Processes of physical treatment of stainless steels obtained by additive manufacturing

With a vista of available stainless steel grades at our disposal, it is possible to manufacture items for a wide range of industries. These include chemicals production, medicine, and pharmacology, aerospace, power engineering, etc. Stainless steels are widely used mostly due to their unique property set, both mechanical and physicochemical ones, achieved by alloying various components. Stainless steel workpieces are usually obtained by melting, alloying, casting, and subsequent rolling to the desired shape. The experience in the study of the microstructure and processes of physical treatment of steel accumulated to the present day mainly concerns the machinability (blade, abrasive, laser, etc.) of such steels obtained by conventional techniques. Meanwhile, approaches to the production of workpieces from stainless steels by additive manufacturing (AM) methods are actively developing. In their turn, additive manufacturing technologies allow for producing workpieces that are structurally as close as possible to the final product shape. However, the use of AM workpieces in the manufacturing of functional products brings questions related to the study of the treatability of such steels by mechanical and physical processes to achieve a wide range of functional characteristics. This article discusses the issues of treatability and the characteristics and properties of stainless steels obtained by AM

Effect of the mass fraction of NiTi–TiB2 SHS-particles on the phase composition, structure, and mechanical properties of inconel 625–NiTi–TiB2 composites produced by direct laser deposition

This paper studies the impact of the mass fraction of NiTi–TiB2 particles obtained by the method of self-propagating high-temperature synthesis (SHS) on the phase composition, structure, and mechanical properties of composites made by direct laser deposition from an Inconel 625–NiTiz–TiB2 powder mixture. Composites were obtained from a powder mixture with the mass fraction of particles at 5–10 wt%, and they consisted of an Inconel 625 metal matrix wherein ceramic inclusions of titanium diboride TiB2 were distributed. Increasing the mass fraction of SHS-produced NiTi particles from 30 to 95 wt% led to the emergence of a NiTi intermetallide phase in the matrix material as wellas an increase in the average TiB2 particle size and formation of their agglomerates. In addition, an increase in the microhardness of the materials was observed. The graph of tensile strength of Inconel 625–NiTi–TiB2 samples has a parabolic shape with a maximum at 1000 MPa (when the mass fraction of SHS-produced NiTi–TiB2 particles is at 30 wt%). A further increase in the mass fraction of NiTi–TiB2 led to a decrease in the tensile strength down to 400 MPa. Here the deformation of samples decreases linearly as the ratio of composite particles in the initial mixture increases. From a comparative analysis of the results obtained, the optimal mass fraction of composite NiTi–TiB2 particles in the Inconel 625-NiTi–TiB2 powder mixture was found to be 5 wt%

Synthesis and properties of the heterospin (S1 = S2 = 1/2) radical-ion salt bis(mesitylene)molybdenum(I) [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazolidyl

