Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “bonding”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 523 records · Page 29
All sourcesNASA NTRSDOE OSTI
DOE OSTI2018

Analysis of Acoustic Emission Propagation in Metal-to-Metal Adhesively Bonded Joints

Acoustic emission (AE) monitoring shows promise as one of the most effective methods for condition monitoring of adhesively-bonded joints. Previous research has demonstrated its ability to detect, locate and classify adhesive joint failure, though in these studies little attention appears to have been paid to the differences in AE wave propagation through the bonded and un-bonded sections of the specimens tested, or to the effects of the wave modes excited or the propagation distances. This paper details an experimental study conducted on large aluminium sheet specimens to identify the effects of the presence of an adhesive layer on AE wave propagation. Three specimens are considered; a single aluminium sheet, two aluminium sheets placed together without adhesive, and an adhesively-bonded specimen. A pencil lead break (PLB) is used as a simulated AE source, and is applied to the three specimens at varying propagation distances and orientations. The acquired signals are processed using wavelet-transforms to explore time-frequency features, and compared with modified group-velocity curves based on the Rayleigh–Lamb equations to allow identification of wave-modes and edge-reflections. The effects of propagation distance and source orientation are investigated while comparison is made between the three specimens. It is concluded that while the wave propagation modes can be approximated as being constant throughout all three specimens, there is a significant change in the received waveforms due to the attenuation of high-frequency components exhibited by the bonded specimen. These findings may be utilised to provide a deeper understanding of acquired AE data, improving the current abilities to identify, locate and characterise damage mechanisms occurring within adhesive joints, ultimately improving safety in the use of adhesive bonding for critical applications.

42 ENGINEERING↗
DOE OSTI2022

The Effect of APS-HVOF Bond Coating Thickness Ratio on TBC Furnace Cycle Lifetime

In this work, combinations of NiCoCrAlY APS and high-velocity oxygen fuel (HVOF) bond coatings were deposited on alloy 247 disk substrates with APS yttria-stabilized zirconia (YSZ) top coatings to assess the benefit of air plasma sprayed (APS) ‘flash’ bond coatings. Using 1-h cycles at 1100 °C in air with 10% H 2 O and HVOF-only and APS-only bond coatings as a baseline, it was found that APS flash coatings extended the average coating lifetime by 16% to 35% with the thicker flash coating performing best. Principal component analysis and energy dispersive spectroscopy (EDS) compositional mapping on coatings characterized after 0, 100, 300 and 500 cycles and after failure showed that the Al in the bond coatings was depleted due to both oxidation and back diffusion into the substrate. The APS-only bond coating had significant oxidation throughout the bond coating and was so depleted in Al, that Al diffused from the substrate to the coating. Residual stress maps of the thermally-grown alumina scale were obtained every 100 cycles using photo-stimulated luminescence piezospectroscopy (PLPS) revealing that the Thick Flash coating had the slowest rate of damage accumulation in the oxide scale.

alumina scale↗
DOE OSTI2018

Wear-Resistant Al/SiC-Gr Hybrid Metal Matrix Composite Fabricated by Multiple Annealing and Roll Bonding

The wear-resistant Al/SiC-Gr hybrid composite with a good combination of strength and ductility is fabricated by multiple annealing and roll bonding. The challenge is that graphite acts as a soft lubricating material and prevents the bonding between the layers. In order to evaluate the bond strength, the peeling test is used after cold roll bonding of Al strips with and without the addition of particles under different conditions. Results show that the bond strength increases with increasing the reduction in thickness, decreasing Gr content and performing the post-rolling annealing. During the multiple annealing and roll bonding process, the tensile strength increases with the cost of a small decrease in elongation. A relatively uniform distribution of particles is achieved at the last stages of the process. The Al/SiC-Gr hybrid composite exhibits an improved wear resistance compared with the monolithic Al and Al/SiC composite produced under the same conditions. The conclusion is drawn that a good combination of wear and mechanical properties can be achieved in the hybrid composite that has less amount of Gr.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Effects of Holding Time on the Sintering of Cemented Tungsten Carbide Powder and Bonding with High-Strength Steel Wire

