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Coaxial one-side resistance spot welding (COS-RSW) is an advanced technique for joining CFRP/metal dissimilar materials. In the present work, a three-dimensional model was developed based upon an in-house finite element code JWRIAN-SPOT to simulate the multi-physical process of the COS-RSW. The thermal cycle and joining strength of COS-RSW joints with different welding parameters were measured experimentally. The sensitivity of material properties of electrode couple and component of accumulated heat generation were discussed in detail. The predicted thermal cycles presented a reasonable agreement with measurements, which also explained the influence of welding parameters on temperature field. The joining strength of COS-RSW joints can be evaluated qualitatively via the area of effective molten zone, which reached about 20 MPa with a 4800 A welding current. The column and cylinder electrodes determined the peak value of interface temperature and molten zone area, respectively. The cylinder electrode was suggested to be fabricated by a high resistivity material to generate sufficient Joule heat. Moreover, the SUS304 electrode and its contact zone provided more than 70% of the entire heat generation. The materials of electrode couple should be determined carefully when employing COS-RSW for joining CFRP and other metals.

Recently, quantitative NMR (qNMR), especially 1H-qNMR, has been widely used to determine the absolute quantitative value of organic molecules. We previously reported an optimal and reproducible sample preparation method for 1H-qNMR. In the present study, we focused on a 31P-qNMR absolute determination method. An organophosphorus compound, cyclophosphamide hydrate (CP), listed in the Japanese Pharmacopeia 17th edition was selected as the target compound, and the 31P-qNMR and 1H-qNMR results were compared under three conditions with potassium dihydrogen phosphate (KH2PO4) or O-phosphorylethanolamine (PEA) as the reference standard for 31P-qNMR and sodium 4,4-dimethyl-4-silapentanesulfonate-d6 (DSS-d6) as the standard for 1H-qNMR. Condition 1: separate sample containing CP and KH2PO4 for 31P-qNMR or CP and DSS-d6 for 1H-qNMR. Condition 2: mixed sample containing CP, DSS-d6, and KH2PO4. Condition 3: mixed sample containing CP, DSS-d6, and PEA. As conditions 1 and 3 provided good results, validation studies at multiple laboratories were further conducted. The purities of CP determined under condition 1 by 1H-qNMR at 11 laboratories and 31P-qNMR at 10 laboratories were 99.76 ± 0.43 and 99.75 ± 0.53%, respectively, and those determined under condition 3 at five laboratories were 99.66 ± 0.08 and 99.61 ± 0.53%, respectively. These data suggested that the CP purities determined by 31P-qNMR are in good agreement with those determined by the established 1H-qNMR method. Since the 31P-qNMR signals are less complicated than the 1H-qNMR signals, 31P-qNMR would be useful for the absolute quantification of compounds that do not have a simple and separate 1H-qNMR signal, such as a singlet or doublet, although further investigation with other compounds is needed.

As a new absolute quantitation method for low-molecular compounds, quantitative NMR (qNMR) has emerged. In the Japanese Pharmacopoeia (JP), 15 compounds evaluated by qNMR are listed as reagents used as the HPLC reference standards in the assay of crude drug section of the JP. In a previous study, we revealed that humidity affects purity values of hygroscopic reagents and that (i) humidity control before and during weighing is important for a reproducible preparation and (ii) indication of the absolute amount (not purity value), which is not affected by water content, is important for hygroscopic products determined by qNMR. In this study, typical and optimal conditions that affect the determination of the purity of ginsenoside Rb1 (GRB1), saikosaponin a (SSA), and barbaloin (BB) (i.e., hygroscopic reagents) by qNMR were examined. First, the effect of humidity before and during weighing on the purity of commercial GRB1, with a purity value determined by qNMR, was examined. The results showed the importance afore-mentioned. The results of SSA, which is relatively unstable in the dissolved state, suggested that the standardization of humidity control before and during weighing for a specific time provides a practical approach for hygroscopic products. In regard to BB, its humidity control for a specific time, only before weighing, is enough for a reproducible purity determination.

