Bridging the Compliance Gap in Hydrogen Analysis

Analysis Solutions for Quality Control of Hydrogen C10G-E102C The Coming Hydrogen Energy Society Fuel cells for domestic use and fuel cell vehicles (FCV) are gradually becoming more common. Fuel cells produce electricity from hydrogen and are indispensable when it comes to realizing a hydrogen energy society. Hydrogen can be produced by various industrial processes, and its conversion with electrical power is easy. Therefore, its use as a fuel for thermal electrical power generation and for storage of natural energy, such as solar and wind, is being evaluated as the hydrogen energy society comes into focus. Topics Title Products Page Measurement of Impurities in Hydrogen Gas Trace Impurity Analysis of Hydrogen Fuel in Fuel Cell Vehicle Gas Chromatograph 5 Determination of Trace Amounts of Sulfur Compounds in Hydrogen Gases by GC-SCD Gas Chromatograph 6 Analysis of Inorganic Gases and Hydrocarbons by GC-MS Gas Chromatograph Mass Spectrometer 7 High-Resolution Analysis of Carbon Monoxide (CO) Fourier Transform Infrared Spectrophotometer 8 Analysis of Hydrogen Fuel for Inorganic Halogens, Formic Acid, Ammonia, and Formaldehyde Ion Chromatograph/ High Performance Liquid Chromatograph 9 Hydrogen Carrier Evaluation of Ammonia Synthesis Gas Chromatograph 10 High-Sensitivity Analysis of Ammonia in Water 11 Analysis of Hydrogen in Solution 12 Analysis of Hydrogen in Gas Analysis of Toluene, Methylcyclohexane (MCH) in Solution Gas Chromatograph Mass Spectrometer 13 Hydrogen Embrittlement Various Tests for Material Strength in Hydrogen Environments Precision Universal Testing Machine 14 Observation of Corroded Copper Pipe with a Microfocus X-ray CT System Microfocus X-ray CT System 15 Accurate Measurements of Micro-Displacements in a Compression Fatigue Test of a Gasket Fatigue and Endurance Testing Machine 16 Catalytic Analysis Evaluation of a Catalyst Used in the Production of Fuel Cell Hydrogen Transportable Gas Analyzer 17 Analysis of an Automotive Three-Way Catalyst Electron Probe Microanalyzer 18 Analysis of an MEA (Membrane/Electrode Assembly) by EPMA 19 Analysis of an MEA (Membrane/Electrode Assembly) by XPS X-Ray Photoelectron Spectrometer 20 Hydrogen Tank Observation of Carbon Fiber Reinforced Thermoplastic Resin with an X-ray CT System Microfocus X-ray CT System 21 Verification and Validation of Uniaxial Tensile Test Simulation Results of Composites Microfocus X-ray CT System Precision Universal Testing Machine 22 Example of Non-Destructive Inspection Using an Ultrasonic Optical Flaw Detector Ultrasonic Optical Flaw Detector 23 Evaluation of Thermal Characteristics of Rubber O-Rings Differential Scanning Calorimeter 24 Interlaminar Fracture Toughness Evaluation of CFRP Precision Universal Testing Machine 25 Water Electrolysis Process Monitoring of PEM H2 Electrolysis Feed Water Total Organic Carbon Analyzer 26 Impurities in hydrogen production affect subsequent industrial processes. Consequently, strict purity standards have been defined for hydrogen used in fuel cells (ISO 14687). This is because if hydrogen contains carbon monoxide, sulfur components, etc., the catalyst of the fuel cell will be damaged. The hydrogen fuel standard for Fuel Cell Vehicles (ISO 14687 Type II Grade D) defines many items to be controlled, and Shimadzu analytical instruments can play a role in analyzing these items. Analysis of Impurities in Hydrogen ISO 14687 Grade D (μmol/mol) (ppm) System GC GC-MS GC IC HPLC FTIR BID TCD FID SCD H2O 5 Total Hydrocarbons (except CH4) 2 CH4 100 O2 5 He 300 N2 300 Ar 300 CO2 2 * CO 0.2 * Formaldehyde 0.2 Total sulfur compounds 0.004 Halogen compounds 0.05 Ammonia 0.1 ISO14687 compliant Less than ISO 14687 standard but measurable * A Jetanizer or a methanizer is needed. Hydrogen Energy Analysis Solutions for Quality Control of Hydrogen 4 Hydrogen is difficult to store and transport long distances efficiently when left as a gas. A hydrogen carrier is an efficient way of storing and transporting hydrogen in the form of a liquid or a hydrogenated compound. Methods include liquefying the hydrogen or increasing the density of the compressed hydrogen gas. Another method involves converting the hydrogen into another substance that has a high hydrogen density and is more easily handled (such as organic hydrides, ammonia, or formic acid) and then removing the hydrogen from this substance for use. Rather than removing the hydrogen for use, the hydrogen energy can also be utilized by burning something like ammonia as is. Hydrogen embrittlement is a phenomenon that occurs when hydrogen atoms are absorbed by a metal. This reduces the ductility of the metal, which reduces its strength. Shimadzu analytical instruments are useful for testing the strength of the materials in pipes and tanks used for the transport and storage of liquid hydrogen and hydrogen gas; for checking the degree of corrosion using X-ray CT scans; and for analysis of the plating process, which may be prone to hydrogen embrittlement. There are various ways to manufacture hydrogen, including steam reforming and water electrolysis. Regardless of the method, catalysts play an important role in improving efficiency and lowering costs. Accordingly, it is important to evaluate the performance of the catalyst and to check on the degree of deterioration. Catalysts involved in hydrogen manufacturing are often metals such as platinum or palladium. Evaluations can be performed using portable gas concentration measurement instruments. Verifying the degree of deterioration and analyses of the causes of deterioration can be performed using electron probe micro-analyzers and X-ray photoelectron spectrometers. Fuel Cell Vehicles (FCVs) are equipped with hydrogen tanks. With the high-pressure hydrogen tanks used in vehicles, the higher the hydrogen storage pressure and compressive pressure, the greater the amount of hydrogen that can be stored, which can extend the cruising range of the FCV. For FCV hydrogen tanks, gas tightness, heat resistance, and pressure resistance are important parameters as is reducing the size, weight, and cost. At present, to satisfy the above-mentioned conditions, plastic liners, carbon fiber reinforced plastics, glass fiber reinforced plastics, and other materials are used to create hydrogen tanks. Universal testing machines and thermomechanical analyzers are effective for determining the characteristics of each material. In addition, X-ray CT systems and ultrasonic optical flaw detectors are useful for observing cracks and voids in hydrogen tanks. Hydrogen Carrier Hydrogen Embrittlement Catalyst Analysis Hydrogen Tanks Pressurized Hydrogen (700 MPa) Liquid Hydrogen Organic Hydride (Methyl Cyclohexane) Ammonia Formic Acid Molecular Weight 2.0 2.0 98.2 17.0 46.0 H2 Content (wt %) 100.0 100.0 6.2 17.8 4.3 Volumetric H2 Density (Kg-H2/m3) 39.6 70.8 47.3 121 53 Boiling Point (°C) = -253 101 -33 101 H2 Release Enthalpy Change* (kJ/mol-H2) = 0.9 67.5 30.6 31 (ΔG 4aq.) *H2 release enthalpy change: Energy required to remove hydrogen Carbon Fiber Reinforced Plastic (CFRP) Polymeric Material (Resin) Glass Fiber Reinforced Plastic (GFRP) SIP Energy Carriers: https://www.jst.go.jp/sip/pdf/SIP_energycarriers2016_en.pdf Extract from the JST News April 2019 edition entitled “Effective Use of Hydrogen Energy with the Power of Formic Acid” 5 Measurement of Impurities in Hydrogen Gas 􀀢􀁑􀁑􀁍􀁊􀁄􀁂􀁕􀁊􀁐􀁏 This instrument separates each compound in the sample, and then quantifies each component using a detector. The data obtained tells the analyst what compounds are in the sample and in what quantities. The Jetanizer is an FID nozzle-type methanizer developed by Activated Research Company in which a catalyst is packed inside the nozzle. Although a conventional FID is not sensitive to CO and CO2, these compounds can be converted to CH4, which can then be analyzed by an FID by replacing the FID nozzle with the Jetanizer and making slight changes to the analysis conditions. Use of the Jetanizer enables highly sensitive simultaneous analysis of CO, CO2, CH4 and other compounds with N2 carrier