The authors are grateful to the Presidium of the Russian Academy of Sciences (Project 8.14), the Royal Society (RS International Joint Project 2010/R3), the Leverhulme Trust (Project IN-2012-094), the Siberian Branch of the Russian Academy of Sciences (Project 13), the Ministry of Education and Science of the Russian Federation (Project of Joint Laboratories of Siberian Branch of the Russian Academy of Sciences and National Research Universities), and the Russian Foundation for Basic Research (Projects 13-03-00072 and 15-03-03242) for financial support of various parts of this work. N.A.S. thanks the Council for Grants of the President of Russian Federation for postdoctoral scholarship (grant MK-4411.2015.3). B.E.B. is grateful for an EaStCHEM Hirst Academic Fellowship. A.V.Z. thanks the Foundation named after D. I. Mendeleev, Tomsk State University, for support of his work.Low-temperature interaction of [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazole (1) with MoMes2 (Mes = mesitylene / 1,3,5-trimethylbenzene) in tetrahydrofuran gave the heterospin (S1 = S2 = 1/2) radical-ion salt [MoMes2]+[1]– (2) whose structure was confirmed by single-crystal X-ray diffraction (XRD). The structure revealed alternating layers of the cations and anions with the Mes ligands perpendicular, and the anions tilted by 45°, to the layer plane. At 300 K the effective magnetic moment of 2 is equal to 2.40 μB (theoretically expected 2.45 μB) and monotonically decreases with lowering of the temperature. In the temperature range 2−300 K, the molar magnetic susceptibility of 2 is well-described by the Curie-Weiss law with parameters C and θ equal to 0.78 cm3⋅K⋅mol–1 and −31.2 K, respectively. Overall, the magnetic behavior of 2 is similar to that of [CrTol2]+[1]– and [CrCp*2]+[1]–, i.e. changing the cation [MAr2]+ 3d atom M = Cr (Z = 24) with weak spin-orbit coupling (SOC) to a 4d atom M = Mo (Z = 42) with stronger SOC does not affect macroscopic magnetic properties of the salts. For the XRD structure of salt 2, parameters of the Heisenberg spin-Hamiltonian were calculated using the broken-symmetry DFT and CASSCF approaches, and the complex 3D magnetic structure with both the ferromagnetic (FM) and antiferromagnetic (AF) exchange interactions was revealed with the latter as dominating. Salt 2 is thermally unstable and slowly loses the Mes ligands upon storage at ambient temperature. Under the same reaction conditions, interaction of 1 with MoTol2 (Tol = toluene) proceeded with partial loss of the Tol ligands to afford diamagnetic product.PostprintPostprintPeer reviewe

Comparative Structural Study of Three Tetrahalophthalic Anhydrides: Recognition of X···O(anhydride) Halogen Bond and πh···O(anhydride) Interaction

Structures of three tetrahalophthalic anhydrides (TXPA: halogen = Cl (TCPA), Br (TBPA), I (TIPA)) were studied by X-ray diffraction, and several types of halogen bonds (HaB) and lone pair···π-hole (lp···πh) contacts were revealed in their structures. HaBs involving the central oxygen atom of anhydride group (further X···O(anhydride) were recognized in the structures of TCPA and TBPA. In contrast, for the O(anhydride) atom of TIPA, only interactions with the π system (π-hole) of the anhydride ring (further lp(O)···πh) were observed. Computational studies by a number of theoretical methods (molecular electrostatic potentials, the quantum theory of atoms in molecules, the independent gradient model, natural bond orbital analyses, the electron density difference, and symmetry-adapted perturbation theory) demonstrated that the X···O(anhydride) contacts in TCPA and TBPA and lp(O)···πh in TIPA are caused by the packing effect. The supramolecular architecture of isostructural TCPA and TBPA was mainly affected by X···O(acyl) and X···X HaBs, and, for TIPA, the main contribution provided I···I HaBs

Conformation-Associated C···<i>d_z</i>²-Pt^II Tetrel Bonding: The Case of Cyclometallated Platinum(II) Complex with 4-Cyanopyridyl Urea Ligand

The nucleophilic addition of 3-(4-cyanopyridin-2-yl)-1,1-dimethylurea (1) to cis-[Pt(CNXyl)2Cl2] (2) gave a new cyclometallated compound 3. It was characterized by NMR spectroscopy (1H, 13C, 195Pt) and high-resolution mass spectrometry, as well as crystallized to obtain two crystalline forms (3 and 3·2MeCN), whose structures were determined by X-ray diffraction. In the crystalline structure of 3, two conformers (3A and 3B) were identified, while the structure 3·2MeCN had only one conformer 3A. The conformers differed by orientation of the N,N-dimethylcarbamoyl moiety relative to the metallacycle plane. In both crystals 3 and 3·2MeCN, the molecules of the Pt(II) complex are associated into supramolecular dimers, either {3A}2 or {3B}2, via stacking interactions between the planes of two metal centers, which are additionally supported by hydrogen bonding. The theoretical consideration, utilizing a number of computational approaches, demonstrates that the C···dz2(Pt) interaction makes a significant contribution in the total stacking forces in the geometrically optimized dimer [3A]2 and reveals the dz2(Pt)→π*(PyCN) charge transfer (CT). The presence of such CT process allowed for marking the C···Pt contact as a new example of a rare studied phenomenon, namely, tetrel bonding, in which the metal site acts as a Lewis base (an acceptor of noncovalent interaction)