NMR spectroscopy has recently been utilized to determine the absolute amounts of organic molecules with metrological traceability since signal intensity is directly proportional to the number of each nucleus in a molecule. The NMR methodology that uses hydrogen nucleus (1H) to quantify chemicals is called quantitative 1H-NMR (1H qNMR). The quantitative method using 1H qNMR for determining the purity or content of chemicals has been adopted into some compendial guidelines and official standards. However, there are still few reports in the literature regarding validation of 1H qNMR methodology. Here, we coordinated an international collaborative study to validate a 1H qNMR based on the use of an internal calibration methodology. Thirteen laboratories participated in this study, and the purities of three samples were individually measured using 1H qNMR method. The three samples were all certified via conventional primary methods of measurement, such as butyl p-hydroxybenzoate Japanese Pharmacopeia (JP) reference standard certified by mass balance; benzoic acid certified reference material (CRM) certified by coulometric titration; fludioxonil CRM certified by a combination of freezing point depression method and 1H qNMR. For each sample, 1H qNMR experiments were optimized before quantitative analysis. The results showed that the measured values of each sample were equivalent to the corresponding reference labeled value. Furthermore, assessment of these 1H qNMR data using the normalized error, En-value, concluded that statistically 1H qNMR has the competence to obtain the same quantification performance and accuracy as the conventional primary methods of measurement.

Quantitative NMR (qNMR) has been developed as an absolute quantitation method to determine the purity or content of organic compounds including marker compounds in crude drugs. The "qNMR test" has been introduced into the crude-drug section of the Japanese Pharmacopoeia (JP) for determining the purity of reagents used for the assay in the JP. In Supplement II to the JP 17th edition published in June 2019, fifteen compounds adopted qNMR test were listed as the reagents for the assay. To establish the "qNMR test" in the crude drug section of the JP, there were several problems to be solved. Previously, we reported that the handling impurity signals from reference substances and targeted marker compounds, chemical shifts of reference substances, and peak unity of signals of targeted marker compounds are important factors to conduct qNMR measurements with intended accuracy. In this study, we investigated that the hygroscopicity of reagents could cause the changes in the compounds' purity depending on increasing their water content. Twenty-one standard products used for the crude-drug test in JP were examined by water sorption-desorption analysis, and ginsenosides and saikosaponins were found to be hygroscopic. To prepare a sample solution of saikosaponin b2 for qNMR analysis, samples need to be maintained for 18 h at 25°C and 76% relative humidity; further, samples need to be weighed at the same humidity for the qNMR analysis.

Recently, quantitative NMR (qNMR), especially

Quantitative NMR (qNMR) is applied to determine the absolute quantitative value of analytical standards for HPLC-based quantification. We have previously reported the optimal and reproducible sample preparation method for qNMR of hygroscopic reagents, such as saikosaponin a, which is used as an analytical standard in the assay of crude drug section of Japanese Pharmacopoeia (JP). In this study, we examined the absolute purity determination of a hygroscopic substance, indocyanine green (ICG), listed in the Japanese Pharmaceutical Codex 2002, using qNMR for standardization by focusing on the adaptation of ICG to JP. The purity of ICG, as an official non-Pharmacopoeial reference standard (non-PRS), had high variation (86.12 ± 2.70%) when preparing qNMR samples under non-controlled humidity (a conventional method). Additionally, residual ethanol (0.26 ± 0.11%) was observed in the non-PRS ICG. Next, the purity of non-PRS ICG was determined via qNMR when preparing samples under controlled humidity using a saturated sodium bromide solution. The purity was 84.19 ± 0.47% with a lower variation than that under non-controlled humidity. Moreover, ethanol signal almost disappeared. We estimated that residual ethanol in non-PRS ICG was replaced with water under controlled humidity. Subsequently, qNMR analysis was performed when preparing samples under controlled humidity in a constant temperature and humidity box. It showed excellent results with the lowest variation (82.26 ± 0.19%). As the use of a constant temperature and humidity box resulted in the lowest variability, it is recommended to use the control box if the reference ICG standard is needed for JP assays.

NMR spectroscopy has recently been utilized to determine the absolute amounts of organic molecules with metrological traceability since signal intensity is directly proportional to the number of each nucleus in a molecule. The NMR methodology that uses hydrogen nucleus (

Dissimilar materials joining of metal to carbon fibre reinforced plastic (CFRP), which consisted of PA6, modified polypropylene (PP) or polyphenylene sulphide (PPS) as matrix polymer with short car...

