Ｎｉ‐Ｐ無電解めっきにおけるＰｄに代わる活性化剤としての水酸化物コロイドの応用

The copper-coated polyester fabric can be used to prepare electromagnetic shielding materials. At present, electroless copper plating mainly using formaldehyde as the reducing agent. But the stability of the bath is poor and it is also volatile and toxic. Using hypophosphite as reducing agent has more advantages for its stability and the plating process does not release any toxic gases. In this paper, The copper-coated polyester fabric was prepared by electroless plating with the sodium hypophosphite as reducing agent. The roughening condition before plating and the deposition process were optimized through orthogonal test. The surface resistances of conductive polyester fabrics, the deposition rate and the coating adhesion were investigated respectively. The optimum roughening conditions obtained are as following: sodium hydroxide concentration of 250g/L; temperature 70 D; time 15min, and the lightweight rate of the plating layer is 0.43% under the experimental conditions. The optimum conditions of electroless copper plating using sodium hypophosphite as reducing agent are: copper sulfate 8g/L; nickel sulfate 1.0g/L; sodium hypophosphite 35g/L; citric acid 20g/L; boric acid 30g/L; pH 9.0; temperature 75D. With these conditions, the deposition rate reaches 1.274g/(m2·min) and the uniform and compact copper layer with excellent electro-conductivity was obtained.

Area-selective copper deposition on screen printed Ag pattern/anodized Al/Al substrate was attempted using a neutral electroless plating processes for printed circuit boards (PCBs), according to a range of variation of pH 6.5-pH 8 at 70 °C. The utilized basic electroless solution consisted of copper(II) sulfate pentahydrate, sodium phosphinate monohydrate, sodium citrate tribasic dihydrate, ammonium chloride, and nickel(II) sulfate hexahydrate. The pH of the copper plating solutions was adjusted from pH 6.5 to pH 8 using NH4OH. Using electroless plating in pH 6.5 and pH 7 baths, surface damage to the anodized Al layer hardly occurred; the structure of the plated Cu-rich films was a typical fcc-Cu, but a small Ni component was co-deposited. In electroless plating at pH 8, the surface of the anodized Al layer was damaged and the Cu film was composed of a lot of Ni and P which were co-deposited with Cu. Finally, in a pH 7 bath, we can make a selectively electroless plated Cu film on a PCB without any lithography and without surface damage to the anodized Al layer.

This study reports the resistance to chromium sulfate (Cr2(SO4)3), nickel sulfate (NiSO4) and copper sulfate (CuSO4) in the Col-0, Lov-1, Ws-2 and Santa Clara strains of Arabidopsis thaliana. Previous reports have shown illness-associated with consuming crops grown in environments contaminated with such heavy metals (Shams, et al., 2018). Plant growth and biomass are also affected by considerable amounts of heavy metals in soil. To investigate the effects of heavy metals on Arabidopsis thaliana, plants were exposed to the heavy metals every two days, after 14 days of growth under normal conditions. Plant height was tallied daily and spectrophotometry was performed. BLAST was conducted to locate characteric similarities/differences between the genome sequences of the strains. Based on phenotypic observations, copper, nickel and chromium sulfate were found to have no significant effect on the plants, in comparison with the control. Interestingly, WS-2 exhibited excessive growth when exposed to nickel sulfate, reaching 125mm on Day 25. Only after exposing the plants to the heavy metals for the fourth time, plants exhibited wilting and leaf browning. However, statistical analysis [p result = 0.048 (<0.05)] indicated that only Col-0 was resistant to nickel sulfate. Significant differences in nucleotide strings of Col-0 include F-Box protein, Homeobox Leucine Zipper protein family (HD Zip), YABBY protein family, radical fringe and SAT gene. The elucidation of a heavy metal-resistant gene in Arabidopsis thaliana could potentially lead to genetic engineering of genes to cultivate heavy metal resistant plants that are safe for human and animal ingestion.

