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DOE OSTI2026

Ionization and temperature measurements in warm dense copper using x-ray absorption spectroscopy

We detail experimental results inferring ionization and temperature for warm dense copper plasmas at several times solid density (15–25 g/cm 3 ) and temperatures of 10–21 eV. Experiments performed at the OMEGA Laser Facility generate uniform warm dense matter conditions via symmetric shock compression of a buried copper layer. The plasma is probed with a laser-generated x-ray source to collect the K-shell x-ray absorption spectrum. Fitting bound-bound absorption contributions from constituent charge states of copper provides an estimated $\overline{Z}$ of approximately 4–7 for these warm dense copper plasmas. We find that these partially ionized plasmas have K-edge shifts of 12–30 eV and bound-bound resonance 1s → 3p absorption shifts of 4–26 eV with respect to the cold K edge. This study provides necessary experimental data to improve ionization and opacity models in the warm dense matter regime.

42 ENGINEERING↗

DOE OSTI2020

Copper-Clad Aluminum Windings as an Alternative Conductor for High-Power Electric Vehicle Wireless Charging

In this paper, copper and copper-clad aluminum winding conductors were compared. The effective resistances as functions of frequency for the cored coils were compared using the 3D finite element model frequency sweep analysis for low, medium, and high frequencies. To compare equivalent designs, both coils were designed to have similar direct-current resistance. Benefits of the copper-clad aluminum over the copper coils are presented.

Wojda, Rafal↗

DOE OSTI2025

Rutherford-in-Copper-Channel Conductor for the MARCO Solenoidal Detector Magnet

MARCO will be a superconducting solenoid for a new particle physics detector of the upcoming Electron Ion Collider (EIC) at Brookhaven National Laboratory (NY, USA). The design field at the interaction point is 2.0 T with a nominal current of about 4 kA at 4.5 K. For this magnet, an aluminumstabilized conductor was considered at the very preliminary design phase. After that, since the lack of manufacturers able to deal with aluminum extrusion, copper has been chosen as stabilizer. Thanks to a dedicated design effort, the copper stabilizer and accompanying material choices provided acceptable hadronic interaction length. The conductor is based on a NbTi Rutherford cable that is soldered in a U-shaped copper profile. Here, this paper goes through the definition of the conductor crosssection according to the project requirements and the supplier capabilities. Its characteristics will be detailed and discussed, in particular the RRR and the yield strength of the copper channel needed for protection and mechanics respectively. Finally, a proposal on how to make the joint between two conductors is presented.

Stacchi, Francesco [Commissariat a l'Energie Atomi↗

DOE OSTI2023

CO electroreduction on single-atom copper

Electroreduction of carbon dioxide (CO 2 ) or carbon monoxide (CO) toward C 2+ hydrocarbons such as ethylene, ethanol, acetate and propanol represents a promising approach toward carbon-negative electrosynthesis of chemicals. Fundamental understanding of the carbon–carbon (C-C) coupling mechanisms in these electrocatalytic processes is the key to the design and development of electrochemical systems at high energy and carbon conversion efficiencies. Here, we report the investigation of CO electreduction on single-atom copper (Cu) electrocatalysts. Atomically dispersed Cu is coordinated on a carbon nitride substrate to form high-density copper–nitrogen moieties. Chemisorption, electrocatalytic, and computational studies are combined to probe the catalytic mechanisms. Unlike the Langmuir-Hinshelwood mechanism known for copper metal surfaces, the confinement of CO adsorption on the single-copper-atom sites enables an Eley-Rideal type of C-C coupling between adsorbed (*CO) and gaseous [CO(g)] carbon moxide molecules. The isolated Cu sites also selectively stabilize the key reaction intermediates determining the bifurcation of reaction pathways toward different C 2+ products.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Electrochemical Behavior of Copper Ion Complexed with Nanoparticle Organic Hybrid Materials