gas. Gas Chromatograph Brevis GC-2050 FID Nozzle-type Methanizer Jetanizer ■ Measurement Results (Extract) A Micropacked ST column supports separation of inorganic gases, including carbon dioxide and lower hydrocarbons, making it suitable for simultaneous analysis of impurities in hydrogen gas. A standard gas was diluted with hydrogen to adjust the component concentrations (other than air components) to about 0.2 ppm, and this gas was analyzed using a Micropacked ST column. The lower limit of detection of carbon monoxide was calculated as 0.078 ppm (S/ N=3). The results include detection of the maximum concentration stipulated by ISO 14687-2. CO gas samples (CO concentration: 0.2 ppm) were prepared using H2 as the dilution gas, and five sequential analyses were conducted. Fig. 2 shows the overlaid chromatograms of the five sequential analyses. The calculated Limit of Detection (S/N = 3) of CO was 0.04 ppm. Analysis of Trace Carbon Monoxide (CO) in Hydrogen Fuel Using Jetanizer • Using a barrier discharge ionization detector (BID) enables the high-sensitivity analysis of carbon monoxide in hydrogen and the batch analysis of impurities in hydrogen. • Using a Jetanizer enables highly sensitive simultaneous analysis of CO, CO2, CH4 and other compounds with N2 carrier gas. benefits If impurities exist in the hydrogen used in fuel cell vehicles, they may poison the catalyst in the cell, reducing catalytic performance. Using a gas chromatograph enables simultaneous analysis of impurities contained in hydrogen. Trace Impurity Analysis of Hydrogen Fuel in Fuel Cell Vehicle Gas Chromatograph Fig. 2 Overlaid Chromatograms of 0.2 ppm CO in H2 Gas (n=5) 5.0 5.1 5.2 5.3 5.4 5.5 5.6 5.7 5.8 5.9 min Data 5 Data 4 Data 3 Data 2 Data 1 Fig. 1 Chromatogram of Simultaneous Analysis of Impurities in Hydrogen (Micropacked ST Column) 􀀰􀀓 􀀯􀀓 􀀤􀀰 􀀩􀀓 􀀤􀀰 􀀯􀀓 􀀤􀀩􀀕 􀀤􀀩􀀕 􀀤􀀰􀀓 􀀤􀀰􀀓 􀀯􀀓􀀰 􀀯􀀓􀀰 􀀤􀀓􀀩􀀓 􀀤􀀓􀀩􀀓 􀀤􀀓􀀩􀀕 􀀤􀀓􀀩􀀕 􀀤􀀓􀀩􀀗 􀀤􀀓􀀩􀀗 􀀒􀀏􀀑 􀀓􀀏􀀑 􀀔􀀏􀀑 􀀕􀀏􀀑 􀀖􀀏􀀑 􀀗􀀏􀀑 􀀘􀀏􀀑 􀀙􀀏􀀑 􀀚􀀏􀀑 􀀒􀀑􀀏􀀑 􀀒􀀒􀀏􀀑 􀀒􀀓􀀏􀀑 􀁎􀁊􀁏 􀀓􀀏􀀑 􀀔􀀏􀀑 􀀖􀀏􀀑 􀀗􀀏􀀑 􀀘􀀏􀀑 􀀙􀀏􀀑 􀀚􀀏􀀑 􀀒􀀑􀀏􀀑 􀀒􀀒􀀏􀀑 􀀰􀀓􀀛􀀁􀀢􀁑􀁑􀁓􀁐􀁙􀀏􀀁􀀓􀀖􀀁􀁑􀁑􀁎􀀍􀀁􀀯􀀓􀀛􀀁􀀢􀁑􀁑􀁓􀁐􀁙􀀏􀀁􀀒􀀗􀀑􀀁􀁑􀁑􀁎􀀍􀀁􀀤􀀰􀀓􀀛􀀁􀀢􀁑􀁑􀁓􀁐􀁙􀀏􀀁􀀑􀀏􀀕􀀕􀀁􀁑􀁑􀁎􀀍􀀁􀀰􀁕􀁉􀁆􀁓􀀁􀀤􀁐􀁎􀁑􀁐􀁏􀁆􀁏􀁕􀁔􀀛􀀁􀀢􀁑􀁑􀁓􀁐􀁙􀀏􀀁􀀑􀀏􀀓􀀁􀁑􀁑􀁎􀀁 􀀴􀀐􀀯 Carbon monoxide (CO) 7.7 Methane (CH4) 27 Carbon dioxide (CO2) 42 Nitrous oxide (N2O) 21 Acetylene (C2H2) 8.3 Ethylene (C2H4) 31 Ethane (C2H6) 42 􀀢􀁑􀁑􀁍􀁊􀁄􀁂􀁕􀁊􀁐􀁏 􀀱􀁓􀁐􀁅􀁖􀁄􀁕 􀀱􀁓􀁐􀁅􀁖􀁄􀁕 6 Measurement of Impurities in Hydrogen Gas 􀀱􀁓􀁐􀁅􀁖􀁄􀁕 􀀢􀁑􀁑􀁍􀁊􀁄􀁂􀁕􀁊􀁐􀁏 The Nexis SCD-2030 is a next-generation sulfur chemiluminescence detection system. It was developed to fulfill the unmet needs of laboratories around the world. The dramatically enhanced sensitivity and reliability, the excellent maintainability, and the automation functions, a first for the industry, will improve laboratory productivity. ■ Measurement Results In ISO 14687, a quantification limit of 4 ppb total sulfur compounds is defined. To achieve this concentration, we used an SCD and a cryotrap device* by liquid nitrogen cooling that allows for sample concentration. To avoid any adsorption, absorption, and reaction of sulfur compounds, the tubing and valves were Sulfinert® treated. * Microjet Cryo-Trap (Frontier Laboratories) To determine repeatability of the analytical method, a 3.9 ppb of a carbonyl sulfide (COS) standard was injected 10 times. Peak area and concentration repeatability was below 2 %, ensuring reliable detection and quantitation of the sulfur compounds at low concentrations. This application was prepared by Shimadzu Europa GmbH with assistance and cooperation of DBI Gas- und Umwelttechnik GmbH in Leipzig (Germany), which also kindly provided standard gases for this investigation. • Using an SCD and a cryotrap device by liquid nitrogen cooling, sulfur compounds in hydrogen can be analyzed down to the ppb level. • Equimolarity of the sulfur detection by SCD allows analysis without individual compound calibration. benefits Among the impurities in the hydrogen used in fuel cell vehicles, particular control is required of the impurities in sulfur compounds. Analysis is possible using a sulfur chemiluminescence detector (SCD) that is selective for sulfur compounds. Determination of Trace Amounts of Sulfur Compounds in Hydrogen Gases by GC-SCD Gas Chromatograph Table 1 Repeatability of 10 Consecutive Measurements of a COS Standard # Area Conc [ppb] 1 51151 3.879 2 50914 3.861 3 52193 3.958 4 51838 3.931 5 51800 3.928 6 50768 3.850 7 50815 3.854 8 50716 3.846 9 50557 3.834 10 50300 3.814 Average 51.105 3.876 %RSD 1.23 1.23 Fig. 1 Chromatogram of Sulfur Sample Including Internal Standard H2S Internal standard (Tertiary butyl mercaptan) Fig. 2 Calibration Curve for COS Nexis SCD-2030 + valve box (option) Sulfur Chemiluminescence Detection Gas Chromatograph System Nexis SCD-2030 7 􀀢􀁑􀁑􀁍􀁊􀁄􀁂􀁕􀁊􀁐􀁏 ■ Measurement Results (Extract) A total ion current chromatogram is shown in Fig. 1. This column does not separate carbon monoxide from the components in air. Furthermore, at this concentration level, water causes baseline fluctuations. Extracted ion chromatograms of respective components are shown in Fig. 2. By selecting ions, all 12 components, including those not separated in the total ion current chromatogram, can be analyzed without being affected by water. Inorganic gases and gaseous hydrocarbons can be measured using a porous layer open tubular (PLOT) column. benefits It is important to measure hydrocarbons as well as N2, N2O and other inorganic gases in hydrogen because if the hydrogen fuel contains these gases or hydrocarbons, the internal fuel cell mechanism will deteriorate. Analysis of Inorganic Gases and Hydrocarbons by GC-MS Gas Chromatograph Mass Spectrometer Fig. 1 Total Ion Current Chromatogram Fig. 2 Mass Chromatograms for Respective Components Measurement of Impurities in Hydrogen Gas 8 Measurement of Impurities in Hydrogen Gas 􀀢􀁑􀁑􀁍􀁊􀁄􀁂􀁕􀁊􀁐􀁏 Measurements are performed of the infrared spectrum of the target gas that was injected into the gas cell. Qualitative and quantitative analyses are then performed based on the peak wavenumber and the peak intensity characteristic of the gas. • The gas injected into the gas cell is measured directly, enabling high-speed analysis. (Approximately 1 minute) •The instrument is capable of simultaneous multicomponent measurements. • Pretreatment is not required, so a gas that is changing continuously can be monitored in real time. Fourier Transform Infrared Spectrophotometer IRXross ■ Measurement Results (Extract) Using CO as an example of a low-molecular weight gas, we measured the spectra of CO samples at different concentrations (95 ppm, 191 ppm, 1207 ppm, 2415 ppm) (Fig. 1), and then generated a calibration curve. In this case (Fig. 2), the resolution of 0.25 cm-1 was used. For the calibration curve, we used the height of the peak in the vicinity of 2170 cm-1, and primary linear calculations were conducted using the multipoint calibration curve method. Use of a 10 cm gas cell and a DLATGS detector makes quantitation possible over a wide range of concentrations, from tens to thousands of ppm. The correlation coefficient of r = 0.999 for the calibration curve indicated excellent linearity. To compare spectral differences due to resolution, we measured the infrared spectra of water vapor at resolutions of 0.25 cm-1, 0.5 cm-1 and 1 cm-1, respectively (Fig. 3). As can be seen here, the peaks that were not separated at 0.5 cm-1 and 1 cm-1 were clearly separated when measured with a resolution of 0.25 cm-1. By conducting measurement at high resolution, the spectral peak intensity is noticeably increased, making it easier to distinguish between two peaks that are closely adjacent to one another. • An FTIR with high-resolution can quantify the gas. benefits • A n FTIR can analyze a gas in real time. FTIR is being used for analysis of gases in various industries, such as the gas manufacturing industry where it is used for production management, and for gas monitoring in such fields as chemical manufacturing and semiconductor manufacturing. High-Resolution Analysis of Carbon Monoxide (CO) Fourier Transform Infrared Spectrophotometer Fig. 1 Overlaid Spectra of CO at Four Concentrations Fig. 2 Calibration Curve of CO Using Four Concentrations 