In the present work, nanohydroxyapatites (nHAp) doped with copper and/or zinc ions were investigated for the assessment of its antibacterial activity and biocompatibility. Three forms of material with diverse surfaces were tested: nanopowder in colloidal suspension, galactose hydrogel (3,6-Anhydro-α-l-Galacto-β-d-Galactan) scaffold and pellet. The structural and morphological properties of the obtained biomaterials were comprehensively determined by using: XRPD, FT-IR, SEM-EDS, AAS, XPS and EPR techniques. The antimicrobial active ions, mostly Cu2+, were successfully released from the apatite structure despite the material being suspended in the porous galactose hydrogel matrix. The colloidal solutions of nanohydroxyapatites on bacterial viability revealed moderate activity of Cu2+-doped materials against Escherichia coli strain and significant activity against Pseudomonas aeruginosa strain. The comparative study of bacterial attachment to the hydrogel and pellet surface indicated that hydrogels were more prone to be colonized by both tested strains. Moreover, an additive of the Cu2+ ion modified bacterial attachment and biofilms forming on nHAp:Cu2+ and nHAp:Cu2+-Zn2+ materials. In the case of hydrogels, the biofilms were scattered while these forming on other materials were more clumped. The cytotoxicity evaluation of tested biomaterials showed biocompatible properties of both nanomaterial colloidal solutions as well as galactose hydrogel eluates toward normal mouse osteoblast cell lines (7F2) and human chondrocytes (TC28A2) and osteosarcoma cell line (U2OS). The biocompatibility of tested materials was additionally confirmed by conducting a hemolysis assay which showed full hemocompatibility of nanopowder colloidal solutions and galactose-based materials. Furthermore, unaltered red blood cell morphology was visible after a short and long time of incubation with the obtained biomaterials by using confocal laser scanning microscopy (CLSM). The comparison research provided data of 7F2, TC28 and U2OS cell attachment to the galactose hydrogel surface.

A new electroless copper plating process was studied to improve throwing power (ratio of thickness of deposited films at the center of through-hole to that of the films at the surface of the board) of high-aspect-ratio through-holes in multilayer printed circuit boards. An alternating one-side air stirring method was devised to supply adequate plating solution into through-holes. In this method, a board was put between peripheral plates via spacers. Plating solution was stirred through supplying air to one side of a narrow flow channel composed of the board and the plate by air-supplying pipes arranged at the bottom of the flow channel, while the solution in the other channel was kept static. Air was alternately supplied for each channel. This operation was expected to generate differential-pressure between the front and the back of a board, leading to supplying the solution into through-holes. Plating tests were conducted to verify the effect of this method on throwing power of the high-aspect through-holes. A plating test by applying a conventional method (both-side air stirring) was also conducted as a reference. Electroless copper plating solution was used that contained copper sulfate, formaldehyde, sodium hydroxide, ethylenediaminetetraacetic acid, dipyridyl and surfactant. Sodium sulfate, sodium formate, and sodium carbonate were also added into the solution as salts accumulated as plating time increased. The plating rate of the solution was approximately 2 to 3 μm/h. Copper sulfate, formaldehyde, and sodium hydroxide were periodically supplied by using the concentrated solution. Temperature and pH were 73 °C and 12.4. Six-mm-thick printed circuit boards with through-holes of 0.25-, 0.20-, and 0.15-mm diameter (aspect ratio: 24, 30 and 40, respectively) were used as substrates. Flow velocity of the solution was controlled by adjusting the flow rate of supplied air. Studied flow velocity was preliminary calculated by applying the Bernoulli and Hagen-Poiseuille equations on the basis of consideration that the supplying rate of reactants, particularly copper ion, needed to be higher than the consumption rate of the ion in a through-hole to improve throwing power. Plating tests revealed that throwing power indicated approximately 0.4 for the through-holes of a 24 aspect ratio in the conventional method. On the other hand, throwing power indicated nearly 1 even for through-holes of a 40 aspect ratio under the conditions in which flow velocity of the solution was more than 7 cm/s by applying our alternating one-side air stirring method. Throwing power was also found to increase as flow velocity of the solution increased at one side for any through-hole (24, 30, or 40 aspect ratio). Throwing power decreased remarkably as flow velocity of the solution decreased, implying that flow velocity of the solution significantly affected throwing power as the aspect ratio of through-hole increased. Moreover, flow velocity theoretically estimated by fluid equation reflected behavior of throwing power measured in the plating tests. Therefore, it is concluded that the alternating one-side air stirring method efficiently improves throwing power of high-aspect-ratio through-holes.