Nanoscale Organic Hybrid Materials (NOHMs) have unique properties that show potential for their use as novel electrolytes that can interact with redox active species. In this work, we probe the effects of adding poly(ethyleneimine)-based NOHMs (NOHM-I-PEI) on copper ion electrochemical reactions. As NOHM-I-PEI is added to a solution containing Cu(II), the voltammetric peak current decreases. This is likely caused by strong complex formation between the PEI nitrogen and the copper, similar to complexation observed in solutions of the polymer with copper. Upon copper addition to a NOHM-I-PEI solution, the pH decreases from 10.1, plateauing at pH = 5.3 at ~3:1 N:Cu ratio indicating that Cu(II) displaces protons. The UV–visible spectra exhibit a Cu-PEI peak, the intensity of which levels off at ~2.8 N:Cu. Acid titration of the N-moieties of the PEI reveals three inflections corresponding to N-environments in the PEI. Upon controlling the pH of the solution by buffering, the "sequestration" of Cu(II) is found to occur when there are unprotonated nitrogens present in the NOHM-I-PEI system; this phenomenon is also supported by UV-vis results. Furthermore, this work highlights the potential of and the design of NOHMs to carry charged electroactive species in solutions along with key factors to control for optimal function.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Manufacturing Full-Scale High Gradient Copper Accelerators: Electron Beam Welding and Allied Processes

This DOE ARDAP-funded study examines the technical and business feasibility of manufacturing high-gradient normal conducting RF (NCRF) copper accelerating structures using electron beam welding (EBW) instead of conventional high-temperature brazing. The core motivation is material performance: brazing softens copper significantly, while hard copper alloys have demonstrated ~75% higher operational gradients in SLAC tests, making cold-joining techniques highly attractive. EBW, applied to split-cell (half or quadrant) structure designs, preserves copper hardness away from the weld joint and simplifies machining — but industrial process optimization remains immature and a substantial learning curve is expected. The business case was modeled for two scenarios: a greenfield EBW linac company (> $10M upfront costs, viable above ~30 units/year) and an EBW division added to an existing accelerator firm to reduce risk and upfront costs, at the expense of being less optimal structure for the higher volume production. The study concludes that without a significant increase in demand, private investment alone cannot sustain this capability, and recommends federal support through R&D grants, procurement incentives, and CAPEX cost-sharing to incubate domestic EBW-NCRF manufacturing — with the existing-company model.

43 PARTICLE ACCELERATORS↗

DOE OSTI2021

Lead Contamination Differences in the Muscle of Wild Turkeys Harvested with Lead and Copper-Plated Lead Shot

Abstract Despite the known deleterious effects lead exposure can have on humans, lead remains the most common type of ammunition used to harvest big game and upland game birds. We sampled wild turkey Meleagris gallopavo breast muscle shot with standard lead and copper-plated lead pellets to quantify lead residue concentrations within the wound channel, and we sampled multiple adjacent locations to measure the extent lead contamination spreads through tissue of harvested turkeys. We found that samples taken from the wound channel contained more lead (mean = 3.76 μg/g dry weight) than both samples taken adjacent to the wound channel (mean = 0.20 μg/g dry weight) and samples taken from >5 cm away (mean = 0.15 μg/g dry weight). Additionally, we found that birds harvested with standard lead ammunition did not differ in lead concentrations from those shot with copper-plated lead, suggesting that copper plating does not aid in reducing lead exposure. Our findings suggest that wild turkeys harvested with either lead or copper-plated lead shot have the potential to expose consumers, especially children due to their lower tolerance, to low levels of lead that could exceed daily consumption limits set by the Food and Drug Administration and Centers for Disease Control. However, elevated lead levels were confined to the wound channel, and thus proper preparation of game to remove tissue surrounding wound channels may eliminate or substantially reduce lead exposure from harvested game birds.

Biodiversity & Conservation↗

DOE OSTI2023

Cationic Copper Species Stabilized by Zinc during the Electrocatalytic Reduction of CO 2 Revealed by In Situ X‐Ray Spectroscopy

Abstract Advanced in situ X‐ray absorption spectroscopy characterization of electrochemically co‐electrodeposited bi‐element copper alloy electrodes shows that zinc yields the formation of a stable cationic Cu species during the electroreduction of CO 2 at high cathodic polarization. In contrast, the formation/stabilization of cationic Cu species in copper oxides, or doping Cu with another element, like Ni, is not possible. It is found that the pure and mixed Cu:Zn electrodes behave similarly in term of electrocatalytic selectivity to multi‐carbon products. At higher Zn concentrations the electrode behaves like the pure Zn catalyst, which indicates that the Cu cationic species do not have a significant influence on the selectivity to multi‐carbon products. It is found that in the non‐monotonically distribution of products is dominated in term of surface energy in which copper prefers the surface. Otherwise, this work highlights the importance of in situ characterization to uncover the mechanisms mediating the catalytic reactions in contrast to ex situ or post mortem analysis, which can be a source of misinterpretation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Polyhydrido Copper Nanoclusters with a Hollow Icosahedral Core: [Cu 30 H 18 {E 2 P(OR) 2 } 12 ] (E=S or Se; R= n Pr, i Pr or i Bu)

