The Role of Chemical Metrology in Transportation Industry

The Role of Chemical Metrology in Transportation Industry Dr Richard Shin Consultant Scientist Chemical Metrology Laboratory, Chemical Metrology Division, Applied Sciences Group Health Sciences Authority, Singapore World Metrology Day 19 May 2017 All rights reserved Health Sciences Authority 1

Chemical Metrology Laboratory, HSA Introduction HSA is a Designated Institute (DI) for Chemical Metrology in the areas of food, healthcare, medical science, pharmaceuticals & health products and forensics. The laboratory is housed in a cleanroom with a rating of ISO Class 7. A special metal free section is created in the laboratory for inorganic analysis. The laboratory has a wide array of instruments to support its measurement activities. The quality system is based on ISO/IEC 17025, ISO 17034 and ISO/IEC 17043. The laboratory participates actively in regional & international chemical metrology activities including relevant regional & international comparisons. All rights reserved Health Sciences Authority 3

Introduction Recent Trends in Transportation Industry Driverless and smart cars Vehicle-to-vehicle communication and precollision technology Sustainable fuels Biodiesel economictimes.indiatimes.com Light weight vehicles Construction material Metal & metal alloys extremebiodiesel.com economictimes.indiatimes.com All rights reserved Health Sciences Authority 4

Biodiesel What is biodiesel? It refers to a vegetable oil or an animal fat-based diesel fuel consisting of long-chain alkyl esters. It is typically made by chemically reacting lipids with an alcohol producing fatty acid esters (in the presence of a catalyst). http://www.alternative-energy-news.info/ All rights reserved Health Sciences Authority 7

Biodiesel Classification of biodiesel Blends of biodiesel and conventional hydrocarbon-based diesel are most commonly found in the retail diesel fuel marketplace. 100% biodiesel is referred to as B100 20% biodiesel, 80% petrodiesel is labeled B20 5% biodiesel, 95% petrodiesel is labeled B5 2% biodiesel, 98% petrodiesel is labeled B2 Blends of 20% biodiesel and lower can be used in diesel equipment with no or only minor modifications. All rights reserved Health Sciences Authority 8

Biodiesel Effects of biodiesel metal and metalloid contents Alkali metals (Na, K) can form deposits in fuel injection system. Sulfur (S) causes corrosion, environmental pollution, bad odour and poisoning of catalyst. Phosphorus (P) at very low concentration significantly affects fuel consumption. Cobalt (Co), copper (Cu), iron (Fe), manganese (Mn) and nickel (Ni) can promote oxidative degradation, whereas other elements such as lead (Pb) and zinc (Zn) can catalyze the biodiesel oxidation. Source of metals and metalloids Raw material (soil or pesticides and fertilizers) Transesterification reaction Additives: anti-knock agents, anti-oxidants, burn improvers, metal deactivators, anti-rust agents, anti-icing agents and detergents Transportation, production or storage All rights reserved Health Sciences Authority 9

Biodiesel Maximum allowable levels of metals and metalloids based on ASTM D6751 a and EN 14214 b. Elements Na + K Ca + Mg S P Content 5 mg/kg 5 mg/kg 15 mg/kg (S15) a or 10 mg/kg b 0.05% (S500) 0.001% (w/w) a or 4 mg/kg b Currently, Singapore regulations on petrol and diesel set the sulfur (S) and lead (Pb) contents limit at 10 mg/kg c and 5 mg/kg, respectively. a ASTM D6751: Standard specification for biodiesel fuel blend stock (B100) for middle distillate fuels set by ASTM International b EN 14214: Standard published by the European Committee for Standardization that describes the requirements and test methods for FAME c www.theicct.org and www.nea.gov.sg All rights reserved Health Sciences Authority 10

Biodiesel What are needed for the analysis? Sensitive techniques Analytical methods that are able to compensate for matrix effects and interferences Challenges faced in the chemical analysis of biodiesel Low concentrations of the analytes (ppm level) Limited availability of certified reference materials (CRMs) Different sources of raw materials may affect the characteristics of the final product Around 300 different organic compounds All rights reserved Health Sciences Authority 11