The work is devoted to the study of the effect of various compounds on the stability of electroless copper plating solution containing Trilon B. as a chelating agent. The stability of electroless copper plating solutions was estimated by the accelerated method as the time before the start of intensive decomposition of the solution after the introduction of 0.15 ml of colloidal palladium activator solution heated to 75 °C in 250 ml. As stabilizers, both known, currently used, and newly selected compounds were investigated. Sulfur- and/or nitrogen-containing organic and inorganic compounds such as: sodium diethyldithiocarbamate, 2,2’–dipyridyl, thiosemicarbazide, potassium hexacyanoferrate (III), potassium hexacyanoferrate (II), thiourea, thioglycolic acid, dimethylglyoxime, potassium rhodanide in concentrations in the range of 1 - 50 μmol/l were among the first studied. It is shown that when the stabilizers are contained in the solution at the optimal concentrations set (for each compound), solutions containing sodium diethyldithiocarbamate, thioglycolic acid, thiosemicarbazide, thiourea (in descending order of stabilizing action), i.e. compounds containing a sulfur-carbon bond, have the greatest stability. With this in mind, other sulfur-containing compounds, including heterocyclic ones, were selected and studied as stabilizers: α-lipoic acid, thiamine chloride, methyl orange, nitroso-p-salt, methylene blue and SPADNS (sodium salt of 2-(psulfophenylazo)-1,8- dihydroxynaphthalene-3,6- disulfonic acids). In addition, nitrogen-containing compounds that were not previously used in electroless copper plating solutions as stabilizers were also studied: nicotine, pyridoxine, Janus Green B (8-(4-dimethylaminophenyl) diazenyl-N, N-diethyl-10-phenylphenazine-10-ium-2-amine chloride), nigrosine, however. Solutions of electroless copper plating in the presence of these compounds did not show high stability. It has been established that the most effective, comparable in effect to the stabilizers currently used, are α-lipoic acid and thiamine chloride. The advantages of the latter are their availability and low toxicity. For citation: Solopchuk M.S., Grigoryan N.S., Asnis N.A., Vagramyan T.A., Shmelkova P.O., Bardina O.I. Stabilizers of solutions of chemical copper plating. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2023. V. 66. N 3. P. 100-107. DOI: 10.6060/ivkkt.20236603.6708.

The objective of this study was to determine the effects of copper sulphate (CS) and copper oxide nanoparticles (NCuO) on haematological characteristics and plasma lipid profile in Cyprinus carpio. Fish were exposed to CS (0.25 mg L−1 Cu) and NCuO [0.25 (LNP) and 25 mg L−1 (HNP) Cu] for 14 days. CS and LNP treatments showed hypochromic anaemia after 3 and 7 days, and macrocytosis and haemolytic anaemia after 14 days. HNP treatment showed hypochromic anaemia and polycythemia after 3 days, and macrocytosis and hypochromic anaemia after 7 days and haemolytic hypochromic anaemia after 14 days. All copper-exposed fish showed leukopenia at all times, except for HNP after 7 days and CS after 3 days. CS treatment at all times, and NCuO treatments after 14 days showed elevated plasma bilirubin. CS (3rd and 7th days) and HNP (3rd day) treatments had significantly higher plasma triglyceride compared to the control. Significant increases in plasma cholesterol and lipoprotein levels were observed after 3 and 14 days in CS, and after 14 days in LNP treatment; whereas HNP treatment had significantly higher high density lipoprotein (HDL) and very low-density lipoprotein (VLDL) levels after 3 days, and cholesterol, HDL and low-density lipoprotein (LDL) after 14 days. In conclusion, CS and NCuO induce anaemia probably due to iron metabolism disorder and RBC destruction in carp. CS and NCuO (at high concentration) alter plasma lipid profile, which may be due to stress-induced lipolysis and hepatobiliary damages. At similar concentrations, copper nanoparticles are less toxic to carp than copper ions.

