bluuebunny/crossref_metadata_2025_split huggingface dataset:
An Alternative Pre-Treatment for Metallization of Polymeric Materials and Its Applications
Authors: Oriani Andrea Vittorio , Cojocaru Paula , Magagnin Luca 
Published: February 2020

Metallization of polymers is a challenging process due to the intrinsic difference in the chemical nature of Polymeric and metallic materials. This leads, in the best scenario, to metallic deposits having poor adhesion to the polymeric substrate1. Neglecting wet processes2, that are based on hazardous chemicals (as chromic acid) and limited to specific polymers, plasma activation has been considered a promising option for more than thirty years. In the past, pioneering studies demonstrated that low pressure plasma is a valid alternative pre-treatment to chemical etching. This is due to the ability of plasma to graft nitrogen-containing functionalities that bind to palladium in the activation bath3–5. Technological advancement in the field of plasmas allowed developing open air systems, thus reducing operational costs and dimensional limitations. Since, in principle, plasma parameters can be tuned to be effective on different classes of polymers6,7, this pre-treatment allows electrochemical metallization of polymers that couldn’t be plated due to the ineffectiveness of wet chemical etching.
In this study open-air roll-to-roll dielectric barrier discharge (DBD) equipment was used to pretreat different polymers including Polyetheretherketone (PEEK), Ethylene ChloroTriFluoroEthylene (ECTFE) and Poly Vinyldene fluoride (PVDF) films with nitrogen-based plasma. The plasma modified surface of the films was therefore coated with metal by means of a commercial electroless copper or nickel lines or homemade silver baths. Different thickness values have been considered for the metallic coating. While thin deposits (up to about 250nm) were obtained by electroless only, thicker coatings were obtained performing electrodeposition on top on the metallic layer previously obtained.
Specific characterization of the metallic-coated polymers was performed depending on their final application: this spans from barrier layer to fluids to flexible concentrator mirror for solar thermodynamic. Further studies were performed to understand the nature of the modification induced by plasma to the polymer surface, both from a chemical and morphological point of view, in the first case by means of XPS and in the second by AFM. Nucleation and growth of the metallic layer was studied by SEM. Adhesion between polymer and metal was studied by cross cut test (ASTM D3359), which confirmed excellent adhesion levels.
References
1. J. M. Burkstrand, J. Appl. Phys., 52, 4795 (1981).
2. R. R. Rye, A. J. Howard, and A. J. Ricco, Thin Solid Films, 262, 73–83 (1995).
3. M. Charbonnier, M. Alami, M. Romand, L. De Sciences, and U. C. Bernard, 143 (1996).
4. M. Alami, M. Charbonnier, and M. Romand, Plasmas Polym., 1, 113–126 (1996).
5. M. Charbonnier, M. Alami, and M. Romand, J. Appl. Electrochem., 28, 449–453 (1998).
6. S.J. Cho, S. P. Shrestha, and J.H. Boo, Curr. Appl. Phys., 11, S135–S139 (2011).
7. M. Šimor et al., Surf. Coatings Technol., 172, 1–6 (2003).
Composition, Structure and Properties of Electroless Deposited Rhenium-Rich Re-Co Thin Films
Authors: Duhin Alla , Inberg Alexandra , Eliaz Noam , Gileadi Eliezer 
Published: February 2020

Rhenium (Re) is a promising refractory metal that has unique combination of properties. Compared to other refractory metals, Re has the greatest tensile strength and excellent creep resistance over a wide range of temperatures (up to ~2000°C). Pure Re does not have a ductile-to-brittle transition temperature. Moreover, unlike other refractory metals, Re does not form stable carbides. Thus, it is potentially attractive coating on different carbon material.
Electroless plating is relatively simple method for generating thin metallic and metal alloy films on conductive and nonconductive surfaces. The ability of electroless plating to coat the inside of holes and recesses without using external current source or vacuum technology equipment makes it an ideal coating technology for many applications. In this study, high Re content (more than 65 at.%) Re-Co coatings were prepared by electroless deposition. The pH dependence of process kinetics, film microstructure and composition was studied. The obtained films were characterized by HRSEM, AFM, XPS and XRD methods. It was shown that as deposited films have amorphous structures with microhardness value of 600 - 620 HV. Crystalline hcp structure of Re-Co coating was detected only after annealing at 550 oC. Thin coatings (250-500 nm) have demonstrated good corrosion protection of copper in salt medium reducing corrosion current at list by one order of magnitude. The annealed deposits have shown improved mechanical and electrical properties. Such films exhibit ferromagnetism and could be applied in mobile magnetic components where soft-magnetic response combined with mechanical stability is required (MEMS devices).
Deposition of Ni-Based Carbon Nanotube Composite Coatings By Using Laser Enhanced Electroless Plating
Authors: Suzuki Tsunehisa 
Published: February 2020

