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At least 739 records · Page 41
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Effect of Cold Deformation and Heat Treatment on the Microstructure and Mechanical Behavior of High Entropy Alloy CuCrFeNi{sub 2}Al{sub 0.5}

CuCrFeNi{sub 2}Al{sub 0.5}, a high entropy alloy (HEA) with a single FCC phase, was deformed at room temperature and then heat treated. The small particles precipitated from the deformed FCC solid solution matrix after heating at 700 °C, softening the solid solution matrix. This outcome confirms that the microstructure of HEAs can be controlled by heat treatment in addition to controlling the chemical composition and the rate of cooling from liquid alloys. The hardness of the samples increased due to precipitation hardening, and the specimen heated at 700 °C with 10% predeformation had the highest hardness. As the predeformation increases, the precipitates tend to interweave in the network morphology. Meanwhile, grains in all specimens became more severely coarse after heat treatment at 1100 °C. Predeformation followed by annealing can obviously slow down the creep rate, indicating that annealing at an appropriate temperature can improve the mechanical properties of deformed HEA.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Microstructural Characterization, Mechanical Properties, and Corrosion Resistance of Dental Co-Cr-Mo-W Alloys Manufactured by Selective Laser Melting

In this paper, the microstructure, mechanical properties, and corrosion resistance of the dental Co-Cr-Mo-W alloys fabricated by selective laser melting (SLM) were systematically investigated and correlated. The microstructure of the SLM group (SG) specimens is composed of extremely fine columnar crystals, exhibiting supersaturated and homogeneous character. The matrix mainly consists of face-centered-cubic (FCC) cobalt solid solutions, and minimal hexagonal-close-packed (HCP) cobalt solid solutions. Mechanical test results showed that the 0.2% yield strength of SG was 775 ± 7 MPa, and the ultimate tensile strength was 1118 ± 25 MPa. The elongation of SG was 8.28 ± 0.4%, and the microhardness of SG was 476 ± 10 HV. All of these values largely exceeded the cast group (CG) specimens. The high strength is attributed to their fine columnar crystals and supersaturated matrices. The fewer content from the HCP phase and a lack of intermetallic compounds or eutectic contribute to the high ductility. Furthermore, a higher E{sub corr}, lower I{sub corr} were acquired for better corrosion resistance compared to cast specimens, due to even less composition segregation and more microstructural homogeneity.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Disorder in M n+1 AX n phases at the atomic scale

Atomic disordering in materials alters their physical and chemical properties and can subsequently affect their performance. In complex ceramic materials, it is a challenge to understand the nature of structural disordering, due to the difficulty of direct, atomic-scale experimental observations. Here we report the direct imaging of ion irradiation-induced antisite defects in M n+1 AX n phases using double CS-corrected scanning transmission electron microscopy and provide compelling evidence of order-to-disorder phase transformations, overturning the conventional view that irradiation causes phase decomposition to binary fcc-structured M n+1 AX n . With the formation of uniformly distributed cation antisite defects and the rearrangement of X anions, disordered solid solution γ-(M n+1 A)X n phases are formed at low ion fluences, followed by gradual transitions to solid solution fcc-structured (M n+1 A)X n phases. This study provides a comprehensive understanding of the order-to-disorder transformations in M n+1 AX n phases and proposes a method for the synthesis of new solid solution (M n+1 A)X n phases by tailoring the disorder.

36 MATERIALS SCIENCE↗
DOE OSTI2014

The stochastic model for ternary and quaternary alloys: Application of the Bernoulli relation to the phonon spectra of mixed crystals

To understand and interpret the experimental data on the phonon spectra of the solid solutions, it is necessary to describe mathematically the non-regular distribution of atoms in their lattices. It appears that such description is possible in case of the strongly stochastically homogenous distribution which requires a great number of atoms and very carefully mixed alloys. These conditions are generally fulfilled in case of high quality homogenous semiconductor solid solutions of the III–V and II–VI semiconductor compounds. In this case, we can use the Bernoulli relation describing probability of the occurrence of one n equivalent event which can be applied, to the probability of finding one from n configurations in the solid solution lattice. The results described in this paper for ternary HgCdTe and GaAsP as well as quaternary ZnCdHgTe can provide an affirmative answer to the question: whether stochastic geometry, e.g., the Bernoulli relation, is enough to describe the observed phonon spectra.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2019