Hybrid 2D Supramolecular Organic Frameworks (SOFs) Assembled by the Cooperative Action of Hydrogen and Halogen Bonding and π⋯π Stacking Interactions

The cis- and trans-isomers of 6-(3-(3,4-dichlorophenyl)-1,2,4-oxadiazol-5-yl)cyclohex-3-ene-1-carboxylic acid (cis-A and trans-A) were obtained by the reaction of 3,4-dichloro-N′-hydroxybenzimidamide and cis-1,2,3,6-tetrahydrophthalic anhydride. Cocrystals of cis-A with appropriate solvents (cis-A‧½(1,2-DCE), cis-A‧½(1,2-DBE), and cis-A‧½C6H14) were grown from 1,2-dichloroethane (1,2-DCE), 1,2-dibromoethane (1,2-DBE), and a n-hexane/CHCl3 mixture and then characterized by X-ray crystallography. In their structures, cis-A is self-assembled to give a hybrid 2D supramolecular organic framework (SOF) formed by the cooperative action of O–H⋯O hydrogen bonding, Cl⋯O halogen bonding, and π⋯π stacking. The self-assembled cis-A divides the space between the 2D SOF layers into infinite hollow tunnels incorporating solvent molecules. The energy contribution of each noncovalent interaction to the occurrence of the 2D SOF was verified by several theoretical approaches, including MEP and combined QTAIM and NCIplot analyses. The consideration of the theoretical data proved that hydrogen bonding (approx. −15.2 kcal/mol) is the most important interaction, followed by π⋯π stacking (approx. −11.1 kcal/mol); meanwhile, the contribution of halogen bonding (approx. −3.6 kcal/mol) is the smallest among these interactions. The structure of the isomeric compound trans-A does not exhibit a 2D SOF architecture. It is assembled by the combined action of hydrogen bonding and π⋯π stacking, without the involvement of halogen bonds. A comparison of the cis-A structures with that of trans-A indicated that halogen bonding, although it has the lowest energy in cis-A-based cocrystals, plays a significant role in the crystal design of the hybrid 2D SOF. The majority of the reported porous halogen-bonded organic frameworks were assembled via iodine and bromine-based contacts, while chlorine-based systems—which, in our case, are structure-directing—were unknown before this study

Noncovalent Chelation by Halogen Bonding in the Design of Metal-Containing Arrays: Assembly of Double σ‑Hole Donating Halolium with Cu^I‑Containing O,O‑Donors

Five new copper(I) complexescomposed of the paired dibenzohalolium and [CuL2]− (L = 1,2,4-oxadiazolate) counterions in which O,O-atoms of the anion are simultaneously linked to the halogen atomwere generated and isolated as the solid via the three-component reaction between [Cu(MeCN)4](BF4), sodium 1,2,4-oxadiazolates, and dibenzohalolium triflates (or trifluoroacetates). This reaction is different from the previously reported CuI-catalyzed arylation of 1,2,4-oxadiazolones by diaryliodonium salts. Inspection of the solid-state X-ray structures of the complexes revealed the strong three-center X···O,O (X = Br, I) halogen bonding occurred between the oxadiazolate moieties and dibenzohalolium cation. According to performed theoretical calculations, this noncovalent interaction (or noncovalent chelation) was recognized as the main force in the stabilization of the copper(I) complexes. An explanation for the different behavior of complexes, which provide either chelate or nonchelate binding, is based on the occurrence of additional −CH3···π interactions, which were also quantified

