Investigation of high temperature phase stability, thermal properties and evaluation of metallurgical compatibility with 304L stainless steel, of indigenously developed ferroboron alternate shielding material for fast reactor applications

Towards the cause of serving economic power production through fast reactors, it is necessary to bring in functionally more efficient and innovative design options, which also includes exploration of cheaper material alternatives, wherever possible. In this regard, the feasibility of using a commercial grade ferroboron alloy as potential alternate shielding material in the outer subassemblies of future Indian fast reactors has been recently investigated from shielding physics point of view. The present study explores in detail the high temperature thermal stability and the metallurgical compatibility of Fe-15.4B-0.3C-0.89Si-0.17Al-0.006S-0.004P-0.003O (wt.%) alloy with SS 304L material. In addition, the high temperature specific heat and lattice thermal expansion characteristics of this alloy have also been investigated as a part of the present comprehensive characterisation program. The Fe-15 wt.%B alloy is constituted of principally of two boride phases, namely tetragonal Fe₂B and orthorhombic FeB phases, which in addition to boron also contains some amount of C and Si dissolved in solid solution form. This Fe-B alloy undergoes a series of phase transformation as a function of increasing temperature; the major ones among them are the dissolution of Fe₂B-lower boride in the matrix through a eutectic type reaction, which results in the formation of the first traces of liquid at 1500 K/1227 °C. This is then followed by the dissolution of the major FeB boride phase in liquid and the melting process is completed at 1723 K/1450 °C. In a similar manner, the thermal stability studies performed on combined Fe-B + 304L steel reaction couples revealed that a pronounced pre-melting or liquid phase formation occurs at a temperature of 1471 K/1198 °C, which is lower than the melting onset of both Fe-B and SS 304L. It is found that within the limits of experimental uncertainty, this pre-melting phenomenon occurred at the same fixed temperature of 1471 K/1198 °C, irrespective of the mass ratios of Fe-B and 304L steel. Further, it is also found that SS 304L is completely soluble in Fe-B alloy and the fused product upon solidification formed a mixture of complex intermetallic borides, such as (Fe,Cr)(B,C), (Fe,Cr)₂(B,C) and (Fe,Ni)₃B. In the temperature range 823-1073 K (550-800 °C), the SS 304L clad is found to interact strongly with the Fe-B alloy. The diffusion layer thickness or the attack layer depth (x) is found to vary with time (t) up to about 5000 h, according to the empirical rate law, x² = k(T)t. The temperature sensitivity of the rate constant, k(T) is found to obey the Arrhenius law, k(T) = k_o exp(−Q/RT), with Q = 57 kJ mol⁻¹, being the effective activation energy for the overall diffusional interaction of Fe-B and SS 304L. The room temperature specific heat capacity of Fe-B alloy is found to be 538 kJ kg⁻¹ K⁻¹. The C_P values measured over 300-1350 K, is found vary smoothly with temperature according to the expression, C_P/kJ kg⁻¹ K⁻¹ = 0.62094 + 0.00012T + 10685.81T⁻². The lattice thermal expansion of both FeB and Fe₂B phases are found to be anisotropic in that the c-axis expansion is found to be more than that along a and b axes. The room temperature volume thermal expansivity of FeB and Fe₂B phases are found to be of the order of 48 × 10⁻⁶ K⁻¹ and 28 × 10⁻⁶ K⁻¹, respectively. The thermal expansion of FeB is found to be more temperature sensitive than that of Fe₂B.     

Uranium monocarbide

Uranium monocarbide is of interest as a possible nuclear fuel and material for nuclear thermoelectrical transformations. In order to accurately define the effect of the conditions for preparing uranium monocarbide (UC) on its composition, studies were made which established the optimum regime for preparing UC with a stoichiometric composition.Studies were made of the conditions for sintering and hot pressing of UC powder and also conditions for sintering UC + U alloys, giving specimens with a porosity of about 5%. The specific gravity of UC powder determined by a pycnometer is 12.97 ± 0.09 g/cm³, microhardness of the phase-923 ± 56 kg/mm².The thermal conductivity of UC in the range 100–700 °C varies from 0.028 to 0.04 cal/cm. sec.deg; the mean thermal coefficient of linear expansion in the range 20–1500 ° is 11.6 · 10^–6. Specimens of UC subjected to cyclic heat-treatment in the range 200–1000 ° withstood 500 cycles without failure. Specimens of UC + U withstood more than 1000 cycles.     