􀀤􀁐􀁓􀁓􀁆􀁄􀁕􀁊􀁐􀁏􀀁􀀩􀁆􀁊􀁈􀁉􀁕 􀀤􀀰 􀀑􀀏􀀒􀀓􀀖 􀀑􀀏􀀒􀀑􀀑 􀀑􀀏􀀑􀀘􀀖 􀀑􀀏􀀑􀀖􀀑 􀀑􀀏􀀑􀀓􀀖 􀀑􀀏􀀑􀀑􀀑 􀀑 􀀖􀀑􀀑 􀀒􀀑􀀑􀀑 􀀓􀀑􀀑􀀑 􀁑􀁑􀁎 􀀒􀀖􀀑􀀑 􀀓􀀖􀀑􀀑 􀀤􀁂􀁍􀁊􀁃􀁓􀁂􀁕􀁊􀁐􀁏􀀁􀀤􀁖􀁓􀁗􀁆􀀁􀀦􀁒􀁖􀁂􀁕􀁊􀁐􀁏 􀀤􀁐􀁓􀁓􀁆􀁄􀁕􀁊􀁐􀁏􀀁􀁉􀁆􀁊􀁈􀁉􀁕􀀁􀊹􀀁􀀕􀀏􀀚􀀕􀀕􀁆􀀎􀀑􀀑􀀖􀊷􀀤􀁐􀁏􀁄􀁆􀁏􀁕􀁓􀁂􀁕􀁊􀁐􀁏􀀁􀀌􀀁􀀔􀀏􀀗􀀑􀀖􀁆􀀎􀀑􀀑􀀔􀀍􀀁􀁓􀀁􀀞􀀁􀀑􀀏􀀚􀀚􀀚 Fig. 3 Overlaid Spectra of Water Vapor Measured at Different Resolutions Gas Cell (5 cm, 10 cm) 􀀱􀁓􀁐􀁅􀁖􀁄􀁕 9 Measurement of Impurities in Hydrogen Gas 􀀱􀁓􀁐􀁅􀁖􀁄􀁕 􀀱􀁓􀁐􀁅􀁖􀁄􀁕 The Nexera lite is a robust system that eliminates the risk of sample adsorption to metals and corrosion of the equipment by mobile phases containing highly concentrated salts and acids. To maintain good system conditions and obtain reliable data at all times, the Nexera lite automates time-consuming manual tasks, contributing to increased operational efficiency. High Performance Liquid Chromatograph Nexera lite System ■ Extraction Impurities are collected by passing hydrogen gas into ultrapure water. The collected water is then introduced into the ion chromatograph or high performance liquid chromatograph according to the compounds to be measured. ■ Measurement Results (Extract) The results from measuring standard samples of each compound are shown. Formaldehyde is derivatized using DNPH. Other compounds can be analyzed by injecting the collected water directly into the ion chromatograph. • Four types of impurities can be measured with the same pretreatment. • Simultaneous analysis of inorganic halogens and formic acid is possible. • Since organic solvents are not used in the pretreatment extraction process, environmental impact is reduced. benefits Data from analysis of inorganic halogens, formic acid, ammonia, and formaldehyde in hydrogen according to ISO 14687 using ion chromatography (IC) and high performance liquid chromatography (HPLC) are shown below. 􀀢􀁑􀁑􀁍􀁊􀁄􀁂􀁕􀁊􀁐􀁏 Analysis of Hydrogen Fuel for Inorganic Halogens, 􀀢􀁑􀁑􀁍􀁊􀁄􀁂􀁕􀁊􀁐􀁏 Formic Acid, Ammonia, and Formaldehyde Ion Chromatograph/ High Performance Liquid Chromatograph Ion Chromatograph HIC-ESP Fig. 1 Hydrogen Gas Impurity Collection Impinger 1st 2nd Hydrogen Cylinder Vent Ultrapure Water Ultrapure Water Fig. 2 Chromatogram of Ammonia using HPLC 0.0 1.0 2.0 3.0 4.0 min 0.0 5.0 10.0 15.0 μS/cm DNPH-HCHO Fig. 4 Chromatogram of Inorganic Halogens and Formic Acid using IC 􀀑􀀏􀀑 􀀖􀀏􀀑 􀀒􀀑􀀏􀀑 􀁎􀁊􀁏 􀀑 􀀒􀀏􀀑 μS/cm 􀀩􀀤􀀰􀀰􀀩 􀀣􀁓 􀀤􀁍 Fig. 3 Chromatogram of Ammonia using IC NH4 0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 min 0 1.0 2.0 3.0 4.0 5.0 μS/cm 10 Hydrogen Carrier 􀀱􀁓􀁐􀁅􀁖􀁄􀁕 The Nexis GC-2030 combines excellent performance, including the world's highest level of sensitivity and reproducibility, with excellent scalability as it can be equipped with multiple injection devices and detectors to meet the analysis requirements of the component and concentration to be measured. Gas Chromatograph Nexis GC-2030 ■ Measurement of Gas Composition Before and After Ammonia Synthesis The high-end Nexis GC-2030 gas chromatograph equipped with two thermal conductivity detectors (TCD), and samples are introduced into both detectors with a single injection. Simultaneous analysis of three components present during ammonia synthesis is possible by measuring hydrogen in one analysis line and nitrogen and ammonia in the other. ■ Measurement of Impurities in Ammonia Gas Ammonia used in semiconductor manufacturing processes requires high purity control to avoid any issues caused by trace impurities. By combining multiple analytical columns with a gas chromatograph, trace components can be separated and sub-ppm level impurities in ammonia can be measured. • Simultaneous analysis of hydrogen, nitrogen, and ammonia, which are raw materials for ammonia, is possible using multiple detectors. benefits • A nalysis of impurities in ammonia and raw gas is possible. Gas composition related to ammonia synthesis can be analyzed using gas chromatography. Evaluation of Ammonia Synthesis Gas Chromatograph Fig. 1 TCD-1 Measurement of Hydrogen Concentration in Mixing Gas Fig. 2 TCD-2 Measurement of Nitrogen and Ammonia Concentrations in Mixing Gas H2 37.3% N2 31.3% NH3 31.4% Fig. 3 Measurement of Impurities in Ammonia Using TCD (10 ppm each) 0 2.0 4.0 O2+Ar N2 CH4 CO 6.0 8.0 10.0 12.0 11 Hydrogen Carrier This instrument separates each compound in the sample, and then quantifies each component using a detector. The data obtained tells the analyst what compounds are in the sample and in what quantities. Barrier discharge ionization detector (BID) Shimadzu's proprietary technology has been adopted for the BID, which incorporates ionization via a new dielectric barrier discharge plasma. It is more sensitive than conventional detectors, is able to detect components that were difficult to detect using FID, TCD and other all-purpose detectors, and delivers long-term stability. Gas Chromatograph Nexis GC-2030 􀀱􀁓􀁐􀁅􀁖􀁄􀁕 ■ Measurement Results (Extract) Ammonia and methylamine were diluted with water to prepare solutions at 4.8 ppm and 24 ppm, respectively, and the solutions were then measured by GC-BID. The 4.8 ppm and 24 ppm chromatograms are shown in Fig. 1 and the linearity is shown in Fig. 2. Calculating the lower limit of detection (S/N = 3) from the 4.8 ppm S/N ratio, the results indicated 1.2 ppm for ammonia and 2.5 ppm for methylamine. Linearity may be sacrificed at low concentrations of components that display adsorption. In this analysis, good linearity was obtained over the range, including at 4.8 ppm and 24 ppm. Using a barrier discharge ionization detector (BID) with a gas chromatograph enables a ppm-order analysis of ammonia in water. benefits Ammonia is a focus of attention as a hydrogen carrier because of its large energy density per unit volume and how easy it is to store and transport. At the same time, it is known to be toxic and bad smelling, so leakage into the environment is viewed as a problem. High-Sensitivity Analysis of Ammonia in Water Gas Chromatograph Nexis GC-2030 + BID-2030 Fig. 1 Chromatograms of 4.8 ppm and 24 ppm Standard Solutions Detection Lower Limit Ammonia (1.2 ppm) Methylamine (2.5 ppm) Ammonia Methylamine 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0 11.0 min 24 ppm 4.8 ppm Fig. 2 Linearity of Ammonia and Methylamine (4.8 ppm, 24 ppm) Area (μV×s) Area (μV×s) Concentration (v/v ppm) Concentration (v/v ppm) R^2 = 0.9999814 Ammonia 0.0 25.0 50.0 75.0 100.0 R^2 = 0.9989209 Methylamine 0.0 25.0 50.0 75.0 100.0 􀀢􀁑􀁑􀁍􀁊􀁄􀁂􀁕􀁊􀁐􀁏 12 Hydrogen Carrier 􀀢􀁑􀁑􀁍􀁊􀁄􀁂􀁕􀁊􀁐􀁏 􀀢􀁑􀁑􀁍􀁊􀁄􀁂􀁕􀁊􀁐􀁏 ■ Measurement Results (Extract) With hydrogen and methane as the target analytes, hexanes, toluene and water were used as the dissolving solutions in this experiment. Gas samples at the concentrations of 10, 50, 100, 500, 1,000, and 5,000 ppm (v/v) were prepared by diluting the standard gases of hydrogen and methane with indoor air. Using a 100 μL gas tight syringe, 100 μL of each calibrator was injected into a gas chromatograph (GC) to establish a calibration curve. The chromatogram for hydrogen dissolved in water, hexane, toluene, and other solutions is shown in Fig. 2. ■ Measurement Results (Extract) Fig. 1 shows the chromatogram from a batch analysis of five gasses, including hydrogen, other inorganic gases, and low-level hydrocarbons, using a dual BID system. Using barrier discharge ionization detectors (BID) enables the high-sensitivity analysis of hydrogen in solution. benefits Inorganic gases and low-level hydrocarbons can be batch analyzed quickly and with high sensitivity by using a dual BID system equipped with two detectors and two columns. benefits To use the hydrogen in MCH or ammonia, it must be removed from the hydrogen carrier, so analyses of the hydrogen in the solution and gas are necessary. Only certain columns can be used for separation of inorganic gases and light hydrocarbons, and it is sometimes impossible to use a single column to separate all of the target components. The Nexis GC-2030 can be equipped with two BID detectors simultaneously and supports two detectors and columns at the same time. Analysis of Hydrogen in Solution Analysis of Hydrogen in Gas Gas Chromatograph Fig. 2 Chromatogram Overlay of Hydrogen Dissolved in Hexanes, Toluene and Water Fig. 1 Chromatogram for 5 ppm Mixed Gas 1: Hydrogen 2: Oxygen 3: Nitrogen 4: Methane 