Electronic structure and atomic level complexity in Al 0.5 TiZrPdCuNi high-entropy alloy in glass phase

We present that high entropy alloys (HEAs), or concentrated solid solution alloys, are chemically complex metallic solid solutions in which five or more elements occupy the same crystallographic lattice sites with nearly equal compositions. The high degree of chemical disorder gives rise to considerable local lattice distortions, atomic-level stresses, and complex electronic structure, resulting in interesting properties. We calculated the electronic structure and the atomic-level stresses of Al x Ti y Zr y Pd y Cu y Ni y , x = 0.5, y = 1 (Al 0.5 TiZrPdCuNi) HEA in the glassy phase using the density functional theory (DFT) approach. We also briefly discuss the electronic structure in its crystalline phase. Whereas it has been reported recently that the crystalline phase of this HEA is obtained as a metastable phase during the crystallization of a glassy phase, the crystalline phase was found to be unstable at T = 0 in the DFT calculation. For this reason, we focus mainly on the glassy phase in this work. Lastly, the importance of charge transfer among elements on the atomic-level pressure and the role for atomic-level stresses to characterize the electronic and structural heterogeneity are discussed.

36 MATERIALS SCIENCE↗
NASA NTRS1974

Matrix isolation technique for the study of some factors affecting the partitioning of trace elements

The factors that affect the preferred positions of cations in ionic solid solutions were investigated utilizing vibrational spectroscopy. Solid solutions of the sulfate and chromate ions codoped with La(+3) and Ca(+2) in a KBr host lattice were examined as a function of the polyvalent cation concentration. The cation-anion pairing process was found to be random for Ca(+2), whereas the formation of La(+3)-SO4(-2) ion pairs with a C2 sub v bonding geometry is highly preferential to any type of La(+3)-CrO4(-2) ion pair formation. The relative populations of ion pair site configurations are discussed in terms of an energy-entropy competition model which can be applied to the partition of trace elements during magmatic processes.

Grzybowski, J. M.↗
DOE OSTI2018

Solution and Solid State Structural Chemistry of Th(IV) and U(IV) 4-Hydroxybenzoates

Organic ligands with carboxylate functionalities have been shown to affect the solubility, speciation, and overall chemical behavior of tetravalent metal ions. While many reports have focused on actinide complexation by relatively simple monocarboxylates such as amino acids, here we examined Th(IV) and U(IV) complexation by 4-hydroxybenzoic acid in water with the aim of understanding the impact that the organic backbone has on the solution and solid state structural chemistry of thorium(IV) and uranium(IV) complexes. Two compounds of the general formula [An 6 O 4 (OH) 4 (H 2 O) 6 (4-HB) 12 ]· n H 2 O [An = Th ( Th-1 ) and U ( U-1 ); 4-HB = 4-hydroxybenzoate] were synthesized via roomtemperature reactions of AnCl 4 and 4-hydroxybenzoic acid in water. Solid state structures were determined by single-crystal X-ray diffraction, and the compounds were further characterized by Raman, infrared, and optical spectroscopies and thermogravimetry. The magnetism of U-1 was also examined. The structures of the Th and U compounds are isomorphous and are built from ligand-decorated oxo/hydroxo-bridged hexanuclear units. The relationship between the building units observed in the solid state structure of U-1 and those that exist in solution prior to crystallization as well as upon dissolution of U-1 in nonaqueous solvents was investigated using small-angle X-ray scattering, ultraviolet-visible optical spectroscopy, and dynamic light scattering. The evolution of U solution speciation as a function of reaction time and temperature was examined. Such effects as well as the impact of the ligand on the formation and evolution of hexanuclear U(IV) clusters to UO 2 nanoparticles compared to prior reported monocarboxylate ligand systems are discussed. Unlike prior reported syntheses of Th and U(IV) hexamers where the pH was adjusted to ~2 and 3, respectively, to drive hydrolysis, hexamer formation with the HB ligand appears to be promoted only by the ligand.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Phase formation and UV luminescence of Gd{sup 3+} doped perovskite-type YScO{sub 3}