Enthalpy measurements of La2Te3O9 and La2Te4O11

Enthalpy increment measurements on La₂Te₃O₉(s) and La₂Te₄O₁₁(s) were carried out using a Calvet micro-calorimeter. The enthalpy values were analyzed using the non-linear curve fitting method. The dependence of enthalpy increments with temperature was given as: H°(T) − H°(298.15 K) (J mol⁻¹) = 360.70T + 0.00409T² + 133.568 × 10⁵/T − 149 923 (373 ? T (K) ? 936) for La₂Te₃O₉ and H°(T) − H°(298.15 K) (J mol⁻¹) = 331.927T + 0.0549T² + 29.3623 × 10⁵/T − 114 587 (373 ? T (K) ? 936) for La₂Te₄O₁₁.     

Thermal expansion studies on Inconel-600 by high temperature X-ray diffraction

The lattice thermal expansion characteristics of Inconel-600^® have been studied by high temperature X-ray diffraction (HT-XRD) technique in the temperature range 298-1200 K. Altogether four experimental runs were conducted on thin foils of about 75-100 μm thickness. The diffraction profiles have been accurately calibrated to offset the shift in 2θ values introduced by sample buckling at elevated temperatures. The corrected lattice parameter data have been used to estimate the instantaneous and mean linear thermal expansion coefficients as a function of temperature. The thermal expansion values estimated in the present study show a fair degree of agreement with other existing dilatometer based bulk thermal expansion estimates. The lattice parameter for this alloy at 300 K is found to be 0.3549(1) nm. The mean linear thermal expansivity is found to be 11.4 × 10⁻⁶ K⁻¹.     

Measurement of thermal properties of a ceramic/metal joint by laser flash method

This work describes the measurement of thermal diffusivity and the subsequent calculation of thermal conductivity and thermal contact resistance (from room temperature to 800 °C in N₂ atmosphere) at the material interface for carbon/carbon composites (C/C) joined to copper by using the laser flash method. According to these measurements, the thermal resistance at the interface, that is related to the heat transfer through the solid, is <10⁻⁶ m² K W⁻¹ up to 800 °C, indicating a high quality of the joint and no limitations for the thermal heat transfer during operation, e.g. in a nuclear fusion reactor. This measurement is proposed as an innovative non-contact and qualitative investigation technique to assess the ceramic/metal joint integrity.     

Measurement of transformation temperatures and specific heat capacity of tungsten added reduced activation ferritic-martensitic steel

The on-heating phase transformation temperatures up to the melting regime and the specific heat capacity of a reduced activation ferritic-martensitic steel (RAFM) with a nominal composition (wt%): 9Cr-0.09C-0.56Mn-0.23V-1W-0.063Ta-0.02N, have been measured using high temperature differential scanning calorimetry. The α-ferrite + carbides → γ-austenite transformation start and finish temperatures, namely Ac₁, and Ac₃, are found to be 1104 and 1144 K, respectively for a typical normalized and tempered microstructure. It is also observed that the martensite start (M_S) and finish (M_f) temperatures are sensitive to the austenitising conditions. Typical M_S and M_f values for the 1273 K normalized and 1033 K tempered samples are of the order 714 and 614 K, respectively. The heat capacity C_P of the RAFM steel has been measured in the temperature range 473-1273 K, for different normalized and tempered samples. In essence, it is found that the C_P of the fully martensitic microstructure is found to be lower than that of its tempered counterpart, and this difference begins to increase in an appreciable manner from about 800 K. The heat capacity of the normalized microstructure is found to vary from 480 to 500 J kg⁻¹ K⁻¹ at 500 K, where as that of the tempered steel is found to be higher by about, 150 J kg⁻¹ K⁻¹.     