Although atomically precise polyhydrido copper nanoclusters are of prime interest for a variety of applications, they have so far remained scarce. Here, we describe the synthesis of a dithiophosphate-protected copper(I) hydride-rich nanocluster (NC), [Cu 30 H 18 {S 2 P(O n Pr) 2 } 12 ] ( 1 H ), fully characterized by various spectroscopic methods and single-crystal X-ray diffraction. The X-ray structure of 1 H reveals an unprecedented central Cu 12 hollow icosahedron. Six faces of this icosahedron are capped by Cu 3 triangles, the whole Cu 30 core being wrapped by twelve dithiophosphate ligands and the whole cluster has ideal S 6 symmetry. The locations of the 18 hydrides in 1 H were ascertained by a single-crystal neutron diffraction study. They are composed of three types: capping μ 3 -H, interstitial μ 4 -H (seesaw) and μ 5 -H ligands (square pyramidal), in good agreement with the DFT simulations. The numbers of hydrides and ligand resonances in the 1 H NMR spectrum of 1 H are in line with their coordination environment in the solid state, retaining the S 6 symmetry in solution. Furthermore, two new Se-protected polyhydrido copper nanoclusters, [Cu 30 H 18 {Se 2 P(OR) 2 } 12 ] ( 2 H : R= i Pr 3 H : R= i Bu) were synthesized from their sulfur relative 1 H via ligand displacement reaction and their X-ray structures feature the exceptional case where both the NC shape and size are fully conserved during the course of ligand exchange. DFT and TD-DFT calculations allow understanding the bonding and optical properties of clusters 1 H – 3 H . In addition, the reaction of 1 H with [Pd(PPh 3 ) 2 Cl 2 ] in the presence of terminal alkynes led to the formation of new bimetallic Cu–Pd alloy clusters [PdCu 14 H 2 {S 2 P(O n Pr) 2 } 6 (C≡CR) 6 ] ( 4 : R=Ph; 5 : R = C 6 H 4 F).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Acute Copper Toxicity Displays a Nonmonotonic Relationship with Age Across the Medaka ( Oryzias latipes ) Life Span

The ability of an organism to cope with environmental stressors varies across the life span because of developmental stage–specific responses and age-related functional declines. In the present study, we examined the effect of age on acute copper toxicity in Japanese medaka (Oryzias latipes). We first determined the median lethal concentration (LC50) at 96 h for embryos, 7-day-old fry, and 6-month-old medaka. Embryos were exposed to 0, 15, 30, 60, 125, 250, and 500 ppb CuSO 4 through hatching. Fry were exposed to 0, 20, 50, 75, 100, 150, 250, and 500 ppb CuSO 4 for 96 h. Adult fish were exposed to 0, 100, 150, 200, 250, and 300 ppb CuSO 4 for 96 h. The 96-h LC50 was 804 ppb for embryos, 262 ppb for embryonically exposed larvae, 60.3 ppb for 7-day-old fry, and 226 ppb for adults. We then challenged cohorts of fish aged 2, 3, 5, 6, 7, 8, 9, 10, 11, 13, 14, 15, and 16 months with a 225-ppb CuSO 4 exposure to determine the acute toxicity across the life span. The fish exhibited a bimodal tolerance to copper, with tolerance peaking in 2- and 3-month-old fish and again at 10 and 11 months of age. Our data demonstrate that copper sensitivity is dynamic throughout the medaka life span and may be influenced by trade-offs with reproduction. Environ Toxicol Chem 2022;41:2999–3006. © 2022 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2023

Comparing π‐complexation capabilities of ionic liquids containing silver(I) and copper(I) ions by headspace single drop microextraction in combination with high‐performance liquid chromatography

