Ｎｉ‐Ｐ共晶合金の連続電気めっき

Silica polyamine composites (SPC) made from silanized amorphous nanoporous silica gel and poly(allylamine) (BP-1) were functionalized with phosphorus acid using the Mannich reaction, resulting in a phosphonic acid modified composite (BPAP). Successful immobilization of the phosphonic acid ligand was confirmed by mass gain, elemental analysis, IR, and solid-state NMR. The modified composite had a ligand loading of 1.5 mmol/g, corresponding to N/P ratio of 0.73. Zirconium(IV) was immobilized on BPAP with a loading of 1.12 mmol/g. Zirconium loading was analyzed by mass gain, ICP/AES, and SEM/EDX. Arsenate anions strongly adsorbed on the ZrBPAP composite in the pH range 2−8, while arsenite only adsorbed well at pH 10. The sorption mechanism is a chelation between arsenate or arsenite and Zr(IV)−phosphonic acid complex of BPAP. Adsorption isotherm data were found to be well modeled by the Langmuir equation for As(V) at pH 4 with Kads = 0.016 L/g and Qm = 98 mg/g; and at pH 6 with Kads = 0.018 L/g and Qm = 56 mg/g. Regeneration of the resin was carried out successfully for As(V) and As(III) using 2M-H2SO4. Four adsorption/desorption cycles were performed for As(V) at pH 4 without significant decrease in the uptake performance. ZrBPAP capture capacity and kinetics for arsenate were tested for longevity over 1000 cycles with only a marginal loss of performance. This composite is highly selective for arsenate over sulfate (As/SO42− = 50/1) and selenate (As/Se = 20/1); lower selectivity was observed with Fe(III) and Th(IV) loaded BPAP. The significance of the observed selectivity is discussed in terms of the chemical properties of the anion and the nature of the interactions with the immobilized metal site.

1. The IR spectra of a number of phosphinic, phosphonic, and phosphoric dithio acids and their solutions in CCl4 were studied in the temperature interval 253–293°K. 2. In pure liquids and their concentrated solutions in CCl4, dimers exist on account of the formation of hydrogen bonds. In this case the SH group emerges as a proton donor; the thione sulfur atom serves as an acceptor in phosphinic acids, while the oxygen of the ether group is the acceptor in phosphonic and phosphoric acids. 3. The hydrogen bond of the SH group with the thiophosphoryl sulfur in phosphinic acids is stronger than that with the oxygen of the substituent of phosphonic and phosphoric acids or dioxane. 4. In dilute solutions in CCl4, noncyclic dithiophosphonic and phosphoric acids exist in the form of two rotational isomers, while cyclic phosphinic acids exist in the form of one isomer. Stabilization of the isomers is probably due to intramolecular hydrogen bonds.

Very Few Interventions after Tumor Lysis Monitoring in Patients with Chronic Lymphocytic Leukemia Who Are Started on Venetoclax in the Real-World Setting- Suggests Less Intensive Monitoring Maybe Safe for Low-Risk Patients

This chapter shows, as in previous years, the most important achievements of the 2021 year in the area of organo-phosphorus compounds containing: three P–O bonds (Section 2: phosphoric acids and their derivatives), two P–O and one P–C bonds (Section 3: phosphonic acids and their derivatives) as well as one P–O and two P–C bonds (Section 4: phosphinic acids and their derivatives), in addition to the phosphoryl group P═O, present in all three groups of compounds. Each of the main sections covers “synthesis and reactions” including pure synthesis without applications, “synthesis and biological applications” and “synthesis and miscellaneous applications” including synthesis directed towards non-biological applications. At the end of each subsection, the corresponding achievements are shown for hetero-analogues in which phosphorus–oxygen bonds have been replaced by phosphorus–heteroatom P–X and/or P═Y bonds (X, Y = N, S or Se). The subsection on quinquevalent phosphorus acids and their derivatives as catalysts has been placed, as usual, at the end of the entire chapter, after a review of all three main groups of compounds. As in previous years, the area devoted to phosphoric and phosphonic acids and their derivatives dominated over a smaller section of phosphinic acids and their derivatives, and literature references for these sections remained at a ratio of 4 : 12 : 1. A dynamic, five-fold increase in the number of works, in the subject of chiral phosphoric acids as catalysts, has been recorded in this year.