Permeability of hydrogen and deuterium of Hastelloy XR

Permeation of hydrogen isotope through a high-temperature alloy used as heat exchanger and steam reformer pipes is an important problem in the hydrogen production system connected to be a high-temperature engineering test reactor (HTTR). An experiment of hydrogen (H₂) and deuterium (D₂) permeation was performed to obtain permeability of H₂ and D₂ of Hastelloy XR, which is adopted as heat transfer pipe of an intermediate heat exchanger of the HTTR. Permeability of H₂ and D₂ of Hastelloy XR were obtained as follows. The activation energy E₀ and pre-exponential factor F₀ of the permeability of H₂ were E₀=67.2±1.2 kJ mol⁻¹ and F₀=(1.0±0.2)×10⁻⁸ m³(STP) m⁻¹ s⁻¹ Pa^−0.5, respectively, in the pipe temperature ranging from 843 K (570 °C) to 1093 K (820 °C). E₀ and F₀ of the permeability of D₂ were respectively E₀=76.6±0.5 kJ mol⁻¹ and F₀=(2.5±0.3)×10⁻⁸ m³(STP) m⁻¹ s⁻¹ Pa^−0.5 in the pipe temperature ranging from 943 K (670 °C) to 1093 K (820 °C).     

Use of concretes for high-temperature shielding of nuclear reactors

The authors have studied the possibility of using chromite and chomotte heat-resistant concretes for the thermal shields of reactors. They observe neutron fluxes of various intensities (up to 10¹³ neutrons/cm²·sec, with spectrum similar to fission spectrum), absorbed by shields of these materials. They compute the transmission of neutrons and of fluxes of gamma quanta and the heat emission in the shielding. They calculate the temperatures in the shielding for various neutron fluxes, concrete thicknesses and cooling conditions. They perform a statistical calculation of the temperature stresses for shielding constructed of heat-resistant ferroconcrete.It was established that nuclear reactor shields can be made from heat-resistant ferroconcrete when the neutron fluxes on the concrete are up to 10¹³ neutrons/cm²·sec, for temperatures up to 1000–1100° C and temperature differences of up to 900° C.Translated from Atomnaya Énergiya, Vol. 19, No. 6, pp. 524–529, December, 1965Report read by G. I. Budker at the International Conference on High-Energy Accelerators (Frascati, Italy).     

Creep behavior of ceramic nuclear fuels under neutron irradiation

A theoretical estimation of the irradiation-induced creep rate of UO₂ resulted in a creep rate range between about 6 × 10⁻⁶/h and 8 × 10⁻⁵/h for a fission rate of 1 × 10¹⁴ f/cm³·s and a stress of 2 kgf/mm². It is essentially due to the “thermal rods” along the fission fragment tracks. Therefore, creep rates should only weakly depend on temperature (below 1000–1200°C) and must be markedly lower for carbide and nitride fuel.     

Effect of temperature on studtite stability: Thermogravimetry and differential scanning calorimetry investigations

The main objective of this work is the study of the influence of temperature on the stability of the uranyl peroxide tetrahydrate (UO₂O₂ · 4H₂O) studtite, which may form on the spent nuclear fuel surface as a secondary solid phase. Preliminary results on the synthesis of studtite in the laboratory at different temperatures have shown that the solid phases formed when mixing hydrogen peroxide and uranyl nitrate depends on temperature. Studtite is obtained at 298 K, meta-studtite (UO₂O₂ · 2H₂O) at 373 K, and meta-schoepite (UO₃ · nH₂O, with n < 2) at 423 K. Because of the temperature effect on the stability of uranyl peroxides, a thermogravimetric (TG) study of studtite has been performed. The main results obtained are that three transformations occur depending on temperature. At 403 K, studtite transforms to meta-studtite, at 504 K, meta-studtite transforms to meta-schoepite, and, finally, at 840 K, meta-schoepite transforms to U₃O₈. By means of the differential scanning calorimetry the molar enthalpies of the transformations occurring at 403 and 504 K have been determined to be −42 ± 10 and −46 ± 2 kJ mol⁻¹, respectively.     