Cemented tungsten carbide (WC-10Co) and high-strength (AISI 4340) steel were successfully bonded by hot compaction diffusion bonding at a low temperature. The effects of holding time (5-50 min) on microstructure and mechanical properties of the sintered carbides and bonding strengths of the dissimilar bilayered composite materials were examined. The results show that the mechanical properties of the carbides increase, but the bonding strength increases firstly and then decreases with the increase in holding time. The maximum density and hardness achieved are 95.92 and 99.5%, respectively. A transitional layer forms at the interface as a result of elemental interdiffusion. The depth of the layer increases with the increase in holding time. The optimal bonding time is determined to be 40 min at a temperature of 1200°C and a pressure 160 MPa, by which the maximum bonding strength of 204 MPa of the WC-10Co/4340 steel joints can be achieved.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Crystal structure details of La- and Bi-substituted hydroxyapatites: Evidence for LaO{sup +} and BiO{sup +} with a very short metal–oxygen bond

Crystal structures of substituted apatites with general formula Ca{sub 10−x}M{sub x}(PO{sub 4}){sub 6}(OH{sub 1−δ}){sub 2−x}O{sub x}, where M=La, Bi, 0≤x<2, were refined using high-resolution X-ray powder diffraction patterns. Individual positions for Ca{sup 2+} and M{sup 3+}-ions localized near Ca2-site were determined. The M{sup 3+}-ion was found shifted toward the hexagonal channel center with respect to the Ca{sup 2+}-ion, forming very short bond with the intrachannel O{sup 2−}, while leaving considerably longer distances to other oxygen atoms, which suggested the existence of a MO{sup +} ion. Distinct bands of stretching M–O modes were observed in the Raman and FT-IR spectra of the compounds. The bond lengths for BiO{sup +} and LaO{sup +} were estimated to be 2.05(1) and 2.09(1) Å correspondingly. The latter was almost 0.3 Å lower than the shortest La–O bond in La{sub 2}O{sub 3}. The realization of such a strong lanthanide–oxygen bond in a crystal lattice could provide a very high axial ligand field and might be implemented to develop high-energy-barrier single-molecule magnets as well as to tune properties of lanthanide-based luminophores. - Graphical abstract: A fragment of the La-for-Ca substituted apatite crystal structure focusing on the La–O bond. - Highlights: • Individual positions in the apatite crystal lattice for a doping atom (La, Bi) and Ca. • The doping atom shifts toward the center of the hexagonal channel. • BiO{sup +} and LaO{sup +} with estimated short bond lengths of 2.05 and 2.09 Å respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Structure and Bonding of 1,2,4-Triazole Thiones Derived from Nitron

The molecular structures of two 1,2,4-triazole thiones derived from Nitron, namely Nitron(S) and Nitron(S) Me , have been determined by single crystal X-ray diffraction. Comparison with the structure of Nitron indicates that the formation of the thiones is accompanied by a shortening of the C–N bond within the 5-membered ring that is opposite to the thione group, and a lengthening of the exocyclic C–N bond. Analysis of the structures of Nitron, Nitron(S) and Nitron(S) Me , together with hypothetical versions in which the phenyl substituents are replaced by hydrogen, indicates that these changes are in accord with bond order differences predicted by natural bond orbital methods. Here, a similar evaluation of the thione groups of Nitron(S) and Nitron(S)Me indicates that the C–S bonds are composed of both covalent and ionic components and are best described by a combination of resonance structures that feature C=S double and C–S single bonds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Role of bond coat processing methods on the durability of plasma sprayed thermal barrier systems