5: Carbon monoxide Fig. 1 Calibration Curve of Hydrogen (1, 5, 10, 50, 100 nL) Area Volume (nL) 13 Hydrogen Carrier 􀀱􀁓􀁐􀁅􀁖􀁄􀁕 􀀢􀁑􀁑􀁍􀁊􀁄􀁂􀁕􀁊􀁐􀁏 With this system, the compounds in the sample are separated by component using the gas chromatograph (GC) and these components are ionized in order to analyze their mass. Qualitative information is obtained on the components, enabling a more accurate qualitative analysis than with GC. Any impurities can also be separated. In addition, higher sensitivity enables lower concentration measurements. The pump has a high discharge capacity, so sufficient measurements are possible when using hydrogen as the carrier gas. Gas Chromatograph Mass Spectrometer GCMS-QP2050 ■ Measurement Results (Extract) Fig. 1 shows the TIC chromatogram from a GC-MS analysis of 56 organic solvents, including toluene and MCH, eluted with carbon disulfide. Many organic solvents, including toluene and MCH, in a solution can be analyzed using GC-MS. benefits When MCH is used as the hydrogen carrier, toluene is produced when the hydrogen is removed from the MCH, so the MCH and toluene in the solution must be analyzed. Analysis of Toluene, Methylcyclohexane (MCH) in Solution Gas Chromatograph Mass Spectrometer 1. n-Hexane, 2. Ethyl ether, 3. Methylcyclohexane, 4. Acetone, 5. Methyl acetate, 6. trans-1,2-Dichloroethylene, 7. Tetrahydrofuran, 8. Carbon tetrachloride, 9. 1,1,1-Trichloroethane, 10. Ethyl Acetate, 11. Isopropyl acetate, 12. Methyl ethyl ketone, 13. Dichloromethane, 14. Benzene, 15. n-Propyl acetate, 16. cis-1,2-Dichloroethylene, 17. Trichloroethylene, 18. Methyl isobutyl ketone, 19. Isobutyl acetate, 20. 2-Butanol, 21. Chloroform, 22. Tetrachloroethylene, 23. Toluene, 24. 1,2-Dichloropropane, 25. 1,4-Dioxane, 26. 1,2-Dichloroethane, 27. n-Butyl acetate, 28. Methyl n-butyl ketone, 29. Isobutyl alcohol, 30. Isopentyl acetate, 31. Ethylbenzene, 32. p-Xylene, 33. 1-Butanol, 34. m-Xylene, 35. n-Pentyl acetate, 36. Methyl Cellosolve, 37. o-Xylene, 38. Isopentyl alcohol, 39. Cellosolve, 40. Chlorobenzene, 41. Styrene, 42. Cellosolve acetate, 43. Cyclohexanone, 44. 2-Methylcyclohexanone, 45. N,N-Dimethylformamide, 46. 3-Methylcyclohexanone, 47. 4-Methylcyclohexanone, 48. Butyl Cellosolve, 49. Cyclohexanol, 50. cis-2-Methylcyclohexanol, 51. trans-2-methyl-cyclohexanol, 52. 1,1,2,2-Tetrachloroethane, 53. ortho-Dichlorobenzene, 54. o-Cresol, 55. p-Cresol, 56. m-Cresol Fig.1 Total Ion Current Chromatogram for 56 Organic Solvents (Stabilwax) 14 Hydrogen Embrittlement ■ Testing Systems Strength Testing under High-Temperature and High- Pressure Hydrogen Gas Environments Tests are performed on solid test specimens placed within a highpressure vessel. • In strength testing under high-temperature and high-pressure hydrogen gas environments, strength tests can be performed under high-pressure hydrogen environments. • In strength testing of hollow test specimens under high-pressure hydrogen gas environments, strength tests can be performed comparatively safely using reduced quantities of hydrogen gas. • Slow Strain Rate Tests (SSRTs) with a hydrogen gas generation tank can be performed under hydrogen gas environments. • In strength testing of materials immersed in liquid hydrogen, strength tests can be performed on material immersed in liquid nitrogen, liquid helium, or liquid hydrogen. benefits Metal pipes used for transporting hydrogen gas are exposed to an environment with high-pressure hydrogen gas, so it is necessary to use a material that is resistant to hydrogen embrittlement. The following introduces a system for tensile testing under hydrogen gas environments and liquefied hydrogen environments to evaluate hydrogen embrittlement. Various Tests for Material Strength in Hydrogen Environments Precision Universal Testing Machine Strength Testing of Hollow Test Specimens under High- Pressure Hydrogen Gas Environments The quantity of hydrogen gas used is extremely small compared with the method using a high-pressure vessel, so it is not necessary to take major safety measures. In combination with an environment tank, the material properties under high-pressure hydrogen environments at temperatures of -50 °C or lower can be simply obtained. Fig. 1 Overview of Strength Testing under High-Temperature and High-Pressure Hydrogen Gas Environments High-pressure vessel Solid test specimen High-pressure hydrogen Fig. 2 Overview of Strength Testing of Hollow Test Specimens under High-Pressure Hydrogen Gas Environments Load cell Hollow test specimen Pressure gauge Load Valve Hydrogen cylinder SSRT Testing with Hydrogen Gas Generation Tank SSRT testing can be performed under an environment of hydrogen gas generated by electrolysis by inserting electrodes into an aqueous solution. The effect of hydrogen embrittlement (delayed failure) on a hydrogen gas container and piping materials can be evaluated. Strength Testing of Material Immersed in Liquid Hydrogen The testing machine incorporates a multi-layer vacuum insulation cryostat, so strength tests can be performed on material immersed in liquid nitrogen, liquid helium, or liquid hydrogen. In combination with a fatigue testing machine, it is possible to also perform fatigue testing in addition to static testing. Also, by replacing the jigs, it is possible to perform bending tests or fracture toughness tests with CT test specimens. Fig. 3 Views of SSRT Testing with Hydrogen Gas Generation Tank Various strength tests can be performed under hydrogen gas environments and liquid hydrogen environments. 􀀱􀁓􀁐􀁅􀁖􀁄􀁕 Precision Universal Testing Machine AUTOGRAPH AGX-V2 Series 15 Hydrogen Embrittlement 􀀢􀁑􀁑􀁍􀁊􀁄􀁂􀁕􀁊􀁐􀁏 􀀱􀁓􀁐􀁅􀁖􀁄􀁕 The inspection target is placed between the X-ray generator and the detector. By rotating the target 360 degrees, X-ray transmittance data can be collected from various angles, enabling the acquisition of cross-sectional images and 3D images. •Speeds up to approximately 50× faster than conventional systems can be achieved. • The optimal imaging conditions can be easily set by selecting the material, the crosssectional image resolution, and the contrast. Microfocus X-ray CT System inspeXio 7000 ■ Measurement Results (Extract) A copper pipe with an outer diameter of 8.0 mm, a thickness of 0.8 mm, and a length of 30 mm was measured. A 10 g/L aqueous solution of formic acid was used as the organic acid for corrosion. CT scans were performed three times: “before exposure,” “after two months exposure," and “after five months exposure“. Fig. 1 shows a three-dimensional data comparison for the outer copper pipe surfaces’ corrosion state – before and after exposure. Fig. 1 (a) and 1 (b) show the states after two and five months of exposure. The shape deviation of the outer surface of the copper pipe after exposure to that before exposure is color mapped by superimposing the data before exposure to each data. With a longer exposure period, corrosion progresses. In addition, deep and large dents are observed on the surface. Fig. 2 is a histogram showing the size of the area for each deviation. The relationship between deviation size and color is unified in Figs. 1 and 2. After two months exposure, we observe an insignificant change; we obtain a large yellow-green area. A significant change is observed after five months of exposure; we observe that the area of blue-green to purple increases with the generation of deep dents, and the histogram spread to the minus side. Changes in the shape of metal pipes due to corrosion can be observed using a microfocus X-ray CT system. benefits Metal is generally used as the material for pipes and tanks used for the transportation and storage of hydrogen gas and liquid hydrogen. Metal materials become brittle due to hydrogen, so it is necessary to check the degree of deterioration and the decrease in strength of these metals. Observation of Corroded Copper Pipe with a Microfocus X-ray CT System Microfocus X-ray CT System Fig. 1 Example of Shape Analysis: Three-Dimensional Representation of the Corroded Copper Pipe (a) After two months exposure (b) After five months exposure (b) After five months exposure Deviation /mm 0.00 -0.10 -0.02 -0.04 -0.06 -0.08 (a) After two months exposure Deviation /mm 0.00 -0.10 -0.02 -0.04 -0.06 -0.08 Fig. 2 Example of Shape Analysis: Histogram of the Corroded Copper Pipe (a) After two months exposure (b) After five months exposure 3 2 Area /mm2 0 (a) After two months exposure -0.08 -0.06 Enlarged histogram of (a) -0.08 -0.06 -0.04 0.2 0 Deviation /mm 1 -0.10 -0.04 -0.02 3 2 Area /mm2 0 (b) After five months exposure -0.08 -0.06 -0.04 Enlarged histogram of (b) -0.08 -0.06 -0.04 0.2 0 1 -0.10 -0.02 Deviation /mm 16 Hydrogen Embrittlement 􀀢􀁑􀁑􀁍􀁊􀁄􀁂􀁕􀁊􀁐􀁏 The fatigue life up to the point of breakage can be evaluated by repeatedly loading a sample with stresses and strains. • Raising/lowering of the crosshead and clamping are easily performed with a single handle. • The test space is wide, which allows for the attachment of various testing jigs and atmospheric instruments. ■ Measurement Results (Extract) Displacement gauges were installed at two locations on the left and right sides of the compression plates, and the average value was used to measure the change in the distance between the compression plates (Fig. 1). This allowed for the displacement of the center of the compression plates (the center of the specimen) to be measured even when the compression plates were slanting against the specimen. Fig. 2 shows the stroke and displacement gauge waveforms at cycle 1000, and Table 1 shows the peak values of each waveform. The tests confirmed that at the maximum value, the stroke was about three times larger than the displacement gauge value. This was because the displacement gauge only measured the change in the distance between the compression plates, while the stroke measured the deformation of the jig, etc. Therefore, the measurement points were different. The test demonstrated that the displacement gauge can measure the deformation of a specimen more accurately than the actuator stroke when measuring a displacement of a few μm to tens of μm. The fatigue life of a gasket can be evaluated using a Servopulser dynamic and fatigue testing machine. benefits Gaskets, which are sealing materials that prevent leakage of gases or liquids and mixing with contaminants, are incorporated at connections in the pipes and tanks used to transport and store hydrogen gas and liquid hydrogen. Evaluating their mechanical characteristics is important. Accurate Measurements of Micro-Displacements in a Compression Fatigue Test of a Gasket Fatigue and Endurance Testing Machine Fig. 1 Test Equipment Compression plate displacement measuring device Upper compression plate Specimen Lower compression plate Fig. 2 Displacement Waveform over Time 7 8 9 10 11 12 13 10 14 18 22 26 30 34 0 10 20 30 40 50 60 70 80 90 100 Stroke Compression plate displacement Time [msec] Stroke [μm] Compression plate displacement [μm] Table 1 Peak Values of Stroke and Displacement Gauge Waveforms Minimum Value [μm] Maximum Value [μm] Stroke 12.3 32.1 Displacement Gauge 7.4 12.4 􀀱􀁓􀁐􀁅􀁖􀁄􀁕 Servopulser Fatigue and EHF-E Series Endurance Testing Machine 17 Catalytic Analysis 􀀱􀁓􀁐􀁅􀁖􀁄􀁕 􀀢􀁑􀁑􀁍􀁊􀁄􀁂􀁕􀁊􀁐􀁏 The CGT-7100 analyzer measures the concentration of gases in a continuous way using a ratio photometric non-dispersive infrared absorption (NDIR) method. • All pretreatment parts required for measurement, such as the pump, filter, and electric dehumidifier, are built-in. • The analyzer can measure two components from CO, CO2 and CH4. O2 measurement is also available as an option. Transportable Gas Analyzer CGT-7100 A transportable gas analyzer allows for measurement of the concentration of the target gases simply by introducing sample gases and can evaluate the catalytic performance. benefits Steam reforming introduces a high-temperature catalyst to a mixture of steam and raw materials such as methane or ethanol to produce hydrogen gas. At this point, the concentration changes in the CO and CO2 produced by the reaction are monitored, enabling an evaluation of the deterioration of the catalyst from changes in the capacity and reaction temperature of the catalyst. Evaluation of a Catalyst Used in the Production of Fuel Cell Hydrogen Transportable Gas Analyzer Fig. 1 System Diagram 650 ˚C to 750 ˚C Gas flow Signal flow CH4 Mass flow meter H2O Mass flow meter Catalyst Data logger Conc. output Flowrate output Fig. 2 Measurement Results 0 100 200 300 400 500 600 700 800 􀀴􀁂􀁎􀁑􀁍􀁆􀀁􀁕􀁆􀁎􀁑􀁆􀁓􀁂􀁕􀁖􀁓􀁆􀀁􀀉􀂅􀀤􀀊 650 ˚C 750 ˚C Sample temperature: 650 °C, 750 °C 0 0.5 1 1.5 2 Gas concentration (vol%) 8:00 10:00 12:00 14:00 16:00 18:00 20:00 Time Duration of CGT-7100 Monitoring CO fraction vol% CO2 fraction vol% Temp sample 􀊙cC Increasing the temperature increases catalyst capacity, and increases the concentrations of CO and CO2. ■ Measurement Results (Extract) Standard methane gas and steam mixed at fixed flowrates were passed through a high-temperature chamber containing a catalyst. Gas discharged from the chamber was cooled to room temperature, liquid generated was drained away, and then gas was introduced to the CGT-7100, which was used to measure concentrations of CO and CO2 in the exhaust gas sample. The changes in the concentration of the CO and CO2 over time were continuously monitored. The system is shown in Fig. 1. The measurement results are shown in Fig. 2. The concentrations of CO and CO2 are heightened by raising the temperature of the catalyst from 650 to 750 °C. It is evident that increasing the temperature of the catalyst increases the reforming capacity. 18 Catalytic Analysis 􀀢􀁑􀁑􀁍􀁊􀁄􀁂􀁕􀁊􀁐􀁏 With this instrument, the surface of a solid sample is irradiated with an electron beam, enabling analysis of the elements in the sample surface and observation of its morphology. •Large beam current enabling ultra-high-sensitivity analysis. •The X-ray take-off angle is high, and the spatial resolution is very high. • All operations can be performed with just a mouse. Electron Probe Microanalyzer EPMA-8050G ■ Measurement Results (Extract) Fig. 1 shows the results of mapping analysis of a Rh-Pd three-way catalyst. It can be understood that trace amounts of the precious metals Rh and Pd are distributed on the upper layer of a two-layer washcoat layer, and promoters such as CeO2, ZrO2, La2O3, Nd2O3, and BaO are composed of different composition ratios in the two (upper and lower) layers. Using EPMA, metal scattering and catalyst permeation can be analyzed, enabling investigation of the degree of deterioration of the catalyst. benefits A three-way catalyst (TWC), an automotive catalyst system that was applied practically in the 1970s, uses a combination of three elements to detoxify the harmful components in exhaust gas. Platinum (Pt) and palladium (Pd) oxidize HC (hydrocarbons) to H2O (water) and CO2 (carbon dioxide) and oxidize CO (carbon monoxide) to CO2, while Rh (rhodium) reduces NOx (nitrogen oxides) to N2 (nitrogen). Analysis of an Automotive Three-Way Catalyst Electron Probe Microanalyzer Fig. 1 Mapping Analysis of Rh-Pd Three-Way Catalyst OM-image 0.3 ×0.23 mm􃻌 Ceramic􃻌 Lower layer of washcoat layer􃻌 Upper layer of washcoat layer􃻌 Embedding resin􃻌 COMPO 20.0 kV 300 ×225 μm􃻌 50 μm􃻌 Al Ka 20.0 kV 300 ×225 μm 50 μm􃻌 17000(counts) 􃻌 􃻌 200􃻌 14900􃻌 12800􃻌 10700􃻌 8600􃻌 6500􃻌 4400􃻌 2300􃻌 Y La 20.0 kV 300 􀊷225 μm􃻌 50 μm􃻌 260(counts)􃻌􃻌 20􃻌 230􃻌 200􃻌 170􃻌 140􃻌 110􃻌 80􃻌 50􃻌 Zr La 20.0 kV 300 􀊷225 μm􃻌 50 μm􃻌 (counts) 2450􃻌 50􃻌 2150􃻌 1850􃻌 1550􃻌 1250􃻌 950􃻌 650􃻌 350􃻌 RhLa 20.0 kV 300 􀊷225 μm􃻌 50 μm􃻌 (counts)􃻌 ) 100􃻌 20􃻌 90􃻌 80􃻌 70􃻌 60􃻌 50􃻌 40􃻌 30􃻌 PdLa 20.0 kV 300 ×225 μm 50 μm􃻌 (counts)􃻌 nts) 1080􃻌 40􃻌 950􃻌 820􃻌 690􃻌 560􃻌 430􃻌 300􃻌 170􃻌 Ba La 20.0 kV 300 􀊷225 μm􃻌 50 μm􃻌 (counts) 1180􃻌 140􃻌 1050􃻌 920􃻌 790􃻌 660􃻌 530􃻌 400􃻌 270􃻌 La La 20.0 kV 300 ×225 μm􃻌 50 μm􃻌 (counts)􃻌 nts) 940􃻌 140􃻌 840􃻌 740􃻌 640􃻌 540􃻌 440􃻌 340􃻌 240􃻌 Ce La 20.0 kV 300 􀊷225 μm􃻌 50 μm􃻌 (counts)􃻌 ) 1080􃻌 40􃻌 950􃻌 820􃻌 690􃻌 560􃻌 430􃻌 300 170􃻌 Nd La 20.0 kV 300 􀊷225 μm􃻌 50 μm (counts)􃻌 ) 320􃻌 40􃻌 285􃻌 250􃻌 215􃻌 180􃻌 145􃻌 110􃻌 75􃻌 Hf La 20.0 kV 300 ×225 μm􃻌 50 μm􃻌 (counts)􃻌 ) 320􃻌 80􃻌 290􃻌 260􃻌 230􃻌 200􃻌 170􃻌 140 110􃻌 􀁰􀀃 w 􀀱􀁓􀁐􀁅􀁖􀁄􀁕 19 Catalytic Analysis 􀀢􀁑􀁑􀁍􀁊􀁄􀁂􀁕􀁊􀁐􀁏 ■ Measurement Results (Extract) Fig. 1 shows a structural diagram of an