Thermal and structural properties of low-fluence irradiated graphite

The release of Wigner energy from graphite irradiated by fast neutrons at a TRIGA Mark II research reactor has been studied by differential scanning calorimetry and simultaneous differential scanning calorimetry / synchrotron powder X-ray diffraction between 25 and 725 °C at a heating rate of 10 °C min⁻¹. The graphite, having been subject to a fast-neutron fluence from 5.67 × 10²⁰ to 1.13 × 10²² n m⁻² at a fast-neutron flux (E > 0.1 MeV) of 7.88 × 10¹⁶ n m⁻² s⁻¹ and at temperatures not exceeding 100 °C, exhibits Wigner energies ranging from 1.2 to 21.8 J g⁻¹ and a Wigner energy accumulation rate of 1.9 × 10⁻²¹ J g⁻¹ n⁻¹ m². The differential-scanning-calorimeter curves exhibit, in addition to the well known peak at ∼200 °C, a pronounced fine structure consisting of additional peaks at ∼150, ∼230, and ∼280 °C. These peaks correspond to activation energies of 1.31, 1.47, 1.57, and 1.72 eV, respectively. Crystal structure of the samples is intact. The dependence of the c lattice parameter on temperature between 25 and 725 °C as determined by Rietveld refinement leads to the expected microscopic thermal expansion coefficient along the c axis of ∼26 × 10⁻⁶ °C⁻¹. At 200 °C, coinciding with the maximum in the differential-scanning-calorimeter curves, no measurable changes in the rate of thermal expansion have been detected - unlike its decrease previously seen in more highly irradiated graphite.     

Structural, electronic, and thermodynamic properties of UN: Systematic density functional calculations

A systematic first-principle study is performed to calculate the lattice parameters, electronic structure, and thermodynamic properties of UN using the local-density approximation (LDA)+U and the generalized gradient approximation (GGA)+U formalisms. To properly describe the strong correlation in the U 5f electrons, we optimized the U parameter in calculating the total energy, lattice parameters, and bulk modulus at the nonmagnetic (NM), ferromagnetic (FM), and antiferromagnetic (AFM) configurations. Our results show that by choosing the Hubbard U around 2 eV within the GGA+U approach, it is promising to correctly and consistently describe the above mentioned properties of UN. The localization behavior of 5f electrons is found to be stronger than that of UC and our electronic analysis indicates that the effective charge of UN can be represented as U^1.71+N^1.71−. As for the thermodynamic study, the phonon dispersion illustrates the stability of UN and we further predict the lattice vibration energy, thermal expansion, and specific heat by utilizing the quasiharmonic approximation. Our calculated specific heat is well consistent with experiments.     

Contribution of thermal neutrons to radiation hardening of pure copper

The paper presents the results of an experiment the aim of which was to estimate directly the effect of the thermal neutron fluence on pure copper hardening. Identical specimens were irradiated in two reactors (SM-2 and RBT-6) in the dose range 10⁻³-10⁻¹ dpa at T_irr=80 °C under substantially different, by a factor of 5, thermal neutron fluences, with other irradiation parameters being close. The results show that the elevated thermal fluence in the SM-2 reactor increases the radiation hardening of pure copper by 50% at a dose of about 10⁻³ dpa as compared with specimens irradiated in the RBT-6 reactor. The contribution of thermal neutrons proved to be much more considerable than the theoretical estimates.     