Selective π‐complexation capabilities of silver(I) and copper(I) ions can be effectively facilitated in ionic liquids. To understand the effects of environmental factors that influence the π‐complexation of these metal ions with analytes, techniques that employ small volumes of ionic liquid that can be readily analyzed are desired. In this study, headspace single drop microextraction coupled with HPLC is used to investigate a diverse set of environmental factors on the metal ion‐mediated complexation with aromatic compounds in ionic liquid media. Silver(I) and copper(I) bis[(trifluoromethyl)sulfonyl]imide salts were both studied by dissolving them in the 1‐decyl‐3‐methylimidazolium bis[(trifluoromethyl)sulfonyl]imide ionic liquid and employing the mixture as extraction media for aromatic compounds. Water and acetonitrile within the sample solution were observed to interfere with the complexation of silver(I) ions and aromatic compounds, while ethylene glycol and triethylene glycol did not. The temperature and extraction times were optimized to fully facilitate the π‐complexation capabilities of metal ions in ionic liquid media. Partition coefficients between the sample headspace and metal ion were determined using a three‐phase equilibria model. Although no discernable difference in analyte partitioning between the headspace and ionic liquid solvent was observed, analyte partition coefficients to silver(I) ion tended to be greater compared to copper(I) ion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2024

Combining 3D printing of copper current collectors and electrophoretic deposition of electrode materials for structural lithium-ion batteries

Serving as a proof of concept, additive manufacturing and electrophoretic deposition are leveraged in this work to enable structural lithium-ion batteries with load-bearing and energy storage dual functionality. The preparation steps of a complex 3D printed copper current collector, involving the formulation of a photocurable resin formulation, as well as the vat photopolymerization process followed by a precursors-based solution soaking step and thermal post-processing are presented. Compression and microhardness testing onto the resulting 3D printed copper current collector are shown to demonstrate adequate mechanical performance. Electrophoretic deposition of graphite as a negative electrode active material and other additives was then performed onto the 3D printed copper collector, with the intention to demonstrate energy storage functionality. Half-cell electrochemical cycling of the 3D multi-material current collector/negative electrode versus lithium metal finally demonstrates that structural battery components can be successfully obtained through this approach.

25 ENERGY STORAGE↗

DOE OSTI2021

A study of corrosion on electrodeposited superhydrophobic copper surfaces

This study considers the corrosion characteristics of superhydrophobic copper surfaces with multiscale asperities formed inherently on a copper substrate, using a facile, low energy, electrodepostion method. A systematic study is presented for the first time on the effect of surface functionalization time on long-term immersion in a wide range of corrosive environments from the extremely acidic to the extremely alkaline. The corrosion resistance is also reported for the first time as a function of temperature in the range 23–85°C. The superhydrophobic surfaces are shown to enhance corrosion resistance by up to four orders of magnitude compared to bare copper.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Nuclear response of additive manufactured GRCop-84 copper for use in Lower hybrid launchers in a fusion environment

Recent advances in selective laser melting (SLM) 3D printing technology allow additive manufacture of lower hybrid current drive (LHCD) RF launchers from a new material, Glenn Research Copper 84 (GRCop-84), a Cr 2 Nb (8 at. % Cr, 4 at. % Nb) precipitation hardened alloy, in configurations unachievable with conventional machining. Tensile strength and thermal conductivity are compared to other competing high conductivity copper alloys for fusion use. Swelling and conductivity at 100 DPA when exposed to the Hanford Fast Flux Test Facility neutron spectrum is predicted in the 1–2 % and 65-70% IACS range, respectively, by comparison to copper alloys with similar precipitate and grain size. Finally, self-similar ion irradiation of a GRCop-84 target at 430 °C to 20 DPA resulted in no noticeable void formation in FIB cross sections or TEM lamella.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2021

Macro copper-graphene composites with enhanced electrical conductivity

Composites demonstrating simultaneously enhanced-electrical conductivity, current density and lowered-temperature coefficient of resistance (TCR) compared to copper have been highly sought after for their advantages in efficient energy transport behavior. While such conductors have been demonstrated in 1D (nanowires) and 2D (films) samples, achieving similar behavior in 3D has been challenging owing to the limitations of the synthesis techniques used. In this paper, novel macro-scale 3D copper conductors were demonstrated with simultaneously increased electrical conductivity and decreased temperature coefficient of resistance (TCR) through the addition of graphene. Hot-extrusion was used to manufacture over 1-m-long, 2-mm-diameter copper-graphene composites with varying graphene content and defect density. Results showed that the electrical conductivity and current density in composites with low defect density graphene increased monotonically as a function of graphene content. They also demonstrated a significant decrease of over 17% in TCR with the addition of only 15 ppm graphene along with over 52% improvement in current density. Comparatively composites with high defect density graphene demonstrated lower electrical conductivity and current density. This study provides first-of-its-kind evidence of 3D metal composites whose bulk electrical performance has been enhanced using graphene additive in minute quantities. Further developments in this area are essential to achieve high performance composite conductors that can improve energy transport efficiency and pave way for industrial adoption of such materials in the future.