MEA. The surface of the anodic side is covered with an electrode catalyst layer and is coated with a mixture of a Pt catalyst and an ionomer (solid polymer electrolyte membrane). The solid polymer electrolyte membrane is positioned under this coating, and a lattice-shaped (+) electrode grid is embedded in the membrane. Fig. 2 shows the results of a mapping analysis of the surface of the anodic side of this MEA. The left side shows the results for a new product, and the right shows a product with deteriorated performance. A relative comparison of intensity values is possible by measuring the new product and deteriorated product under the same conditions. Looking at the distribution of Pt in the deteriorated product, the intensity has decreased, while the intensity of S, which is an ionomer component (sulfonic acid), has increased. Because C and O display particularly high intensities in the electrode grid part, and conversely, the intensity of F has decreased in this grid part, the elevated levels of C and O are thought to show the effects of adhering contamination and surface oxidation. Using EPMA, it is possible to perform a comparative evaluation of a new MEA before use and a deteriorated MEA. benefits Electrochemical devices in which electrode catalyst layers are bonded on a solid polymer electrolyte membrane, which is a hydrogen ion conductor, are called membrane electrode assemblies (MEA), and are used in diverse applications, including fuel cells, technologies for water electrolysis hydrogen production technologies, and dehumidifying cells. Catalytic cohesion is one example of MEA performance deterioration, so it is important to assess the distribution of elements in the vicinity of the MEA surface. Analysis of an MEA (Membrane/Electrode Assembly) by EPMA Electron Probe Microanalyzer Fig. 2 Mapping Analysis of MEA Surface (Left: New product, Right: Deteriorated product) New product Deteriorated product COMPO 15.0 kV 5.4􀁵4.1mm 1.0 mm O Ka 15.0 kV 5.4􀁵4.1mm 1.0 mm S Ka 15.0 kV 5.4􀁵4.1mm 1.0 mm (counts) 780 690 600 510 420 330 240 150 60 (counts) 90 80 70 60 50 40 30 20 10 C Ka 15.0 kV 5.4􀁵4.1mm 1.0 mm F Ka 15.0 kV 5.4􀁵4.1mm 1.0 mm Pt La 15.0 kV 5.4􀁵4.1mm 1.0 mm (counts) 752 660 568 476 384 292 200 108 16 (counts) 450 400 350 300 250 200 150 100 50 COMPO 15.0 kV 5.4􀁵4.1mm 1.0 mm O Ka 15.0 kV 5.4􀁵4.1mm 1.0 mm S Ka 15.0 kV 5.4􀁵4.1mm 1.0 mm (counts) 780 690 600 510 420 330 240 150 60 (counts) 90 80 70 60 50 40 30 20 10 C Ka 15.0 kV 5.4􀁵4.1mm 1.0 mm F Ka 15.0 kV 5.4􀁵4.1mm 1.0 mm Pt La 15.0 kV 5.4􀁵4.1mm 1.0 mm (counts) 752 660 568 476 384 292 200 108 16 (counts) 450 400 350 300 250 200 150 100 50 (counts) 3400 3000 2600 2200 1800 1400 1000 600 200 (counts) 3400 3000 2600 2200 1800 1400 1000 600 200 Fig. 1 Structural Diagram of MEA Electrode catalyst layer Solid polymer electrolyte membrane (+) electrode Anode Cathode Nafion membrane Electrode catalyst layer (–) electrode 20 Catalytic Analysis In addition to a qualitative and quantitative analysis of elements, a chemical state analysis can be performed. AXIS Supra+ provides unrivalled large area spectroscopic performance, and fast, high spatial resolution XPS imaging capability. •Fully automated sample handling • Multi-technique capability - Compatible with AES, REELS, UPS, ISS and other analytical techniques Imaging X-ray Photoelectron Spectrometer AXIS Supra+ ■ Measurement Results (Extract) Two MEAs were studied: a new, unused one (sample A), and a degraded one with reduced performance due to long-term use in a particular environment (sample B). Fig. 1 shows the peak fitting results for the Pt 4f spectrum. Pt(0), PtO, Pt(OH)2, and PtO2 were present in the electrode catalyst layers of samples A and B. However, there were clear differences in the ratio of components between each sample. In sample B, while the ratio of Pt(0) was reduced, it can be confirmed that the amount of PtO2 had increased. These results suggest that the platinum in the surface layer of the anode electrode catalyst in sample B is oxidized. Using an X-ray photoelectron spectrometer (XPS), information about the chemical state of the surface of a degraded MEA can be obtained. benefits An MEA is an electrochemical device in which an electrode catalyst is bonded to a solid polymer electrolyte membrane. MEAs are utilized in fuel cells and water electrolysis hydrogen production technologies. It is necessary to increase the chemical stability of the electrolyte membrane to improve the performance and operating life of MEAs. For this reason, it is important to analyze the layered structure and deterioration in proximity to the surface of MEAs. Analysis of an MEA (Membrane/Electrode Assembly) by XPS X-ray Photoelectron Spectrometer Fig. 1 Pt 4f Peak Fitting Results for Samples A (left) and B (right) Binding Energy (eV) Binding Energy (eV) Name BE [eV] Ratio[%] Pt(0) 71.8 50.6 Pt(OH)2 72.8 28.8 PtO 74.4 17.5 PtO2 75.0 3.1 Name BE [eV] Ratio[%] Pt(0) 71.9 22.8 Pt(OH)2 72.9 11.4 PtO 74.4 11.8 PtO2 75.1 54.0 sample A sample B 􀀱􀁓􀁐􀁅􀁖􀁄􀁕 21 Hydrogen Tank 􀀢􀁑􀁑􀁍􀁊􀁄􀁂􀁕􀁊􀁐􀁏 ■ Measurement Results (Extract) Fig. 1 shows the external appearance of the carbon fiber reinforced thermoplastic (CFRTP) sample scanned in this experiment. This is a multilayered laminated material with overall dimensions of 30 mm × 3 mm × 1 mm. Fig. 2 shows an MPR (Multi Planar Reconstruction) screen, in which cross sections seen from multiple angles are displayed on the same screen after a portion of the sample has been scanned by a CT system. The numbers at the upper left of each screen and the lines drawn in the screens show the location of each cross section in the sample. In the cross-sectional images, higher density areas are whiter as the density increases, while lower density areas are blacker, making it possible to observe voids, cracks, resin, and carbon fibers from the screen. As shown in Fig. 3, the CT data are displayed on screens showing 3-dimensional representations for easier understanding of the structure of the scanned sample. Here, the laminated structure formed by the orthogonally-arranged layers of carbon fibers and a crack near the surface can be observed. Fig. 4 is a screen showing the result of an analysis of the fiber orientation. The standard orientation is set to 0°in the data, and the fibers in the CFRTP are colored corresponding to their deviation angles. In the histogram (Fig. 5), the horizontal axis shows the angle of deviation from the standard for the fibers, and the vertical axis shows the frequency of each angle of deviation. These results show that many of the fibers are oriented at 90° to the standard orientation. Using an X-ray CT system, it is possible to observe voids and cracks nondestructively. Additionally, graphs can be displayed in which the color corresponds to the angle of deviation of the fibers. benefits Carbon fiber reinforced plastic (CFRP) is used for the hydrogen tanks built into fuel cell vehicles. CFRP has better mechanical properties than conventional plastic materials, but voids and cracks in the interior produced during the manufacturing process can lead to product malfunctions. To stabilize the quality of the CFRP, it is important to investigate whether there are any voids or cracks within the resin, and whether the fiber orientation is as designed. Observation of Carbon Fiber Reinforced Thermoplastic Resin with an X-ray CT System Microfocus X-ray CT System Fig. 4 Screen Showing 3D Representation of CFRTP: Fiber Orientation Analysis 0° 90° Deviation angle [deg] Fig. 1 External Appearance of CFRTP Sample Fig. 5 Histogram Showing Fiber Orientation Angles of CFRTP 1.0 Frequency [%] 0.8 0.6 0 0.2 0.4 0 90 Deviation angle [deg] 10 20 30 40 50 60 70 80 Fig. 2 MPR Screen Showing Cross-Sectional Images of CFRTP Crack 1 2 2 1 3 3 1 4 4 Void Fiber Resin Fig. 3 Screens Showing 3D Representations of CFRTP Location of cutaway portion 􁶄 􁶆 􁶃 􁶅 Delamination Foreign matter Fibers Crack Orientation 1 Orientation 2 22 Hydrogen Tank 􀀢􀁑􀁑􀁍􀁊􀁄􀁂􀁕􀁊􀁐􀁏 ■ Flow of Analysis For the analysis, virtual material testing (hereinafter, numerical material testing or NMT) was conducted for the default