Metallic alloy bond coats are used as an interlayer to promote adhesion of ceramic Thermal Barrier Coatings (TBCs) to the superalloy substrates. These bond coats can be applied through a variety of processing means such as Air Plasma Spray (APS), High-Velocity Oxy Fuel spray (HVOF), and Vacuum Plasma Spray (VPS). While widely adopted in the industry, some uncertainties remain as to the specific microstructural attributes which are influenced by the processing routes and their implications on durability. This paper seeks to elucidate these subtleties between bond coat deposition processing routes through an integrated study of processing to connect to furnace cycle durability on a single bond coat chemistry of NiCoCrAlYHfSi. A standard porous APS TBC top coating based on yttria stabilized zirconia (7YSZ) was consistently applied on these distinct bond coats and tested for durability in cyclic furnace testing at 1100 °C. The results point to substantial differences in durability which are not readily explained only by the variances in coating roughness. Detailed assessment of deposited bond coat properties (modulus, thermal expansion, chemistry) provided some explanation relative to durability. Here, the results suggest a complex interplay among roughness, compliance, aluminum diffusion pathway, and thermal expansion mismatch. Photo-stimulated luminescence piezospectroscopy (PLPS) provided additional insights enabling a comprehensive assessment of processing-performance linkages.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Recycling of additively printed rare-earth bonded magnets

Here, we describe an efficient and environmentally benign method of recycling of additive printed Nd-Fe-B polymer bonded magnets. Rapid pulverization of bonded magnets into composite powder containing Nd-Fe-B particles and polymer binder was achieved by milling at cryogenic temperatures. The recycled bonded magnets fabricated by warm compaction of ground cryomilled coarse composite powders and nylon particles showed improved magnetic properties and density. Remanent magnetization and saturation magnetization increased by 4% and 6.5% respectively, due to enhanced density while coercivity and energy product were retained from the original additive printed bonded magnets. This work presents a facile method that enables the direct reuse of end-of-life bonded magnets for remaking new bonded magnets. In addition to magnetic properties, mechanical properties comparable to commercial products have been achieved. This research advances efforts to ensure sustainability in critical materials by forming close loop supply chain.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Discovery of S···C≡N Intramolecular Bonding in a Thiophenylcyanoacrylate-Based Dye: Realizing Charge Transfer Pathways and Dye···TiO 2 Anchoring Characteristics for Dye-Sensitized Solar Cells

Donor-pi-acceptor dyes containing thiophenyl pi-conjugated units and cyanoacrylate acceptor groups are among the best-performing organic chromophores used in dye-sensitized solar cell (DSC) applications. Yet, the molecular origins of their high photovoltaic output have remained unclear until now. This synchrotron-based X-ray diffraction study elucidates these origins for the high-performance thiophenylcyanoacrylate-based dye MK-2 (7.7% DSC device efficiency) and its molecular building block, MK-44. The crystal structures of MK-2 and MK-44 are both determined, while a high-resolution charge-density mapping of the smaller molecule was also possible, enabling the nature of its bonding to be detailed. A strong S center dot center dot center dot C equivalent to N intramolecular interaction is discovered, which bears a bond critical point, thus proving that this interaction should be formally classified as a chemical bond. A topological analysis of the pi-conjugated portion of MK-44 shows that this S center dot center dot center dot C equivalent to N bonding underpins the highly efficient intramolecular charge transfer(ICT) in thiophenylcyanoacrylate dyes. This manifests as two bipartite ICT pathways bearing carboxylate and nitrile end points. In turn, these pathways dictate a preferred COO/CN anchoring mode for the dye as it adsorbs onto TiO2 surfaces, to form the dye TiO2 interface that constitutes the DSC working electrode. These results corroborate a recent proposal that all cyanoacrylate groups anchor onto TiO2 in this COO/CN binding configuration. Conformational analysis of the MK-44 and MK-2 crystal structures reveals that this S center dot center dot center dot C equivalent to N bonding will persist in MK-2. Accordingly, this newly discovered bond affords a rational explanation for the attractive photovoltaic properties of,MK-2. More generally, this study provides the first unequivocal evidence for an S center dot center dot center dot C equivalent to N interaction, confirming previous speculative assignments of such interactions in other compounds.