Synthesis and properties of the heterospin (S1=S2=1/2) radical-ion salt bis(mesitylene)molybdenum(I)[1,2,5]thiadiazolo[3,4c][1,2,5]thiadiazolidyl

Low-temperature interaction of [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazole (1) with MoMes2 (Mes = mesitylene/1,3,5-trimethylbenzene) in tetrahydrofuran gave the heterospin (S1 = S2 = 1/2) radical-ion salt [MoMes2]+[1]− (2) whose structure was confirmed by single-crystal X-ray diffraction (XRD). The structure revealed alternating layers of the cations and anions with the Mes ligands perpendicular, and the anions tilted by 45°, to the layer plane. At 300 K the effective magnetic moment of 2 is equal to 2.40 μB (theoretically expected 2.45 μB) and monotonically decreases with lowering of the temperature. In the temperature range 2–300 K, the molar magnetic susceptibility of 2 is well-described by the Curie–Weiss law with parameters C and θ equal to 0.78 cm3 K mol–1 and −31.2 K, respectively. Overall, the magnetic behavior of 2 is similar to that of [CrTol2]+[1]− and [CrCp*2]+[1]−, i.e., changing the cation [MAr2]+ 3d atom M = Cr (Z = 24) with weak spin–orbit coupling (SOC) to a 4d atom M = Mo (Z = 42) with stronger SOC does not affect macroscopic magnetic properties of the salts. For the XRD structure of salt 2, parameters of the Heisenberg spin-Hamiltonian were calculated using the broken-symmetry DFT and CASSCF approaches, and the complex 3D magnetic structure with both the ferromagnetic (FM) and antiferromagnetic (AF) exchange interactions was revealed with the latter as dominating. Salt 2 is thermally unstable and slowly loses the Mes ligands upon storage at ambient temperature. Under the same reaction conditions, interaction of 1 with MoTol2 (Tol = toluene) proceeded with partial loss of the Tol ligands to afford diamagnetic product

Synthesis and properties of the heterospin (S1=S2=1/2) radical-ion salt bis(mesitylene)molybdenum(I)[1,2,5]thiadiazolo[3,4c][1,2,5]thiadiazolidyl

Low-temperature interaction of [1,2,5]thiadiazolo[3,4-c][1,2,5]thiadiazole (1) with MoMes2 (Mes = mesitylene/1,3,5-trimethylbenzene) in tetrahydrofuran gave the heterospin (S1 = S2 = 1/2) radical-ion salt [MoMes2]+[1]− (2) whose structure was confirmed by single-crystal X-ray diffraction (XRD). The structure revealed alternating layers of the cations and anions with the Mes ligands perpendicular, and the anions tilted by 45°, to the layer plane. At 300 K the effective magnetic moment of 2 is equal to 2.40 μB (theoretically expected 2.45 μB) and monotonically decreases with lowering of the temperature. In the temperature range 2–300 K, the molar magnetic susceptibility of 2 is well-described by the Curie–Weiss law with parameters C and θ equal to 0.78 cm3 K mol–1 and −31.2 K, respectively. Overall, the magnetic behavior of 2 is similar to that of [CrTol2]+[1]− and [CrCp*2]+[1]−, i.e., changing the cation [MAr2]+ 3d atom M = Cr (Z = 24) with weak spin–orbit coupling (SOC) to a 4d atom M = Mo (Z = 42) with stronger SOC does not affect macroscopic magnetic properties of the salts. For the XRD structure of salt 2, parameters of the Heisenberg spin-Hamiltonian were calculated using the broken-symmetry DFT and CASSCF approaches, and the complex 3D magnetic structure with both the ferromagnetic (FM) and antiferromagnetic (AF) exchange interactions was revealed with the latter as dominating. Salt 2 is thermally unstable and slowly loses the Mes ligands upon storage at ambient temperature. Under the same reaction conditions, interaction of 1 with MoTol2 (Tol = toluene) proceeded with partial loss of the Tol ligands to afford diamagnetic product