36 MATERIALS SCIENCE↗

DOE OSTI2022

Friction extrusion of ODS copper rod made from powder

Meters-long oxide dispersion strengthened copper rods were manufactured directly from powder by a single-step process, called friction extrusion. The average grain size was 880 nm, which was refined 40 times from powder precursor due to extensive shear deformation. Meanwhile, the average size of alumina particles was 60 nm which retains a decent oxide dispersion strengthening. Here, mechanical properties, including hardness, tensile strength, and ductility, were tested and found to have better or similar values than conventional sintered-then-extruded oxide dispersion strengthened copper materials. The presented technique promises a convenient avenue for the fabrication of oxide dispersion strengthened copper from powder.

36 MATERIALS SCIENCE↗

DOE OSTI2026

Encumbering the Copper(I)-Diimine Coordination Sphere with a Benzyl Group: Impact on the Stability and Photoredox Properties

Copper(I)-bisdiimine complexes, [Cu(NN) 2 ] + (where NN represents a diimine such as phenanthroline or bipyridine derivatives), are considered promising photosensitizers for various photochemical applications. However, their effectiveness is subject to several key challenges. In particular, controlling steric strain around the copper(I) center by introducing appropriate substituents (R) at the α-position of the nitrogen atoms is crucial for optimizing the excited-state properties of the complex. In brief, increasing the size of R leads to longer emission lifetimes and higher quantum yields. Additionally, the energy of the singlet excited state rises with increasing steric bulk, enhancing photoinduced reactivity. However, excessive steric strain from bulky substituents can significantly destabilize the coordination sphere. To balance complex stability with increased steric bulk around the metal center, we have developed two novel non-symmetrical ligands featuring branched alkyl chains and benzyl groups at the α-position of the nitrogen atoms. Here, our findings demonstrate that intramolecular π-stacking interactions between the benzyl group and the opposing phenanthroline ligand contribute to stabilizing the coordination sphere. Furthermore, the flexibility of the benzyl group reinforces the tetrahedral geometry around copper(I), resulting in an increased singlet excitedstate energy compared to benchmark complexes. Notably, we show that this enhancement in excited-state energy translates into greater excited-state reactivity.

Copper(I)↗

DOE OSTI2021

Insights into the Dynamic Interfacial and Bulk Composition of Copper-Modified, Hydrogen-Alloyed, Palladium Nanocubes under Electrocatalytic Conditions

Understanding and controlling the alloying properties of nanomaterials under electrochemical conditions are critically important for fields ranging from energy storage and catalysis to electrochromic window technology. Hydrogen-absorbing nanomaterials, like palladium, are especially interesting due to their ability to reversibly absorb and store hydrogen in their lattice at near-stoichiometric amounts. Palladium’s work function is also significantly deeper than that of most transition metals, which enables electrochemical underpotential deposition of conformal monolayer and submonolayer amounts of transition metals onto the palladium surface. The simultaneous existence of these two properties is unique and opens new and exciting avenues for electrochemical applications. However, the intersection of surface-modified, hydrogen-alloyed palladium nanomaterials is poorly understood, and specifically, how these structures evolve during electrochemical operating conditions remains an open question. Here, we synthesize {100}-terminated palladium nanocubes and deposit between 0.5 and 22 monolayers of copper at the palladium surface. We then electrochemically alloy these surface-modified structures with hydrogen. Using a combination of analytical electrochemistry, spectroscopy, and microscopy, we track the positional evolution of the Cu at the surface of Pd, its impact on palladium’s ability to absorb hydrogen, and copper’s effect on hydrogen evolution electrocatalysis. We show that Cu readily alloys into the palladium nanocube at potentials more negative than the Cu 2+/0 deposition, but a 0.5 monolayer thick copper layer remains at the Pd surface regardless of potential. Finally, we discuss the implications of these findings within the framework of CO 2 reduction catalysis for carbon–carbon bond-forming chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