Thermal conductivity of (U,Pu,Np)O2 solid solutions

The thermal conductivities of (U_,Pu_,Np)O₂ solid solutions were studied at temperatures from 900 to 1770 K. Thermal conductivities were obtained from the thermal diffusivity measured by the laser flash method. The thermal conductivities obtained below 1400 K were analyzed with the data of (U,Pu,Am)O₂ obtained previously, assuming that the B-value was constant, and could be expressed by a classical phonon transport model, λ = (A + BT)⁻¹, A(z₁, z₂) = 3.583 × 10⁻¹ × z₁ + 6.317 × 10⁻² × z₂ + 1.595 × 10⁻² (m K/W) and B = 2.493 × 10⁻⁴ (m/W), where z₁ and z₂ are the contents of Am- and Np-oxides. It was found that the A-values increased linearly with increasing Np- and Am-oxide contents slightly, and the effect of Np-oxide content on A-values was smaller than that of Am-oxide content. The results obtained from the theoretical calculation based on the classical phonon transport model showed good agreement with the experimental results.     

Calorimetric measurements on (U,Th)O2 solid solutions

Enthalpy increments of urania - thoria solid solutions, (U_0.10Th_0.90)O₂, (U_0.50Th_0.50)O₂ and (U_0.90Th_0.10)O₂ were measured by drop calorimetry in the temperature range 479 - 1805 K. Heat capacity, entropy and Gibbs energy function were computed. The heat capacity measurements were carried out also with differential scanning calorimetry in the temperature range 298 - 800 K. The heat capacity values of (U_0.10Th_0.90)O₂, (U_0.50Th_0.50)O₂ and (U_0.90Th_0.10)O₂ at 298 K are 59.62, 61.02, 63.56 J K⁻¹ mol⁻¹, respectively. The results were compared with the data available in the literature. From the study, the heat capacity of (U,Th)O₂ solid solutions was shown to obey the Neumann - Kopp’s rule.     

Porosity dependence on thermal diffusivity and thermal conductivity of lithium oxide Li2O from 200 to 900°C

The porosity dependence on thermal diffusivity and thermal conductivity of Li₂O was studied in the temperature range of 200 to 900°C. The relationship between thermal diffusivity α_M and porosity P was expressed as α_M = α_T(1?ζP), $\text{}\text{?}$gz being 0.93, and also as $\text{α}{}_{\mathrm{M}}\text{=}\text{α}{}_{\mathrm{T}}\text{(1 + ηP)}$, η being 1.74 (200°C) ~ 1.11 (900°C). The relationship between thermal conductivity k_M and porosity obeyed the generalized Loeb equation k_M = k_T(1?γP), $\text{}\text{?}$gg being 1.70, and obeyed the modified Maxwell-Eucken equation $\text{k}{}_{\mathrm{M}}\text{=}\text{k}{}_{\mathrm{T}}\text{(1?P)}\text{(1 + βP)}$, β being 1.81 (200°C) ~ 1.32 (900°C). Alternative empirical equations were also attempted as α_M = α_T(1?P)^m and k_M = k_T(1?P)ⁿ, m? being 0.91 and $\text{n}\text{?}\text{= 1.06}$. The temperature dependence on thermal diffusivity and thermal conductivity was found to be expressed as α = (A' + B'T)^?1 and k = (A + BT)^?1. The pore correction factors are discussed in terms of porosity and temperature compared to published results.     

Tungsten behavior under proton flux and high temperature

An experimental study of the physico-chemical behavior of tungsten under severe conditions is presented. High temperatures (1300 ? T ? 2500 K) generated by concentrated solar energy, high vacuum (∼10⁻⁶ hPa) and proton flux (1 keV, ∼10¹⁷ ions m⁻² s⁻¹) have been applied on polycrystalline W samples to simulate expected and also unexpected high heat loads that can occur on the ITER divertor (nominal and accidental conditions). During experiment, in situ measurements are performed and the material degradation, the mass loss kinetics, the characterization of the different species coming from the materials under coupled proton flux and high temperatures and the optical properties (reflectivity) are followed. Material characterization using SEM and XRD was investigated before and after treatment to understand the observed behavior. Bidirectional reflectivity measurements were carried out on the tested samples to explain the surface modifications, between the reference sample, the heated sample and the heated and ion irradiated one that can act on the thermo-radiative properties of tungsten.     