1 Introduction
In recent years, the mask-less direct metal patterning on 3D shape plastic substrates has received considerable attention from the perspective of potential applications to such as 3D-molded interconnect device (3D-MID). 2-shot injection molding and Laser direct structuring (LDS) are the leading technology in this field. However, these technology are not direct metal patterning. In the case of LDS, The laser-activatable thermoplastic doped with a special additive was required for making a sensitized-activated surface by laser. When the thermoplastic was irradiation by laser beam, it was activated. A physical-chemical reaction forms metallic nuclei. These act as a catalyst for electroless plating. The metallization on activated pass was performed by electroless plating after laser-activation.
Some recent researches have investigated the laser enhanced electroless plating and have reported that they could successfully and directly formed metal patterning on the plastic substrates by the laser enhanced electroless plating. The metallization on activated pass were performed by electroless plating after laser-activation. However, the effects of the laser wavelength and additives in plating bath is not clear. In this study, their effects on the laser enhanced electroless plating were investigated. Carbon nanotubes (CNTs) were used as additives for improving laser absorption.
2 Experimental Procedure
Polyimide films as substrates were immersed in low phosphorus electroless nickel plating bath (Meltex, NI-426, 1-3% phosphorus). The polyimide films were not sensitized and were not activated. Laser beam irradiation performed on the substrates through quartz glass rods at room temperature. Laser wavelengths of 405nm, 532nm, 980nm were chosen. CNTs (Showa denko, VGCF-H, 0.4g/L) were added in the plating bath.
3. Results and discussion
In the case of non-addition of CNTs, no nickel deposited on the polyimide film by laser irradiation of 405nm (0.15W), 532nm (1.5W), 980nm (6W) in wavelength. Non-deposition results from non-pretreatment, such as sensitizing and activating, and from the less laser absorption of substrates.
In the case of addition of CNTs, Island-like nickel deposited on the polyimide films by using 980 nm Laser beam. The nickel deposits were nickel-based CNT composites. CNTs improved the absorption of Laser and led local heating on the substrates so that the composite coatings formed on the non-pretreated substrates.

Figure 1
(Invited) The Interaction of Organic Additive in Magnetic Alloy Plating
Authors: Sun Ming , Jiang Ming 
Published: February 2020

Organic additives can play an important role in thin magnetic alloy electrodeposition. To understand how the additive interacts with the film nucleation/growth, then alters the film property still remains as the very interesting topic.
In this study, we have evaluated several sulfur-containing organic additives with different structures in NiFe or CoFe electrodeposition electrolytes. First, the molecule adsorption on metal surface via unsaturated bonds are evaluated and compared; then, post hydrogenation reduction products of those compounds are verified in the deposit, to identify if the additive active function groups are actually desorbed from surface, or incorporated in deposit; lastly, the associated film properties are studied and compared.
(Invited) Electrodeposition of Thermally Stable Soft Magnetic Materials
Authors: Gong Jie , Riemer Steve , Tabakovic Ibro , Kautzky Michael 
Published: February 2020