The aim of our research was to study the influence of citrate and sulfate of copper, manganese and zinc on the carbohydrates composition of biomass of the medicinal mushroom Trametes versicolor (L.) Lloyd. cultivated in a liquid medium. The studied strain of Trametes versicolor 353 was obtained from the Culture Collection of Mushrooms (IBK) from the M. G. Kholodny Institute of Botany, National Academy of Sciences of Ukraine. Citrates of copper, manganese and zinc were obtained from the Institute of Nanobiotechnologies and Resource Conservation of Ukraine, Kyiv. In this study we used glucose-peptone-yeast extract medium (GPY) with the following composition of (g/L): glucose – 25, peptone – 3, yeast extract – 3, K2HPO4 – 1, KH2PO4 – 1, MgSO4 ∙ 7H2O – 0.25, distilled water – 1,000 ml; pH 6,5 (control medium). Cu2+ (sulfate form or citrate form) were added to control medium in concentration 4 mg/L, Zn2+ and Mn2+ (sulfate form or citrate form) were added to control medium in concentration 1 mg/L. Mycelium was grown in a submerged culture on a rotary shaker (120 rpm) at 26 °C in 250 ml Erlenmeyer flasks, containing 50 ml of liquid medium. The biomass was harvested after 9 days of cultivation in the liquid medium. Monosaccharides and sugar alcohols was analyzed by high-performance liquid chromatography Agilent 1200 (Agilent technologies, USA). The results of our research demonstrated that the fraction of total carbohydrates from T. versicolor 353, which were cultivated on the control medium, consists of glucose (91.5%), galactose (1.9%), mannose (5.4%), fucose (0.6%) and xylose (0.7%). The adding of sulfate of zinc or copper to the liquid medium didn’t change the content of monosaccharides of T. versicolor 353 biomass relative to the control medium. At the same time, in the medium with citrate of zinc the amount of glucose increased and the amount of mannose decreased relative to the control medium. Xylose and fucose were not detected in this case. In mycelium of T. versicolor 353 that was cultivated in the medium with manganese sulfate or manganese citrate we detected a small amount of ribose. But the content of other monosaccharides didn’t change in the medium with sulfate of manganese. At the same time, the addition of citrate of manganese to the medium raised the amount of mannose and reduced the amount of glucose in the biomass of T. versicolor 353 relative to the control medium. Also copper citrate reduced the content of glucose in mycelium of T. versicolor 353 relative to the control medium. But in this case we detected mannitol and sorbitol in the biomass. This data indicates that synthesis of sugur alcohols in T. versicolor 353 depend on copper ions in bioactive forms of citrate.

Multi-ion fabrics (especially silver ion fabrics) have special advantages as electromagnetic radiation, but the use of noble metals enhances its cost. Electroless nickel plating (EP-Ni) has great potential application in fabricating low-cost metallized material. Here, EP-Ni on pure cotton surface to fabricate radiation protection suits for pregnant woman was established to replace traditional protection suits with silver film. The active groups on the cotton/polyester blend fiber surface could absorb tin and palladium ions, acting as catalytic centers, which can catalyze the reduction of Ni2+ in the plating solution. Ni particle with (111) crystal plane preferential oriented crystal structure deposited on cotton surface with a coarse microstructure. The Ni deposited amount is about 19%. The fabricated material exhibited a shielding effectiveness of 29.5 dB. Studies also shown that bending has no negative effect on crystallinity and electrical property. But more bending times could lead to crack, which would decline electromagnetic shielding performance by 24%.