Synthesis of pure and Gd{sup 3+}doped perovskite-type YScO{sub 3} was attempted by a polymerized complex (PC) method and solid state reaction (SSR) method. Crystalline phases and UV luminescence of samples were examined with varying heating temperatures. The perovskite-type single phase was not simply formed in the SSR method, as reported in some literatures, and two cubic C-type phases of starting oxide materials remained forming slightly mixed solid solutions. UV luminescence of Gd{sup 3+} doped samples increased with an increase in heating temperatures and volume of the perovskite-type phase. In contrast, a non-crystalline precursor was crystallized to a single C-type phase at 800 °C in the PC method forming a completely mixed solid solution. Then, the phase of perovskite-type YScO{sub 3} formed at 1200 °C and its single phase was obtained at 1400 °C. It was revealed that high homogeneousness of cations was essential to generate the single perovskite-phase of YScO{sub 3}. Because Gd{sup 3+} ions were also dissolved into the single C-type phase in Gd{sup 3+} doped samples, intense UV luminescence was observed above 800 °C in both C-type phase and perovskite-type phase. - Graphical abstract: A pure perovskite-type YScO{sub 3} phase was successfully synthesized by a polymerized complex (PC) method. The perovskite-type YScO{sub 3} was generated through a solid solution of C-type (Y{sub 0.5}Sc{sub 0.5}){sub 2}O{sub 3} with drastic change of morphology. The PC method enabled a preparation of the single phase of the perovskite-type YScO{sub 3} at lower temperature and in shorter heating time. Gd{sup 3+} doped perovskite-type YScO{sub 3} was found to show a strong sharp UV emission at 314 nm. - Highlights: • Pure YScO{sub 3} phase was successfully synthesized by polymerized complex (PC) method. • Pure perovskite-type YScO{sub 3} phase was generated from pure C-type (Y{sub 0.5}Sc{sub 0.5}){sub 2}O{sub 3} one. • YScO{sub 3} was obtained at lower temperature and in shorter heating time by PC method. • Perovskite-type YScO{sub 3}:Gd{sup 3+} was found to show strong sharp UV emission at 314 nm.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

In situ Raman spectroscopy of pressure-induced phase transformations in polycrystalline TbPO 4 , DyPO 4 , and Gd x Dy (1– x ) PO 4 [ In situ Raman spectroscopy of pressure-induced phase transformations in DyPO 4 and Gd x Dy (1– x ) PO 4 ]

Xenotime DyPO 4 and Gd x Dy (1–x) PO 4 (x = 0.4, 0.5, 0.6) (tetragonal I41amd zircon structure) have been studied at ambient temperature under high pressures inside a diamond anvil cell with in situ Raman spectroscopy. The typical Raman–active modes of the xenotime structure were observed at low pressures and the appearance of new Raman peaks at higher pressures indicated a phase transformation to a lower symmetry structure—likely monoclinic. Raman mode softening was observed, resulting in a line crossing at approximately 7–8 GPa for each material and preceding the phase transformation. The onset of phase transformation for DyPO 4 occurred at a pressure of 15.3 GPa. DyPO 4 underwent a reversible phase transformation and returned to the xenotime phase after decompression. The transformation pressures of the solid solutions (Gd x Dy (1–x) PO 4 ) were in the range 10–12 GPa. The GdxDy(1–x)PO 4 solid solutions yielded partially reversible phase transformations, retaining some of the high–pressure phase spectrum while reforming xenotime peaks during decompression. The substitution of Gd into DyPO 4 decreased the transformation pressure relative to pure DyPO 4 . In conclusion, the ability to modify the phase transformation pressures of xenotime rare–earth orthophosphates by chemical variations of solid solutions may provide additional methods to improve the performance of ceramic matrix composites.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Reactive sintering of tungsten-doped high strength ZrB{sub 2}–SiC porous ceramics using metastable precursors