Advanced reader technology requires high reader annealing temperature (300-450°C) to achieve good TMR ratio, to realize high density and low noise reader performance. 1) However, during the reader stack anneal, the bottom shield will also be exposed to the high temperature and possibly a cross magnetic field. Generally, the bottom shield is regular electrodeposited Permalloy Ni80Fe20 prepared from an electrodeposition solution containing saccharin additive. The significant grain growth of the NiFe bottom shield would cause deterioration of the magnetic properties as annealing temperature increases over 300°C, resulting in disordered shield domain structures and high reader noise. As one of the paths to improve the thermal stability, we have been studying and developing by using a third element to pin the grain growth caused by thermal annealing, while still keeping good magnetic softness. In this work nanocrystalline NiFeX (X=Co, Mo, O etc) films were prepared by electrodeposition, which can be stable up to 450°C. The relationship between preparation method and magnetic properties, domain structure, microstructure, crystal structure, corrosion resistance, and their thermal stability were studied. Figure 1 shows the comparison of the microstructure and domain structure of regular Permalloy and the thermally stable NiFeO after 400C 2hr annealing. Reference: 1) S. Ikeda, J. Hayakawa, Y. Ashizawa, Y. M. Lee, K. Miura, H. Hasegawa, M. Tsunoda, F. Matsukura, and H. Ohno, Appl. Phys. Lett., 93, 082508 (2008).

Figure 1
Lifecycle Characterization of a High Magnetostriction Cobalt Iron Electroplating Chemistry
Authors: St. John Christopher R. , Pillars Jamin Ryan , Hollowell Andrew E , Finnegan Patrick , Langlois Eric Donald , Arrington Christian L. 
Published: February 2020

Electrodeposition of iron alloy metals is problematic due to the undesired oxidation of Fe+2 to Fe+3 [1]. A custom cobalt iron electroplating chemistry targeting properties of magnetostriction was used at the beaker scale 80 mL in size. The chemistry is stable for long periods of time, maintains current efficiency, and yields the desired atomic ratios in the deposited cobalt iron film with high values of magnetostriction. However, upon scaling to a 2.5-liter chemistry needed to accommodate four to six inch wafer fabrication, the bath deteriorates much more quickly over time. The current efficiency drops and oxygen is deposited into the film. This is undesirable as the atomic ratio changes the properties of the material and the resulting structures. An investigation into counteracting the undesired iron oxidation in the chemistry was undertaken in order to characterize the deterioration and to prevent this deterioration from occurring.
Our experiments tracked on a weekly basis the decrease of current efficiency within the chemistry, along with the stoichiometry of the deposited cobalt iron and the resulting magnetostriction of the films. Various chemistry storage concepts were tested to determine the effect on current efficiency. When fresh, both the beaker and 2.5-liter sized chemistries electroplate near 80% current efficiency, with a majority of wasted current attributed to hydrogen gas formation. As the chemistry ages, much of the decrease in current efficiency is believed to occur as a result of iron oxidation. Both the solution and the plated films take on a darker color common with oxygen poisoning. During plating, nitrogen is bubbled into the bath in order to reduce this issue. However, it takes the beaker scale approximately 70 days to drop below a usable efficiency, while the 2.5 liter wafer-scale takes approximately 35 days to do the same.

Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-AC04-94AL85000. SAND2015-10657A

Tabakovic, I.; Riemer, S.; Jayaraju, N.; Venkatasamy, V.; Gong, J. Electrochim Acta 2011, 58, 25-32.
Electrodeposition of Ag-Ni-W Alloys
Authors: Kola Avinash R. , Podlaha Elizabeth J 
Published: February 2020

The induced codeposition of tungstate has been widely examined in the presence of nickel, cobalt and iron ions.1 On the other hand, more noble elements, such as Ag, can also induce the reduction of tungstate ions, but to a lesser extent, resulting in silver-rich alloys, by either electrodeposition2 or electroless deposition.3,4 Since both nickel and silver species can induce tungstate, the combined effect is investigated here. Electrodeposited Ag-Ni-W alloys from a stable, thiourea-citrate electrolyte, is examined using rotating cylinder electrodes. The deposit composition was determined with x-ray fluorescence, and used to calculate partial current densities. The increase of nickel ions to a Ag-W electrolyte did not further induce the reduction of tungstate ions, but inhibited it. To probe if the type of nickel species were responsible for affecting the tungsten rate, citrate concentration in the electrolyte was also varied. A significant factor in inducing tungsten was attributed to the presence of silver species compared to nickel species suggesting a thermodynamic control for tungstate reduction.

Acknowledgements

The authors wish to thank the AESF foundation and Tyco Electronics Connectivity Ltd. for partial support of this project.