Dissimilar materials joining of SUS304 and carbon-fibre-reinforced plastics consisting of short fibres and thermoplastics was performed. The materials were joined by series resistance spot welding. The electrodes were pressed on the metal plate of the lap joint of metal/carbon-fibre-reinforced plastics. The SUS304 plate was heated by resistance heating, causing the thermoplastic near the interface to melt slightly because of heat conduction. SUS304 could be joined directly to carbon-fibre-reinforced polyamide and modified polypropylene, but not to polyphenylene sulphide. The joining area increased with an increase in the welding current and welding time, so did the tensile shear fracture load. Furthermore, the silane coupling agent treatment of SUS304 was highly effective in increasing the joining strength.

Carbon fibre reinforced plastics (CFRP) and Al5052 sheets were joined by coaxial one-side resistance spot welding (COS-RSW). The cross-section features and mechanical behaviour of the joints in single lap shear (SLS) test were investigated. The underlying joining mechanism was found to be the N C O covalent bond between silane coupling agent and CFRP via the X-ray photoelectron spectroscopy (XPS) analysis. The joints of low welding current exhibited interfacial fracture with low strength and small displacement during the SLS test, while the joints of high welding current presented a staged failure process with tearing of the CFRP, which gave higher strength and larger displacement. The bonding zone was divided into three subzones, which showed specific surface morphologies and distinct contributions to the load-bearing capacity of the joint. The joining strength showed a positive correlation with welding current until the occurrence of decomposition in CFRP, which reduced the area of effective bonding zone and played a negative effect on strength.

Carbon fiber reinforced plastic (CFRP) is a prospective lightweight material in automobile industry. However, joining metal and CFRP is a great challenge. In the present study, an innovative process called coaxial one-side resistance spot welding (COS-RSW) is proposed to fabricate Al5052 (Al) and CFRP joints. Based upon our newly developed finite element code JWRIAN, the electric-thermal-mechanical coupled process of COS-RSW is modeled and validated with experiments. The influences of welding current, welding time and electrode force on CFRP molten zone are investigated in detail. The results show that the depth of molten zone has a strong correlation with both welding current and welding time. A relative low welding current or short welding time that results in the Al/CFRP interface temperature below the melting temperature of the resin matrix is insufficient to form a sound connection between the two sheets. While excessive current or too long welding time may lead to overheating of CFRP and decomposition of the resin matrix, which increases the risk of weak joining. Furthermore, it is found that the depth of molten zone increases even at the cooling stage, which indicates accurate simulation for both the heating and the cooling stages of the COS-RSW process is indispensable. Keywords: Coaxial one-side resistance spot welding, Carbon fiber reinforced plastic, Al5052, Dissimilar materials, Multiphysics coupling simulation

A new fluorescent approach was developed to visualize grouting processes. The evaluation of the effect of grouting is carried out by methods based mainly on physical measurements such as permeability and porosity characteristics. However, these estimates do not necessarily correlate with practical grouting data. In this paper, the distributions of various grout mixtures containing fluorescent substances were clearly visualized under ultraviolet light, using a borehole television system or a microscope. Since this approach enabled direct observation of grout distribution, it is considered that this approach is useful for analysis of grouting mechanisms, designing grout curtains, etc.

Efficient syntheses of 2′-bromo-2′-deoxy-3′,5′-O-TPDS-uridine (5a) and 1-(2-bromo-3,5-O-TPDS-β-D-ribofuranosyl)thymine (5b) from uridine and 1-(β-D-ribofuranosyl)thymine are described, respectively. The key step is a treatment of 3′,5′-O-TPDS-O2,2′-anhydro-1-(β-D-ardbinofuranosyl)uracil (4a) and -thymine (4b) with LiBr in the presence of BF3-OEt2 in 1,4-dioxane at 60°C to give 5a and 5b in 98%, and 96% yield, respectively. 1. Partial Protection of Carbohydrate Derivatives. Part 30. For Part 29, see Kawashima, E; Aoyama, Y.; Sekine, T.; Miyahara, M.; Radowan, M. F.; Nakamura, E.; Kainosho, M.: Kyogoku, Y.; Ishido, Y.I. Org. Chem. submitted. #This paper is dedicated to Dr. Yoshihisa Mizuno, an Emeritus Professor of Hokkaido University, on the occasion of his 75th birthday.