The heat capacity and enthalpy of condensed UO2: Critical review and assessment

Having established the role of the heat capacity, C_p(T), of condensed UO₂ in various FBR accident scenarios, e.g. HCDA and PAHR, and having noted the unsatisfactory state of present knowledge concerning this basic thermophysical property of the fuel, all existing enthalpy and heat capacity data are collated and assessed, and certain recommendations made. The conventional method of obtaining C_p(T) by analytical differentiation of some adopted fit to this enthalpy data is then critically examined. The attendant problems are illustrated both for solid UO₂, where the contribution to C_p(T) from the weak, sigmoidal, enthalpy structure (which is just discernible in the data of Hein and Flagella) is missed and for molten UO₂, where not even the direction of the trend of C_p(T) with T can be definitively established, resulting, upon extrapolation to 5000 K, in C_p values which can differ by as much as 60 J mol⁻¹K⁻¹.Some recent progress towards a more acceptable, “model-independent” approach, known as quasi-local linear regression (QLLR), is then reviewed and applied to enthalpy data of UO₂ on both sides of its melting point, T_m. In the case of solid UO₂, a pronounced heat capacity peak, extending over about 100 K and centred on 2610 K., is revealed, whose magnitude and location is very similar to that found in other fluorite structured materials near 0.8T_m wherein it indicates a (Bredig) transition to a state characterised by giant ionic conductivities.Whilst it is impossible to establish any definite T-dependence for the C_p(QLLR) values in molten UO₂, the tendency to slightly decrease appears to marginally outweigh the converse, in qualitative accord with the dependence advocated by Hoch and Vernardakis. In the post-transitional region T_t<T<T_m the opposite holds, as is necessary for consistency between the independently established T-dependences of the thermal conductivity and diffusivity, which requires that C_p(T) increases with T faster than the density decreases.Attention is then drawn to some interesting comparisons which exist between the behaviour of UO₂ and other (non-actinide) fluorites near their melting points, which suggest the existence, in UO₂ of a significant degree of (i) cation disorder in the post-transitional region, 0.8T_m<T <T_m and (ii) electronic disorder in the melt. The review concludes with an extended, retrospective overview of the present situation regarding the heat capacity of condensed UO₂, and identifies some specific experimental goals in connection with the current experimental programme of the Joint Research Centre, Karlsruhe, Fed. Rep. Germany.     

Electroluminescence from metal-oxide-silicon tunneling diode with ion-beam-synthesized β-FeSi2 precipitates embedded in the active region

A metal-oxide-silicon (MOS) tunneling light-emitting diode is fabricated with ion-beam-synthesized β-FeSi₂ precipitates embedded in the active region. Fe ions were implanted into p⁻-100 silicon substrate at cryogenic temperature (∼−120 °C), followed by rapid thermal oxidation (RTO). Under constant voltage biased in accumulation and at temperatures down to 80 K, electroluminescence (EL) with wavelength peaking at ∼1.5 μm is observed at a current density of about 2.0 A/cm². Light output increases linearly with current density. Temperature dependence of the EL shows that the luminescence is due to interband recombination in the crystalline precipitates. The strain in these isolated precipitates may contribute to the luminescence properties of β-FeSi₂ in silicon.     

Magnetic and related properties of PuPdSn

A new phase PuPdSn was prepared and studied by X-ray diffraction, magnetization and heat capacity measurements, performed in the temperature range 2-300 K and in magnetic fields up to 14 T. The crystal structure determined from single-crystal X-ray data is the hexagonal ZrNiAl-type [space group ] with lattice parameters: a = 7.5057 Å and c = 4.0853 Å. PuPdSn orders antiferromagnetically at T_N = 21 K. Moreover, another antiferromagnetic-like transition takes place at 9.6 K. Above T_N the susceptibility follows a modified Curie-Weiss law with μ_eff = 1.0 μ_B, Θ_p = −14 K and χ₀ = 2.1 × 10⁻⁴ emu/mol. The low-temperature linear specific heat coefficient is small (γ ∼ 8 mJ/mol K²) pointing to well localized 5f electrons.