References

1. N. Tsyntsaru, H. Cesiulis, M. Donten, J. Sort, E. Pellicer, and E. J. Podlaha_Murphy, Surf. Eng. Appl. Electrochem., 48, 491 (2013).
2. A. Kola, X. Geng, and E. J. Podlaha, J. Electroanal. Chem., 761, 125 (2016).
3. Y. Shacham-Diamand, A. Inberg, Y. Sverdlov, and N. Croitoru, J. Electrochem. Soc., 147,3345 (2000).
4. E. E. Glickman, V. Bogush, A. Inberg, Y. Shacham-Diamand, and N. Croitoru, Microelectron. Eng., 70, 495 (2003).
(Invited) In-Situ Analysis of Lithium Ion Batteries
Authors: Ogumi Zempachi 
Published: February 2020

Twenty-five years have passed since the first lithium ion battery (LIB) was commercialized, which work on the basis of ion shuttle mechanisms. Reactions in LIBs are very simple at first glance; insertion and extraction of Li+at positive and negative electrodes, and electron transfer occurs through a schottky contact between current collectors and active masses.
When we look insight of the reaction, the situation is not so simple as the first glance. Even during insertion and extraction of positive ions, i.e. Li+, charge neutrality through the system must be retained, which means that the valences of the elements, mainly transition metals, composing the host lattice must change during the reaction. The valence change causes structural changes in the lattice, namely, phase transition should occur.
Carbon materials, generally graphite, are used as the negative active mass in LIB. The fully charged state of graphite shows the potential as low as that of lithium metal, 90 – 200 mV vs Li/Li+. Organic species composing the electrolyte and binder of LIB are inherently unstable against such reductive circumstances. Nevertheless LIB shows stable and long life compared with other rechargeable batteries and is now produced in an enormous scale and widely used. This is due to the surface stabilization of the graphite negative electrode by the formation of a passivating film called SEI.Its energy density has increased over twice since the commercialization. There remain some issues to enhance the property and extend the application of LIBs.
Innovation in materials for LIB is essential for advancing LIB properties but it is no less important to clarify reactions occurring in LIBs. The latter would supply information and cues to develop innovative materials for future LIBs.
Reactions proceeding inside LIB range widely in scale of time and space. A variety of analytical technologies including FT-IR, Raman, SPM, NMR, SR-X-ray diffraction and absorption, neutron diffraction, SEM, TEM, EC-MS have been developed and used to elucidate reactions inside LIBs in situ and ex situ.
The author’s group has developed some of these technologies, some of that are summarized and explained here.
There are plenty of analytical technologies further-more that have high potential for clarifying reactions of batteries. Main battery reactions should be focused and in addition to the main reactions side reactions and slow reactions that give major influences on life and safety of battery required to be solved.
Each analytical technology has some merits and demerits in focusing on reactions to be clarified. Adequate technologies should be selected depending on the phenomena to be solved.

Figure 1
in-Operando Imaging Studies on Dynamics of Sulfur/Polysulfides in Li-S Batteries
Authors: Wu Nae-Lih 
Published: February 2020

Lithium-sulfur (Li-S) battery is a promising rechargeable battery system that has both high theoretical capacity and energy density. Moreover, sulfur (S) is inexpensive and nontoxic, making Li-S suitable for large-scale energy storage applications. Sulfur (S8) lithiation during the operation of Li-S battery is a multi-step electrochemical process that involves different lithium polysulfide (Li2Sn) intermediates. The long-chain polysulfides (PSs) are highly soluble in the aprotic organic electrolyte. There has been a broad consensus that polysulfide dissolution is strongly linked to the key performance indexes, such as columbic efficiency, self-discharge, capacity fading and etc., of Li-S batteries. Re-deposition of S/PS takes place during de-lithaition, which has never been investigated in the literature but is believed to play equally important part as the dissolution process in affecting the cycle stability of the S electrode. We carry out in this work operando observations at two different scales on the dynamics of dissolution and re-deposition processes of polysulfide/S particles during the operation of Li-S batteries. In-operando synchrotron transmission X-ray microscopy (TXM) has been used to monitor in real-time the dynamics of the S/PS dissolution and re-deposition based on the dimensional variation of the micron-sized S-containing active particles. On the other hand, in-operando optical microscopy has been used to reveal the large-scale motion of the polysulfides within a model cell. The combined information from these two in-operando studies provides valuable evidences that unravel the existence of unprecedented chemical-reaction driven charge-transfer mechanisms for S lithiation/delithiation.