charge-density mapping↗
DOE OSTI2020

Formic Acid: A Hydrogen-Bonding Cocatalyst for Formate Decomposition

Hydrogen bonding accelerates many catalytic reactions by orienting intermediates, stabilizing transition states, and even opening reaction pathways. However, most mechanistic studies regarding the decomposition of formic acid (FA), a promising hydrogen storage material, neglect hydrogen-bonding interactions even though FA is a strong hydrogen-bond donor and acceptor. Here, we probe the formation of bimolecular hydrogen-bonded complexes between FA and formate (FA–HCOO complexes) adsorbed on metal surfaces and how these complexes affect HCOO* decomposition. Using first-principles density functional theory (DFT) calculations on 12 close-packed (111)/(0001) and 8 open (100) surfaces of 12 transition metals—Ag, Au, Co, Cu, Ir, Ni, Os, Re, Pd, Pt, Rh, and Ru, we—show that FA–HCOO complexes are generally thermodynamically stable, even at elevated temperatures and pressures. We then illustrate that these complexes produce infrared spectroscopic signatures consistent with as yet unassigned experimental peaks. We last demonstrate that by stabilizing the dangling bond of monodentate HCOO*, these complexes significantly lower the barriers for rotation of HCOO* from a bidentate to a monodentate configuration, the rate-limiting step for HCOO* decomposition on many surfaces. FA thus acts as a cocatalyst for HCOO* decomposition. Our results may guide the community toward improved catalysts for reactions involving HCOO* such as FA decomposition, methanol steam reforming, and the water gas shift reaction. More broadly, our work highlights the ability of hydrogen bonding to modify the adsorbed structures of intermediates and lower the barriers for their reaction on heterogeneous catalysts. Lastly, this phenomenon can be relevant for other reactions involving ammonia, alcohols, and carboxylic acids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Hydrogen Bonding Analysis of Structural Transition-Induced Symmetry Breaking and Spin Splitting in a Hybrid Perovskite Employing a Synergistic Diffraction-DFT Approach

Two-dimensional (2D) hybrid organic–inorganic perovskites (HOIPs) offer an outstanding opportunity for spin-related technologies owing in part to their tunable structural symmetry breaking and distortions driven by organic–inorganic hydrogen (H) bonds. However, understanding how H-bonds tailor inorganic symmetry and distortions and therefore enhance spin splitting for more effective spin manipulation remains imprecise due to challenges in measuring H atom positions using X-ray diffraction. Here, we report a thermally induced structural transition (at ~209 K) for a 2D HOIP, (2-BrPEA) 2 PbI 4 [2-BrPEA = 2-(2-bromophenyl)ethylammonium], which induces inversion asymmetry and a strong spin splitting (ΔE > 30 meV). While X-ray diffraction generally establishes heavy atom coordinates, we utilize neutron diffraction for accurate H atom position determination, demonstrating that the structural transition-induced rearrangement of H-bonds with distinct bond strengths asymmetrically shifts associated iodine atom positions. Further, consequences of this shift include an increased structural asymmetry, an enhanced difference between adjacent interoctahedra distortions (i.e., Pb–I–Pb bond angles), and therefore significant spin splitting. We further show that H-only density-functional theory (DFT) relaxation of the X-ray structure shifts H atoms to positions that are consistent with the neutron experimental data, validating a convenient pathway to more generally improve upon HOIP H-bonding analyses derived from quicker/less-expensive X-ray data.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Synthesis and Computational Analysis of Uranium(III)-Pnictogen Bonds

In this report, we describe the synthesis and characterization of two novel complexes that contain uranium(III)-pnictogen (P: 1-PMes 2 ; As: 1-AsMes 2 ) bonds to elucidate the degrees of covalency among these bonds. To our knowledge, this is the first reported uranium(III)-arsenic complex to be synthesized and characterized. Analysis of the phosphorus and arsenic bonds reveals a similar electronic environment, assessed by UV–vis NIR, that is comparable to other previously reported uranium(III) complexes. A computational analysis of these compounds and their congeners, N, Sb, and Bi, was performed to identify trends in the overall bonding character of the complexes. This analysis shows that bond covalency decreases as the pnictogen becomes heavier and that overall the interaction energy and its components decrease down the group. Here, this study provides an in-depth analysis and understanding of the nature of bonding between hard actinide and soft pnictogen centers.