Pyrite tailings from operating industrial facilities, beyond their primary component, frequently contain valuable base metal minerals (e.g., Co, Ni, Cu) that are in constant demand and are critical for 'green energy' technologies. Despite the comparatively low concentration of Ni and Co in these tailings, their overall reserves are potentially significant. The objective of this study was to investigate the recovery of nickel, cobalt, and copper from leach sulfuric solutions derived from nickel-cobalt-bearing pyrite concentrate using solvent extraction. It was established that selective metal recovery necessitates the preliminary precipitation of iron as jarosite at a controlled pH. From the resultant iron-free solution, selective copper extraction was achieved using Acorga 5640 in kerosine at a pH range of 2.8�3.0. This was followed by the co-extraction of Ni and Co using Cyanex 272 combined with TBP at a pH of 5.0. To obtain high-purity cobalt and nickel sulfate, the optimal solvent extraction scheme was determined to be 2E+1Sc+1S (2 Extraction stages + 1 scrabbing stage + 1 Stripping stage). As a result of this research, pure iron hydroxide, along with marketable nickel, cobalt, and copper sulfates, were successfully recovered. Further concentration of the final cobalt sulfate solution requires a subsequent sorption process.

Selective electroless copper plating micro-coil assisted by 248 nm excimer laser

Sedimentation Rate in Sheep

Electrodeposited White bronze (speculum : Cu-Sn 40mass%) shows promise as an alternative to nickel coating. Copper-tin(40mass%) alloy film was deposited over a current density range from 0.5 to 4A/dm2 and at a temperature of 25oC in the following bath composition : 0.1474mol/L CuSO4, 0.0526mol/L SnSO4, 1.0mol/L sulfosuccinic acid, 0.4mol/L L-methionine and 3g/L polyoxyethylene-α-naphthol. The coexistence of L-methionine and polyoxyethylene-α-naphthol markedly inhibited the deposition of copper over a noble potential range, and markedly reduced subreaction.The copper-tin(40mass%) alloy film obtained was silvery white. Copper and tin ions in the effluent were separated as hydroxide, and the residual concentration of tin and copper ions in the bath shown above decreased to less than 5mg/L.

The hardness and tribological properties of multilayered Cu/Ni-P coatings prepared via electrodeposition with a single bath containing nickel sulfate, copper sulfate, phosphoric acid and sodium citrate have been examined. The location of Cu and Ni-P sublayers that were alternately deposited at 1mA/cm2 and 50mA/cm2, respectively, was analyzed. These sublayers consist of crystalline Cu and amorphous Ni-P. Results have indicated that the hardness of the multilayered coating is lower than that of Ni-P single coating and increases with an increase in the thickness of Ni-P sublayers. A remarkable finding is that wear resistance of the multilayered coating is superior to that of Ni-P single coating, which may be attributed to the suppression of the propagation of cracks in the multilayered structure.

The study included 300 samples collected from 150 clinical and 150 hospital environmental sources. Only 43 (14.3%) isolates belonged to Ps. aeruginosa. The isolates were tested for their susceptibility to 7 types of heavy metals (HM) namely Copper Sulfate, Silver Sulfate, Mercury chloride, Lead nitrate, Zinc sulfate, Cadmium sulfate, and Nickel sulfate. The screening test for ability of the isolates to resist HM was detected using lead nitrate in concentration of 400μg/ml. Results revealed that 37/43 were resistant to lead nitrate (400μg/ml). The MIC of 7 HM was detected by agar dilution and pouring method. Results revealed that most of the isolates were resistant to 7 HM in some of concentrations. The plasmid content was investigated for all 37 isolates of Ps. aeruginosa (34 clinical and 3 environmental). Results revealed that most isolates 32/37 harbored large (mega) plasmid. Biofilm production of Ps. aeruginosa isolates was investigated; results showed that 20/43 (47%) of isolates had biofilm. This study concluded that the increase of HM resistance was correlated with biofilm production for some HM used. The bacterial curing is proceeding for one isolate of Ps. aeruginosa (Ps.3). The results showed survived resistance to all HM used, which may be due to HM resistance trait was carried out on bacterial chromosome rather than plasmid.