Graphical abstract: - Highlights: • Tungsten-doped porous ZrB{sub 2}–SiC specimens were fabricated by reactive sintering. • Both sintering and mechanical properties were improved by doping with tungsten. • Optimum concentration to obtain high mechanical properties was W/Zr (mol) = 0.05. • Sintering might be promoted by self-accelerated diffusion. • Mechanical properties might be improved by solid solution strengthening. - Abstract: Tungsten-doped porous ZrB{sub 2}-20 vol.% SiC specimens with a high strength skeleton were fabricated by reactive sintering using metastable reactants, i.e., as-synthesized amorphous hydrous ZrO{sub 2}–WO{sub 3}/ZrO{sub 2}, amorphous boron, nanocarbon, and β-SiC. Doping with tungsten clearly promoted sintering and improved mechanical properties; the optimum tungsten concentration to obtain high mechanical properties was investigated. A single-phase solid solution (Zr,W)B{sub 2} was formed in the specimens with tungsten. We suggest that sintering was promoted by self-accelerated diffusion owing to the formation of point defects caused by doping with tungsten. The improvement of mechanical properties could be attributed to solid solution strengthening.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Syntheses, structures, and ionic conductivities of perovskite-structured lithium–strontium–aluminum/gallium–tantalum-oxides

The ionic conductivities of new perovskite-structured lithium–strontium–aluminum/gallium–tantalum oxides were investigated. Solid solutions of the new perovskite oxides, (Li{sub x}Sr{sub 1−x})(Al{sub (1−x)/2}Ta{sub (1+x)/2})O{sub 3} and (Li{sub x}Sr{sub 1−x})(Ga{sub (1−x)/2}Ta{sub (1+x)/2})O{sub 3}, were synthesized using a ball-milled-assisted solid-state method. The partial substitution of the smaller Ga{sup +3} for Ta{sup +5} resulted in new compositions, the structures of which were determined by neutron diffraction measurements using a cubic perovskite structural model with the Pm−3m space group. Vacancies were introduced into the Sr(Li) sites by the formation of solid solutions with compositions (Li{sub x}Sr{sub 1−x−y}☐{sub y})(Ga{sub [(1−x)/2]−y}Ta{sub [(1+x)/2]+y})O{sub 3}, where the composition range of 0≤y≤0.20 was examined for x=0.2 and 0.25. The highest conductivity, 1.85×10{sup −3} S cm{sup −1} at 250 °C, was obtained for (Li{sub 0.25}Sr{sub 0.625}☐{sub 0.125})(Ga{sub 0.25}Ta{sub 0.75})O{sub 3} (x=0.25, y=0.125). Enhanced ionic conductivities were achieved by the introduction of vacancies at the A-sites. - Graphical abstract: Novel lithium-conducting oxides with the cubic perovskite structure (Li{sub x}Sr{sub 1−x−y}☐{sub y})(Ga{sub [(1−x)/2]−y}Ta{sub [(1+x)/2]+y})O{sub 3} provide a specific solid-solution region with various x and y values, exhibiting the highest ionic conductivity (1.85 S cm{sup −1} at 250 °C) for (Li{sub 0.25}Sr{sub 0.625}☐{sub 0.125})(Ga{sub 0.25}Ta{sub 0.75})O{sub 3} (x=0.25, y=0.125 in (Li{sub x}Sr{sub 1−x−y}☐{sub y})(Ga{sub [(1−x)/2]−y}Ta{sub [(1+x)/2]+y})O{sub 3}). The vacancies (☐) introduced into the A-sites contribute to the enhancement of lithium diffusion in the perovskite structure because of the enlargement of the bottleneck size and suppression of the interaction between lithium and oxygen. - Highlights: • The perovskite-structured novel Li–Sr–Al/Ga–Ta oxides were investigated. • The Ga cation offers a larger bottleneck by increasing the B−O bond length. • The greater conductivity was observed upon Ga-containing perovskite. • The ionic conductivity was improved by the introduction of vacancies into A-site.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Creep-Fatigue Behavior of Alloy 617 at 850°C