structural data (Model 1) generated automatically by Multiscale.Sim™ and for the structural data (Model 2) generated by using data acquired by a microfocus X-ray CT system, as described below. In NMT, the two models (Model 1 and Model 2) shown in Fig. 2 were used. For Model 1, the default structural data registered in the software was used. The cross-sectional shape is uniform for fiber bundles, and the fiber bundle shape displays sinewave-like undulations. On the other hand, with model 2, the cross-sectional shape of the fiber bundles is not uniform, and the undulations deviate from the sinewave form and follow the cross-sectional shape of the fibers. Table 1 summarizes the results of comparison of the elastic modulus identified by NMT and the elastic modulus obtained in the uniaxial tensile test (actual measurement). Fig. 3 shows the nominal stress-nominal strain curves obtained from the uniaxial tensile test (actual measurement) and NMT. The elastic modulus in the direction of uniaxial tension was 55.46 [GPa] in the uniaxial tensile test (actual measurement), but was 32.56 [GPa] with Model 1, showing a large error in the simulation result. In contrast, the modulus of longitudinal elasticity with Model 2 was 51.75 [GPa], which was close to the measured value. Relative error was reduced by reflecting the structural data obtained with the microfocus X-ray CT system in the analysis model. • The structural information obtained by the X-ray CT system can be reflected in the structural analysis simulation models. • Using a universal testing machine and a non-contact extensometer, it is possible to acquire image benefits data synchronized to the load. Unlike metal materials, composite materials have a complex internal structure and display complex fracture behavior, depending on the principal axis of applied stress, making it difficult to establish highly accurate structural analysis models. Improved reproducibility of CAE analysis is expected to increase efficiency and reduce costs in development work, and to improve the reliability of the designs of both complex and large-scale structures, which is difficult to assess by actual measurement. Verification and Validation of Uniaxial Tensile Test Simulation Results of Composites Microfocus X-ray CT System Precision Universal Testing Machine Fig. 2 Two Analysis Models Examined 􀀁 Fig. 3 Comparison of Results of Nominal Stress-Nominal Strain Curves in Actual Measurement and NMT Actual measurement Model 2 Model 1 A (a) Homogenization model expressing undulation of fibers by ideal sine curve (Model 1) (b) Strict model using structural data obtained by X-ray CT (Model 2) Fig. 1 Flow of Analysis Acquisition of structural data Identification of microstructure shape parameters by image processing Creation of fabric model Virtual material testing Acquisition of actual measurement data for validation Acquire elastic modulus of anisotropy in 3 directions from stress-strain characteristics for each direction ANSYS® & Multiscale.Sim™ Simpleware™ Software ANSYS® & Multiscale.Sim™ Actual measurement Numerical Material Testing (NMT) Comparison & Verification Comparison & Verification Measure strain distribution at microscopic scale by zooming analysis of model of rectangular test specimen Data transfer Model 1 (Use default structural data) Model 2 (Use X-ray CT measurement data) Measure the strain distribution of the test piece surface by the digital image correlation (DIC) technique Acquire modulus of longitudinal elasticity (Young’s modulus) from the relationship of stress and strain Table 1 Comparison of Modulus of Longitudinal Elasticity Obtained by Homogenization Analysis and Actual Measurement Results Material Homogenization analysis (Model 1) Homogenization analysis (Model 2) Uniaxial tensile test (Actual measurement) Modulus of longitudinal elasticity (GPa) Rate of agreement with actual measurement (%) Modulus of longitudinal elasticity (GPa) Rate of agreement with actual measurement (%) Modulus of longitudinal elasticity (GPa) CFRP 32.555 58.7 51.751 93.3 55.46 23 Hydrogen Tank ■ Inspection of Adhesive Surface Delamination between CFRP and Stainless Steel [Sample provided by: Nagoya Municipal Industrial Research Institute] Artificially created delamination is detected non-destructively. Further, with X-ray fluoroscopy, unconfirmed delamination (bottom right) is detected. With its light imaging technique, which combines an ultrasonic oscillator with a stroboscope, defects near the surface of a material, including peeling of the bonding and adhesive surfaces of heterogeneous materials, as well as paint, thermal sprays, and coatings can be inspected easily and non-destructively. benefits Plastic liners, carbon fiber reinforced plastics, glass fiber reinforced plastics, and other materials are used to create hydrogen tanks, and the junctions between these materials must be inspected. Example of Non-Destructive Inspection Using an Ultrasonic Optical Flaw Detector Ultrasonic Optical Flaw Detector X-ray fluoroscopic image Blue frame: Simulated defect Plate thickness CFRP: 2 mm Stainless steel: 0.5 mm Adhesively bonded CFRP/ stainless steel material (CFRP surface) Inspection results (ultrasonic field image) Blue frame: Flawed region Overlay Blue frame: Flawed region Fig. 1 Inspection of Adhesive Surface Delamination between CFRP and Stainless Steel Sample delamination Void Crack Ultrasonic wave Laser irradiation Camera Oscillator Synchronized MIV-X Conventional ultrasonic testing Layout of the observation system Visualization example Observation region Peeling of coating film Crack Crack Peeling of coating film Camera Observation region Ultrasonic probe Region insensitive to ultrasonic inspection Coating film Coating film Crack Peeling of coating film (difficult to inspect) 􀀒 􀀔 􀀓 With ultrasonic optical flaw detection technology the displacement of the surface is detected optically, and the propagation of the ultrasonic wave on the surface is observed. •The sample is loaded by continuous ultrasonic vibrations. • Microscopic out-of-plane displacement of the surface due to propagation of the ultrasonic wave is visualized optically using laser irradiation and a camera. • Defects are detected by observing disturbances in the propagation of the ultrasonic wave. Ultrasonic Optical Flaw Detector MIV-X 􀀱􀁓􀁐􀁅􀁖􀁄􀁕 The MIV-X Ultrasonic Optical Flaw Detector assists with regions where ultrasonic testing (UT) is difficult. 􀀮􀁐􀁗􀁊􀁆 24 Hydrogen Tank 􀀢􀁑􀁑􀁍􀁊􀁄􀁂􀁕􀁊􀁐􀁏 A differential scanning calorimeter (DSC) is an instrument that changes the temperature of a sample and a reference substance according to a program, records the temperature difference, and converts it into heat quantity. Differential Scanning Calorimeter DSC-60 Plus Series ■ Measurement Results (Extract) Rubber generally loses its elasticity when the temperature drops to the glass transition point. If the seal material loses its elasticity, its sealability decreases and there is a danger of leakage. Thus, it is important to confirm the glass transition point in order to set the applicable temperature range in the low temperature region and ensure safety. In this example, EPDM, NBR and FKM samples were measured using a DSC-60 Plus. From the results in Fig. 1, it can be said that NBR has the lowest glass transition temperature and the highest cold resistance. Unlike EPDM, NBR and FKM, silicone rubber undergoes crystallization and loses its elasticity due to hardening at low temperatures. Therefore, the crystallization temperature was determined by a temperature-fall measurement from room temperature. • DSC-60 Plus enables measurements down to temperatures as low as -140 ˚C. • Cold resistance of rubber can be evaluated. benefits High sealability is required in piping and vessels used in the transportation and storage of liquid hydrogen in order to prevent leaks. In particular, because leaks occur easily at joints, rubber seal materials such as O-rings are frequently used to improve the sealability of these parts. Evaluation of Thermal Characteristics of Rubber O-Rings Differential Scanning Calorimeter 􀀱􀁓􀁐􀁅􀁖􀁄􀁕 Fig. 1 DSC Measurement