This chapter shows, as in previous years, the most important achievements of the 2020 year in the area of organo-phosphorus compounds containing: three P–O bonds (section: phosphoric acids and their derivatives), two P–O and one P–C bonds (section: phosphonic acids and their derivatives) as well as one P–O and two P–C bonds (section: phosphinic acids and their derivatives), in addition to the phosphoryl group P═O. Each of the main sections covers “synthesis and reactions” including pure synthesis without applications, “synthesis and biological applications” and “synthesis and miscellaneous applications” including synthesis directed towards non-biological applications. At the end of each subsection, the corresponding achievements are shown for hetero-analogues in which phosphorus–oxygen bonds have been replaced by phosphorus–heteroatom P–X and/or P═Y bonds (X, Y = N, S or Se). The subsection on quinquevalent phosphorus acids and their derivatives as catalysts has been placed, as usual, at the end of the entire chapter, after a review of all three main groups of compounds. In this year, the area devoted to phosphoric and phosphonic acids and their derivatives dominated traditionally over a smaller section of phosphinic acids and their derivatives, and all sections remained in a ratio 1 : 2 : 0.5, respectively.

Direct synthesis of free (alpha-hydroxyalkyl)phosphinic acid amphiphiles 1 can be readily realized by sonication of the heterogeneous mixture of 50% aqueous hypophosphorous acid and long-chain aldehydes in the presence of catalytic amounts of hydrochloric acid. Oxidation of these phosphinic acids by DMSO in the presence of catalytic amounts of iodine quantitatively leads to the corresponding phosphonic acids 3. IR spectra of the phosphinic acids 1 in the condensed phase and in solution reveal the presence of intra- and intermolecular associations. Dissociation constants of the phosphorus acids 1 and 3 determined by potentiometric and (31)P NMR titrations show a good correlation between the two methods. The phosphinic acid amphiphiles 1 are slightly stronger than the corresponding phosphonic acids 3. (alpha-Hydroxyalkyl)phosphonium chlorides are prepared in good yields from the phosphine PH(3) and long-chain aldehydes in acidic media.

Surface metallization of silicon (Si) substrates, that is, adhesive metal films formation on Si is important for obtaining infallible electrical contacts in various devices such as solar cells and power devices. Autocatalytic electroless deposition, which is a conventional method to metallize non-conductive substrates, has several advantages like simplicity of process, uniformity of deposited films, and the covering of complicated structures. The autocatalytic electroless deposition is expected to replace sputtering process of back metal of power devices and screen printing process of electrodes of solar cells. This process requires surface-activation pretreatment of non-conductive substrates (1). Adhesion of metal films obtained by using conventional pretreatments is much lower than that is necessary for the electrical contacts. We recently developed a new surface-activation process for the direct electroless deposition of adhesive metal films on Si substrates (2, 3). The process consists of two steps: Step 1) formation of gold (Au) nanoparticles by electroless displacement deposition; and Step 2) metal films formation on the Si surface by autocatalytic electroless deposition. In previous study, we found that Au nanoparticles have an excellent ability to bind metal films to Si surfaces. In this study, we have investigated the effect of interfacial structure of Au and Si. At the first step of the two-step process, Au nanoparticles were deposited on a p-Si(100) substrate by electroless displacement deposition using a HAuCl4 solution containing HF. At the second step, the nickel-phosphorus alloy (Ni-P) film was electrolessly formed on the Si substrates by using NiSO4 as a metal salt and NaPH2O2as a reducing agent. The adhesion of the electrolessly deposited Ni-P films on Si substrates was examined by a tape test based on Japanese Industrial Standard JIS H8504 corresponding to ISO 2819. The adhesion was evaluated by maximum Ni-P film thickness that occurred no peeling by the tape test. We analyzed the interfacial structure of Au/Si by X-ray diffraction (XRD, Rigaku Ultima IV) and transmission electron microscopy (TEM, JEOL JEM-2100). Figure 1 shows the XRD patterns of Au nanoparticles on p-Si(100) substrates. Only Au(200) diffraction line was obtained for the sample immersed in the Au-deposition-solution for 120 s (Fig.1 (a)). The cross-sectional TEM observation of Si wafer Au-nanoparticle-deposited for 210 s revealed that Au nanoparticles epitaxially grew on Si and each particle was single crystalline. At the interface between Au and Si, Au-Si alloy formation was observed by TEM and XPS (3). Farther deposition yielded Au(200) and (111) diffraction lines such as Fig.1 (b) for immersion deposition time of 240 s. Figure 2 shows the maximum film thickness (adhesion) of electrolessly deposited Ni-P alloy films on Si substrates as a function of Au nanoparticle deposition time. The maximum film thickness increased with deposition time of Au nanoparticles, reached maximum at 120 ~ 210 s, and decreased afterwards. This result indicates that the electrolessly deposited Ni-P films have high adhesion in case that the Au nanoparticles epitaxially deposited on Si substrates. The growth of polycrystalline Au on epitaxially deposited Au nanoparticles on Si decreases the adhesion of the electrolessly deposited Ni-P films. In conclusion, it was revealed that single crystalline Au nanoparticles epitaxially grown on Si substrates yield high adhesion of electrolessly deposited metal films. ACKNOWLEDGEMENTS The present work was partly supported by KAKENHI (26289276) from JSPS. REFERENCES M. Paunovic and M. Schlesinger, Fundamentals of Electrochemical Deposition, 2nd ed., Wiley, NY (2006).S. Yae, M. Enomoto, H. Atsushiba, A. Hasegawa,N. Fukumuro, S. Sakamoto, and H. Matsuda., ECS Trans., 53 (6), 99 (2013).H. Atsushiba, Y. Orita, S. Sakamoto, N. Fukumuro, and S. Yae; ECS Trans., 61(10), 9 (2014). Figure 1