Creep-fatigue deformation is expected to be a significant contributor to the potential factors that limit the useful life of the Intermediate Heat Exchanger (IHX) in the Very High Temperature Reactor (VHTR) nuclear system. The IHX of a high temperature gas reactor will be subjected to a limited number of transient cycles due to start-up and shut-down operations imparting high local stresses on the component. This cycling introduces a creep-fatigue type of interaction as dwell times occur intermittently. The leading candidate alloy for the IHX is a nickel-base solid solution strengthened alloy, Alloy 617, which must safely operate near the expected reactor outlet temperature of up to 950 °C. This solid solution strengthened nickel-base alloy provides an interesting creep-fatigue deformation case study because it has characteristics of two different alloy systems for which the cyclic behavior has been extensively investigated. Compositionally, it resembles nickel-base superalloys, such as Waspalloy, IN100, and IN718, with the exception of its lower levels of Al. At temperatures above 800 °C, the microstructure of Alloy 617, however, does not contain the ordered γ’ or γ’’ phases. Thus microstructurally, it is more similar to an austenitic stainless steel, such as 316 or 304, or Alloy 800H comprised of a predominantly solid solution strengthened matrix phase with a dispersion of inter- and intragranular carbides. Previous studies of the creep-fatigue behavior of Alloy 617 at 950 °C indicate that the fatigue life is reduced when a constant strain dwell is added at peak tensile strain. This results from the combination of faster crack initiation occurring at surface-connected grain boundaries due to oxidation from the air environment along with faster, and intergranular, crack propagation resulting from the linking of extensive interior grain boundary cracking. Saturation, defined as the point at which further increases in the strain-controlled hold time duration no longer decreases the cycle life, has been observed for Alloy 617 at 950 °C at least to the investigated hold times, as illustrated through a plot of cycles to failure v. hold time in Figure 1. The 950 °C creep-fatigue data set generated by Totemeier and Tian at the 0.3% and 1.0% strain range is consistent in magnitude in terms of the cycles to failure data of that of Carroll et al., however, 0.3% strain range data did not exhibit saturation at hold times of up to 10 min. At 1.0% total strain, saturation in the number of cycles to failure was observed within the investigated peak tensile hold times of up to 10 min. The data of Carroll et al. in Figure 1 and Totemeier and Tian is also consistent in magnitude with the data of Rao and coworkers investigated at the 0.6% strain range. It should be noted that saturation in the number of cycles to failure is not present in the data published by Rao and coworkers for tensile hold times of up to 120 min. The latter testing was in a simulated primary-circuit helium gas as opposed to air and a single data point is reported for the longer hold time conditions.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2018

Isodimorphism in a binary system BaBi4Ti4O15-CaBi4Ti4O15

Highlights: • Isodimorphism for two Aurivillius phases BaBi{sub 4}Ti{sub 4}O{sub 15} and CaBi{sub 4}Ti{sub 4}O{sub 15} with different symmetry was studied. • The structure of the compounds has been studied using X-ray diffraction and Raman spectroscopy. • The solid solutions with tetragonal and orthorhombic symmetry were formed in the range of 0 • The basic laws of thermal expansion for the binary system BaBi{sub 4}Ti{sub 4}O{sub 15} –CaBi{sub 4}Ti{sub 4}O{sub 15} have been established. - Abstract: Isodimorphism for two Aurivillius phases BaBi{sub 4}Ti{sub 4}O{sub 15} and CaBi{sub 4}Ti{sub 4}O{sub 15} with different symmetry was studied. Synthesis techniques have been optimized and solid solution with the composition Ba{sub 1-x}Ca{sub x}Bi{sub 4}Ti{sub 4}O{sub 15} (x – molar part of the component, x = 0, 0.25, 0.5, 0.75, 1) have been prepared. The structure of the compounds has been studied using X-ray diffraction and Raman spectroscopy. It was found that solid solutions with tetragonal and orthorhombic symmetry were formed in the range of 04Ti{sub 4}O{sub 15} –CaBi{sub 4}Ti{sub 4}O{sub 15} have been established.

36 MATERIALS SCIENCE↗
DOE OSTI2013

A new way of phase identification, of AgGaGeS{sub 4}∙nGeS{sub 2} crystals

The phase identification of AgGaGeS{sub 4}·nGeS{sub 2} (n=0–4) crystals grown by vertical Bridgman–Stockbarger technique was carried out to find the boundary value n between a homogeneous solid solution and its mixture with GeS{sub 2}. To obtain reliable results, the conventional methods of X-ray diffraction (XRD) and energy dispersive X-ray spectroscopy (EDX) were completed by less common vapor pressure measurement in a closed volume and precise density measurements, which are very sensitive to the detection of small amounts of crystalline and glassy GeS{sub 2} and heterogeneous state of the crystals. The boundary value n=1.5 at 1045 K and the coexistence of the solid solution AgGaGeS{sub 4}·1.5GeS{sub 2} with the β-GeS{sub 2} phase for n>1.5 was found. Glassy GeS{sub 2} (∼2 mol%) was revealed by vapor pressure measurement and XRD studies in all the crystals. This is discussed in terms of the supersaturated solid solution decomposition upon temperature decreasing and the microphase separation of overcooled melt near the melting point under non-equilibrium crystallization. For the first time, the p–T dependence for glassy GeS{sub 2} was measured by the vapor pressure measurements. - Graphical abstract: lg p–1/T dependences of as-grown AgGaGeS{sub 4}·nGeS{sub 2} crystals. - Highlights: • Vapor pressure measurement as a powerful tool of phase identification. • Thermal characteristics of glassy GeS{sub 2}. • The homogeneity range of AgGaGeS{sub 4} from the GeS{sub 2} side.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Spin-glass behavior of Sn{sub 0.9}Fe{sub 3.1}N: An experimental and quantum-theoretical study