Actinides↗
DOE OSTI2021

Breaking a dative bond with mechanical forces

Bond breaking and forming are essential components of chemical reactions. Recently, the structure and formation of covalent bonds in single molecules have been studied by non-contact atomic force microscopy (AFM). Here, we report the details of a single dative bond breaking process using non-contact AFM. The dative bond between carbon monoxide and ferrous phthalocyanine was ruptured via mechanical forces applied by atomic force microscope tips; the process was quantitatively measured and characterized both experimentally and via quantum-based simulations. Our results show that the bond can be ruptured either by applying an attractive force of ~150 pN or by a repulsive force of ~220 pN with a significant contribution of shear forces, accompanied by changes of the spin state of the system. Our combined experimental and computational studies provide a deeper understanding of the chemical bond breaking process.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Influence of the bonding front propagation on the wafer stack curvature

The influence of the dynamics of the direct wafer bonding process on the curvature of the final wafer stack is investigated. An analytical model for the final curvature of the bonded wafers is developed, as a function of the different load components acting during the bonding front propagation, using thin plate theory and considering a strain discontinuity locked at the bonding interface. Experimental profiles are measured for different bonding conditions and wafer thicknesses. A very good agreement with the model prediction is obtained and the influence of the thin air layer trapped in-between the two wafers is demonstrated. The proposed model contributes to further improvement of the bonding process, in particular, for the stacking of layers of electronic devices, which requires a high accuracy of wafer-to-wafer alignment and a very low distortion level.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Tetrel, chalcogen, and CH⋅⋅O hydrogen bonds in complexes pairing carbonyl-containing molecules with 1, 2, and 3 molecules of CO{sub 2}

The complexes formed by H{sub 2}CO, CH{sub 3}CHO, and (CH{sub 3}){sub 2}CO with 1, 2, and 3 molecules of CO{sub 2} are studied by ab initio calculations. Three different types of heterodimers are observed, most containing a tetrel bond to the C atom of CO{sub 2}, and some supplemented by a CH⋅⋅O H-bond. One type of heterodimer is stabilized by an anti-parallel arrangement of the C=O bonds of the two molecules. The binding energies are enhanced by methyl substitution on the carbonyl, and vary between 2.4 and 3.5 kcal/mol. Natural bond orbital analysis identifies a prime source of interaction as charge transfer into the π*(CO) antibonding orbital. Heterotrimers and tetramers carry over many of the geometrical and bonding features of the binary complexes, but also introduce O⋅⋅O chalcogen bonds. These larger complexes exhibit only small amounts of cooperativity.

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

Photoelectron spectroscopy of B{sub 4}O{sub 4}{sup −}: Dual 3c-4e π hyperbonds and rhombic 4c-4e o-bond in boron oxide clusters