Organophosphorus antioxidants: Part X—Mechanism of antioxidant action of aryl phosphites and phosphonites at higher temperatures

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Die Thiophosphor und Thiophosphonsäureester (I) und (V) isomerisieren bei 20°C zu den O‐2‐Mercaptoalkylestern (II) und (VI), die bei 130‐160°C zu den Estern (III) und (VII) zersetzt werden.

Introduction Preparation Handling; Physical Properties Nucleophilic Reactions Electrophilic Reactions Other Reactions

The Sn-rich eutectic alloy (90 wt% Sn) in the Au–Sn system offers a potentially cheaper alternative to the Au-rich eutectic alloy (20 wt% Sn) for optoelectronic and microelectromechanical systems device packaging and may be applicable as a Pb-free solder for microelectronic packaging. A simple electrodeposition method was utilized to fabricate Sn-rich, Au–Sn solder films, including the eutectic composition for this purpose. The electrolyte consisted of a solution of Sn chloride and ammonium citrate. Gold was added to the electrolyte in the form of either a Au nanoparticle (<20 nm) suspension, prepared with Na citrate, or by directly adding Au powder (500–800 nm particles). The resultant suspensions were used to electrodeposit eutectic and near-eutectic alloy films. Uniform thicknesses and compositions were obtained with the latter approach, i.e., direct addition of Au powder. Gold content in the deposits increased with increasing Au particle loading in the electrolyte and increasing current density. Room temperature aging led to the formation of AuSn4 at the Au particle-Sn matrix interface. Reflow of deposits with near-eutectic compositions resulted in the formation of the two eutectic phases, Sn and AuSn4.

Ni-P, Co-P, and Ni-Co-P alloys (0≤P≤16wt%) were electrodeposited from Watts-type plating bath containing phosphorous acid. Effects of bath temperature, current density, content of phosphorous acid in the bath, and molar ratio of metal ions in the bath on the deposition rate and the composition of the deposited alloys were studied. The relation between Vicker's hardness and phosphorous content in the deposited Ni-P and Co-P alloys were also discussed. Moreover, for better understandings of the conformation or the nature of the chemical state of phosphorous, its properties and stability in the deposited Co-P alloys, the differential scanning calorimetry, the small angle X-ray scattering, and the P-Kβ X-ray spectroscopy were measured on the alloys. The results are summerized as follows; (1) The deposition rate and composition of the deposited alloys are greatly influenced by the plating conditions, that is, temperature of the bath, current density, and composition of electrolytes in the bath. (2) The Ni-P, Co-P, and Ni-P, Co-P deposited alloys containing more than 5 wt% phosphorous exhibited the hardness of 600-800Hv. (3) Phosphorous in the Co-P alloys as deposited is bonded to cobalt by metallic bond, and it is suggested that phosphorous in the alloy is neither at the elementary state (red or white) nor constitutes stoichiometric cobalt-phosphides such as CoP, Co1.6 P, and that the deposits are at the state of a super-saturated solid-solution of phosphorous in hcp Co (P<-5wt%) and an amorphous solid (P>-5wt%).

The dissociation processes of a series of phosphoric, phosphonic, and phosphinic acids have been studied by the modified method of potentiometry in water and water-ethanol media at 25°C. The influence of substituents on the acidic properties of these compounds has been investigated. As a measure of the substituents steric effects the Rs constants, calculated on the basis of frontal steric model (1), nave been used. A good linear relationship between pKa values in different media has been found. For all series of acids a linear relationship between pKa values and Rs constants of substituents at phosphorus has also been established. In the case of dialkylphosphates in water, for example, such a relationship is expressed by equation: pKa = (-0.717 ± 0.028)-(0.556 ± 0.009) Rs N = 7, R = 0.9932, So = 0.011 pKa value rises with the increase of the steric effect of the substituents at phosphorus which may be conditioned by the steric hindrance to the anion solvatation.

Electrochemistry of Phosphorous and Hypophosphorous Acid on a Pt electrode