Figure 1
Using Thin Films to Study Capacity Fade Mechanisms Observed in Conventional LiV3O8 cathodes
Authors: Kercher Andrew Keith , Sarbada Varun S.V. , Zhang Qing , Takeuchi Kenneth J , Marschilok Amy C , Hull Robert , Dudney Nancy J , Takeuchi Esther S 
Published: February 2020

Capacity fade mechanisms can be difficult to pinpoint in conventional composite cathodes for Li-ion batteries. Capacity fade associated with the cathode can be caused by: (1) irreversible reactions involving the active material, possibly with the electrolyte, (2) degraded integrity of the composite structure, or (3) anode contamination by cathode dissolution products. Post-cycling characterization can be difficult, because these potential capacity fade mechanisms would occur in a complicated cathode structure with: porosity, possible microcracks, irregular surfaces, and multiple particulate phases (active material, binder, and conducting additive).
Thin film cathodes were used to study how LiV3O8 (LVO) microstructure affects cycling performance without the added complications associated with a conventional composite cathode structure. Thin film cathodes were produced by magnetron sputtering a Pt current collector layer and an LVO layer onto alumina disks. The thin film geometry with its uniform layered structure was well suited for analysis of pristine and cycled LVO cathodes by several characterization techniques, including transmission electron microscopy, energy dispersive x-ray spectroscopy, and x-ray photoelectron spectroscopy.
The cycling performance of heat-treated thin film cathodes was directly compared to that of conventional composite cathodes with heat-treated sol-gel derived LVO powder. Thin film and sol-gel derived LVO cathodes showed excellent microstructural and electrochemical agreement as a function of heat-treatment temperature. Depending on heat-treatment temperature, the microstructure ranged from amorphous (as-deposited or low temperature heat-treatment) to coarse-grained crystalline material (higher temperature). The maximum specific capacity and the maximum capacity fade were both observed for LVO nanocrystalline material fired at intermediate temperature, where reduced capacity and reduced capacity fade were observed for higher and lower firing temperatures. Capacity fade was linked to vanadium dissolution, where amorphous LVO cathodes showed much lower vanadium dissolution than nanocrystalline LVO material.

This work was supported as part of the Center for Mesoscale Transport Properties, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE-SC0012673.
(Invited) In-Situ and Operando Structure Analysis of Lithium Battery Reactions Using Neutron Scattering
Authors: Kanno Ryoji , Taminato Sou , Yonemura Masao , Shiotani Shinya , Kamiyama Takashi , Torii Shuki , Nagao Miki , Ishikawa Yoshihisa , Mori Kazuhiro , Fukunaga Toshiharu , Onodera Yohei , Naka Takahiro , Morishima Makoto , Ukyo Yoshio , Adipranoto Dyah Sulistyanintyas , Arai Hajime , Uchimoto Yoshiharu , Ogumi Zempachi , Suzuki Kota , Hirayama Masaaki 
Published: February 2020

Among the in situ and operando techniques proposed for elucidating the reactions, a structural analysis would provide essential and fundamental information. The high-intensity and high-resolution diffraction is one of the best techniques for observing the changes in the cell components during operation, which may provide clues that help us to recognize the significant issues affecting the deterioration of the battery. However, the operando systems are rather difficult to apply in the commercial-size cells. Many approaches have therefore been proposed based on stationary neutron and high energy X-rays, and structural changes in the electrode materials have been detected under slow reaction kinetics conditions or a repeated data accumulation process. However, comprehensive observations that can detect deterioration-related changes in the components under actual operations remain difficult.
We developed an experimental system that uses high-intensity time-of-flight (TOF) neutrons and a high-resolution SPICA diffractometer. The structure changes in the cathode and anode materials were analysed at each charge-discharge reaction step. The new measurement system could provide information for a wide range of reactions related to real battery operation conditions.

Acknowledgements

This work was supported by the Research and Development Initiative for Scientific Innovation of New Generation Batteries (RISING) project of the New Energy and Industrial Technology Development Organization (NEDO).