Based on comprehensive experimental and quantum-theoretical investigations, we identify Sn{sub 0.9}Fe{sub 3.1}N as a canonical spin glass and the first ternary iron nitride with a frustrated spin ground state. Sn{sub 0.9}Fe{sub 3.1}N is the end member of the solid solution Sn{sub x}Fe{sub 4−x}N (0 < x ≤ 0.9) derived from ferromagnetic γ′-Fe{sub 4}N. Within the solid solution, the gradual incorporation of tin is accompanied by a drastic weakening of the ferromagnetic interactions. To explore the dilution of the ferromagnetic coupling, the highly tin-substituted Sn{sub 0.9}Fe{sub 3.1}N has been magnetically reinvestigated. DC magnetometry reveals diverging susceptibilities for FC and ZFC measurements at low temperatures and an unsaturated hysteretic loop even at high magnetic fields. The temperature dependence of the real component of the AC susceptibility at different frequencies proves the spin-glass transition with the characteristic parameters T{sub g} = 12.83(6) K, τ{sup *} = 10{sup −11.8(2)} s, zv = 5.6(1) and ΔT{sub m}/(T{sub m} ⋅ Δlgω) = 0.015. The time-dependent response of the magnetic spins to the external field has been studied by extracting the distribution function of relaxation times g(τ, T) up to T{sub g} from the complex plane of AC susceptibilities. The weakening of the ferromagnetic coupling by substituting tin into γ′-Fe{sub 4}N is explained by the Stoner criterion on the basis of electronic structure calculations and a quantum-theoretical bonding analysis.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Crystal chemistry and optical investigations of the Cu{sub 2}Zn(Sn,Si)S{sub 4} series for photovoltaic applications

Different compounds in the Cu{sub 2}ZnSnS{sub 4}–Cu{sub 2}ZnSiS{sub 4} system have been prepared via ceramic route and structurally characterized via X-ray diffraction on powders and single crystals. Two solid solutions were identified along the Cu{sub 2}Zn(Sn,Si)S{sub 4} series. Namely, materials with Si-content x=Si/(Sn+Si) lower than 0.5 crystallize with the Cu{sub 2}ZnSnS{sub 4} kesterite structure type while materials with x higher than 0.8 adopt the Cu{sub 2}ZnSiS{sub 4} enargite structure type. In between, a miscibility gap occurs where the Cu{sub 2}ZnSn{sub 0.5}Si{sub 0.5}S{sub 4} and Cu{sub 2}ZnSn{sub 0.2}Si{sub 0.8}S{sub 4} compounds co-exist. The optical bandgap increases continuously with the Si content in the whole series. This opens up the possibility to fine tune the absorption threshold and to adjust it to 1.7 eV for x∼0.5, the optimum value for the top cell of tandem solar devises to achieve high photovoltaic conversion efficiency. - Graphical abstract: Two solid solutions have been pointed out in the Cu{sub 2}Zn(Sn{sub 1−x}Si{sub x})S{sub 4} series with the kesterite and the enargite type structures. - Highlights: • New compounds in Cu{sub 2}Zn(Sn,Si)S{sub 4} series have been prepared. • Two solid solutions Cu{sub 2}ZnSn{sub 1−x}Si{sub x}S{sub 4} were identified for x≤0.5 and x≥0.8. • In the miscibility gap 2 phases co-exist with kesterite and enargite structure types. • The optical bandgap increases continuously with the Si-content in the whole series. • These materials could be envisioned as absorber in thin-film solar cells.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