Results of EPDM, NBR and FKM -50.00 0.00 50.00 Temp [ﾟC] -1.00 0.00 1.00 mW DSC オンセット -34.31ﾟC エンドセット -22.35ﾟC 中間点 -31.60ﾟC オンセット -35.68ﾟC エンドセット -25.02ﾟC 中間点 -29.77ﾟC オンセット -23.80ﾟC エンドセット -17.06ﾟC 中間点 -20.37ﾟC EPDM NBR FKM Onset Endset Midpoint Onset Endset Midpoint Onset Endset Midpoint Fig. 2 DSC Measurement Results of Silicone Rubber -100.00 -50.00 0.00 Temp [ﾟC] -2.00 0.00 2.00 4.00 mW DSC -61.52xﾟC Sシiliリcコonーeン ゴム rubber 25 Hydrogen Tank 􀀢􀁑􀁑􀁍􀁊􀁄􀁂􀁕􀁊􀁐􀁏 Fracture toughness tests can be performed to check the impact of interlaminar peeling and damage in CFRP laminate materials. While film elongation measurements are difficult with a contact extensometer, the TRViewX non-contact digital video extensometer can perform accurate elongation measurements across a wide elongation range without affecting the sample. Precision Universal Testing Machine AUTOGRAPH AGX-V2 Series Non-Contact Digital Video Extensometer TRViewX 􀀱􀁓􀁐􀁅􀁖􀁄􀁕 􀀱􀁓􀁐􀁅􀁖􀁄􀁕 ■ Measurement Results (Extract) In these tests, a scale for confirming the delamination growth was marked on one side of the test specimen, while on the other side a crack gauge was installed for confirming the delamination length (Fig. 1). In these tests, the extent of delamination growth was monitored up to a length of 50 mm from the tip of the initial delamination. Using TRViewX to save the video made it possible to perform the calculations while reviewing the video synchronized with the results after the tests. In the specimens tested, delamination growth was initially unstable, with the force dropping suddenly at point A. Subsequent delamination growth was stable, with fracture occurring at 45 to 50 mm (Fig. 2). With the TRViewX image, it was possible to check the propagation of cracks all the way to the end (Fig. 3). • It is possible to measure the interlaminar fracture toughness, which is necessary for designing CFRP. • The delamination length can be observed after testing by video recording the delamination growth benefits using TRViewX. CFRP laminates are not impact-resistant, and damages such as delamination can occur on impact. Therefore damage-tolerant designs, which take into consideration the effect of internal damage on the strength of the material, are incorporated in design and product development. In order to implement damage-tolerant designs, it is necessary to determine the resistance to delamination growth, so fracture toughness tests are performed. Interlaminar Fracture Toughness Evaluation of CFRP with Double Cantilever Beam Test Precision Universal Testing Machine Fig. 1 Test Specimen (Left: Scale Side, Right: Crack Gauge Side) Crack gage Scale Initial delamination Fig. 3 Test Results and Linked TRViewX Images P13􀉿Delamination 45 mm P10􀉿Delamination 30 mm P1 : Delamination 1 mm P6􀉿Delamination 10 mm P7􀉿Delamination 15 mm 15 mm slide 15 mm slide Fig. 2 Test Results 試験力（N） ストローク（mm） Test Force (N) Stroke (mm) A 26 Water Electrolysis 􀀱􀁓􀁐􀁅􀁖􀁄􀁕 􀀢􀁑􀁑􀁍􀁊􀁄􀁂􀁕􀁊􀁐􀁏 The TOC-1000e specializes in online monitoring of ultrapure water applications. With a detection limit of 0.1 ppb and fast oxidation technology, the TOC-1000e accurately measures both the TOC content and electrical conductivity of water. It can be used for a wide range of applications related to ultrapure water, wastewater, solid samples and swab tests. •Vial sampler allows annual calibration at the installation site. • Built-in web server allows easy remote diagnosis and detailed data view including history. • Small and lightweight. Weights less than 3 kg with front plate area the size of an A4 paper sheet. Total Organic Carbon Analyzer TOC-1000e ■ Measurement Results (Extract) Fig. 1 shows continuous measurement of ultrapure water over a period of approximately two days with a cycle time of 2.5 minutes. Contaminants can be detected quickly and with high sensitivity before they cause problems. Detecting contamination or nearcontamination events can facilitate recovery of an electrolyzer. • The quality of ultrapure water is critical to the reliability and economic viability of green hydrogen production. • Online analysis by TOC-1000e allows monitoring of PEM electrolysis feed water for ionic and organic contamination. • High portability enables both continuous analysis and flexible deployment to key locations throughout the plant. benefits Hydrogen generation using water electrolysis requires pure water with few impurities, so it is important to constantly manage its quality. Process Monitoring of PEM H2 Electrolysis Feed Water Total Organic Carbon Analyzer 0 0.01 0.02 0.03 0.04 0.05 0.06 0.07 0.08 0.09 0.1 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 1 51 101 151 201 251 301 351 401 451 501 551 601 651 701 751 801 851 901 951 1001 1051 1101 1151 Conductivity [μs/cm] TOC [ppb] "TOC [ppb]" "Conductivity [μS/cm]" Fig. 1 Ultrapure Water Measurement Results at 2.5 minutes Intervals for Two Days 27 Sulfinert is a registered trademark of SilcoTek® Corporation. Multiscale.Sim is a trademark of Cybernet Systems Co., Ltd. ANSYS is a trademark or registered trademark of ANSYS Inc. or its subsidiaries located in the United States or other countries. Simpleware is a trademark of Synopsys, Inc. www.shimadzu.com/an/ For Research Use Only. Not for use in diagnostic procedures. This publication may contain references to products that are not available in your country. Please contact us to check the availability of these products in your country. Company names, products/service names and logos used in this publication are trademarks and trade names of Shimadzu Corporation, its subsidiaries or its affiliates, whether or not they are used with trademark symbol “TM” or “®”. Third-party trademarks and trade names may be used in this publication to refer to either the entities or their products/services, whether or not they are used with trademark symbol “TM” or “®”. Shimadzu disclaims any proprietary interest in trademarks and trade names other than its own. The contents of this publication are provided to you “as is” without warranty of any kind, and are subject to change without notice. Shimadzu does not assume any responsibility or liability for any damage, whether direct or indirect, relating to the use of this publication. © Shimadzu Corporation, 2026 / First Edition: December 2023, 3655-01606-PDFIT, C10G-E102C Analysis Solutions for Quality Control of Hydrogen Analytical Solutions for Artificial Photosynthesis Clean Energy Related Material Artificial photosynthesis is gaining increasing attention in the realisation of a carbon neutral society. Artificial photosynthesis is a technology that artificially performs photosynthesis using photocatalysts and sunlight. It is expected to be a next-generation renewable energy technology because it can convert light energy into useful compounds. Research is being conducted using artificial photosynthesis to produce “green hydrogen”, which is hydrogen that does not emit carbon dioxide during production. This solution guide contains analytical techniques for photocatalyst characterization and reaction products. C10G-E104 Artificial Photosynthesis © Shimadzu Corporation, 2024 / First Edition: March 2024, 3655-12306-PDFIT, C10G-E104 Not for use in diagnostic procedures. contain references to products that are not available in your country. Please contact us to check the availability of country. products/service names and logos used in this publication are trademarks and trade names of Shimadzu Corporation, affiliates, whether or not they are used with trademark symbol “TM” or “®”. and trade names may be used in this publication to refer to either the entities or their products/services, whether with trademark symbol “TM” or “®”. proprietary interest in trademarks and trade names other than its own. publication are provided to you “as is” without warranty of any kind, and are subject to change without notice. assume any responsibility or liability for any damage, whether direct or indirect, relating to the use of this publication. Analytical Solutions for Artificial Photosynthesis 􀊵Photocatalyst Characterization and Product Quantification 􀊵 Download PDF (C10G-E104)