätebau GmbH requirement butalsoexceed youreveryexpectation. hensive serviceofferings ensure thatoursolutionswillnotonlymeetyourevery years ofapplicationsexperience,broad state-of-the-art product lineandcompre determination ofThermophysicalProperties, NETZSCHhasitcovered. Our50 When itcomestoThermalAnalysis,Calorimetry(adiabatic&reaction) andthe [email protected] +49 9287881505 +49 9287881-0

NGB · Characterization of Nuclear Materials · EN · 1000 · 0214 · LH · Technical specifications are subject to change.