Gas-phase anion photoelectron spectroscopy (PES) is combined with global structural searches and electronic structure calculations at the hybrid Becke 3-parameter exchange functional and Lee-Yang-Parr correlation functional (B3LYP) and single-point coupled-cluster with single, double, and perturbative triple excitations (CCSD(T)) levels to probe the structural and electronic properties and chemical bonding of the B{sub 4}O{sub 4}{sup 0/−} clusters. The measured PES spectra of B{sub 4}O{sub 4}{sup −} exhibit a major band with the adiabatic and vertical detachment energies (ADE and VDE) of 2.64 ± 0.10 and 2.81 ± 0.10 eV, respectively, as well as a weak peak with the ADE and VDE of 1.42 ± 0.08 and 1.48 ± 0.08 eV. The former band proves to correspond to the Y-shaped global minimum of C{sub s} B{sub 4}O{sub 4}{sup −} ({sup 2}A″), with the calculated ADE/VDE of 2.57/2.84 eV at the CCSD(T) level, whereas the weak band is associated with the second lowest-energy, rhombic isomer of D{sub 2h} B{sub 4}O{sub 4}{sup −} ({sup 2}B{sub 2g}) with the predicted ADE/VDE of 1.43/1.49 eV. Both anion structures are planar, featuring a B atom or a B{sub 2}O{sub 2} core bonded with terminal BO and/or BO{sub 2} groups. The same Y-shaped and rhombic structures are also located for the B{sub 4}O{sub 4} neutral cluster, albeit with a reversed energy order. Bonding analyses reveal dual three-center four-electron (3c-4e) π hyperbonds in the Y-shaped B{sub 4}O{sub 4}{sup 0/−} clusters and a four-center four-electron (4c-4e) π bond, that is, the so-called o-bond in the rhombic B{sub 4}O{sub 4}{sup 0/−} clusters. This work is the first experimental study on a molecular system with an o-bond.

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

A periodic energy decomposition analysis method for the investigation of chemical bonding in extended systems

The development and first applications of a new periodic energy decomposition analysis (pEDA) scheme for extended systems based on the Kohn-Sham approach to density functional theory are described. The pEDA decomposes the bonding energy between two fragments (e.g., the adsorption energy of a molecule on a surface) into several well-defined terms: preparation, electrostatic, Pauli repulsion, and orbital relaxation energies. This is complemented by consideration of dispersion interactions via a pairwise scheme. One major extension toward a previous implementation [Philipsen and Baerends, J. Phys. Chem. B 110, 12470 (2006)] lies in the separate discussion of electrostatic and Pauli and the addition of a dispersion term. The pEDA presented here for an implementation based on atomic orbitals can handle restricted and unrestricted fragments for 0D to 3D systems considering periodic boundary conditions with and without the determination of fragment occupations. For the latter case, reciprocal space sampling is enabled. The new method gives comparable results to established schemes for molecular systems and shows good convergence with respect to the basis set (TZ2P), the integration accuracy, and k-space sampling. Four typical bonding scenarios for surface-adsorbate complexes were chosen to highlight the performance of the method representing insulating (CO on MgO(001)), metallic (H{sub 2} on M(001), M = Pd, Cu), and semiconducting (CO and C{sub 2}H{sub 2} on Si(001)) substrates. These examples cover diverse substrates as well as bonding scenarios ranging from weakly interacting to covalent (shared electron and donor acceptor) bonding. The results presented lend confidence that the pEDA will be a powerful tool for the analysis of surface-adsorbate bonding in the future, enabling the transfer of concepts like ionic and covalent bonding, donor-acceptor interaction, steric repulsion, and others to extended systems.

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

Pressure-induced localisation of the hydrogen-bond network in KOH-VI

Using a combination of ab initio crystal structure prediction and neutron diffraction techniques, we have solved the full structure of KOH-VI at 7 GPa. Rather than being orthorhombic and proton-ordered as had previously be proposed, we find that this high-pressure phase of potassium hydroxide is tetragonal (space group I4/mmm) and proton disordered. It has an unusual hydrogen bond topology, where the hydroxyl groups form isolated hydrogen-bonded square planar (OH){sub 4} units. This structure is stable above 6.5 GPa and, despite being macroscopically proton-disordered, local ice rules enforce microscopic order of the hydrogen bonds. We suggest the use of this novel type of structure to study concerted proton tunneling in the solid state, while the topology of the hydrogen bond network could conceivably be exploited in data storage applications based solely on the manipulations of hydrogen bonds. The unusual localisation of the hydrogen bond network under applied pressure is found to be favored by a more compact packing of the constituents in a distorted cesium chloride structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