Biodiesel Biodiesel CRMs Matrix Element Source Biodiesel B100 (Soy-based) Biodiesel B100 (Animal-based) Biodiesel B100 (Palm Oil-based) Ca, Cu, Fe, Mg, P, K, Na Ca, Cu, Fe, Mg, P, K, Na Na, Mg, K, Ca, P, S NIST, USA NMIJ, Japan NIST: National Institute of Standards and Technology NMIJ: National Metrology Institute of Japan All rights reserved Health Sciences Authority 12

Biodiesel Techniques employed for the analysis of metals and metalloids in biodiesel Red line: the number of studies dealing with the determination of the elements All rights reserved Health Sciences Authority 13

Metal and Metal Alloys Steel and steel alloy The simplest steels are iron (Fe) alloyed with carbon (C) (about 0.1% to 1%, depending on type). Steel alloy refers to steel that is alloyed with a variety of elements in total amounts between 1.0% and 50% by weight to improve its mechanical properties. Common alloying elements include manganese (Mn), nickel (Ni), chromium (Cr), molybdenum (Mo), vanadium (V), silicon (Si) and boron (B). Improved properties in steel alloys: strength, hardness, toughness, wear resistance, corrosion resistance, hardenability and hot hardness. Applications: turbine blades of jet engines, spacecraft, nuclear reactors, electric motors and transformers. All rights reserved Health Sciences Authority 16

Metal and Metal Alloys Effects of alloying elements for steel Element Percentage Function B 0.001 0.003 Hardenability agent Cr Mn 0.5 2 Increases hardenability 4 18 Increases corrosion resistance 0.25 0.40 Combines with S and P to reduce brittleness and remove excess oxygen from molten steel > 1 Increases hardenability Mo 0.2 5 Increases toughness Ni 2 5 Toughener V 0.15 12 20 Increases corrosion resistance Increases strength while retaining ductility and increases toughness at high temperature Degarmo, E. P.; Black, J. T.; Kohser, R. A. (2007) Materials and Processes in Manufacturing 10 th Ed. p. 144. All rights reserved Health Sciences Authority 17

Metal and Metal Alloys Optimising the properties of a material is often related to determining its precise elemental composition and monitoring contaminants or impurities. Challenges faced in the chemical analysis of metal and metal alloys Insufficient sensitivities (X-ray based techniques). Low sample throughput and/or high instrument costs (mass spectrometric techniques). The need of appropriate matrix matched standards or CRMs for quantitative determinations. All rights reserved Health Sciences Authority 18

Metal and Metal Alloys Routine analysis of trace elements is usually performed with AAS A single-element method (although modern continuous source instruments can give access to more than one element simultaneously) Low sample throughput ICP-OES and ICP-MS The dissolution of materials often requires the use of highly corrosive/toxic reagents and/or harsh reaction conditions. Hence, further dilution is required. Excessive sample-handling can increase blank levels, may contribute to matrix-effects and can introduce contaminations causing additional interferences in sample analysis. What are needed for the analysis? Sensitive techniques Analytical methods that are able to compensate for matrix effects and interferences All rights reserved Health Sciences Authority 19

HSA Involvements in the Chemical Metrology Community Consultative Committee for Amount of Substance Metrology in Chemistry & Biology (CCQM) - Member Protein Analysis Working Group Inorganic Analysis Working Group Organic Analysis Working Group Asia Pacific Metrology Programme (APMP)- Member Technical Committee for Amount of Substance Technical Committee on Quality Systems All rights reserved Health Sciences Authority 20

International Comparisons in the Area of Fuel & Biodiesel International comparisons on fuel and biodiesel fuel CCQM-P26: Sulfur in Fuel Organised by IRMM/NIST in 2001 CCQM-K35 and P26.1: Sulfur in Fuels (Lower Level) Organised by NIST in 2003 CCQM-K123 and P157: Trace Elements in Biodiesel Fuel Organised by NMIJ/NIST in 2014 IRMM: Institute for Reference Materials and Measurements NIST: National Institute of Standards and Technology NMIJ: National Metrology Institute of Japan All rights reserved Health Sciences Authority 21

International Comparisons in the Area of Metal and Metal Alloys International comparisons on metal and metal alloys CCQM-P34: Constituents in Al Alloy Organised by BAM in 2001 CCQM-K33 and P56: Minor Elements in Steel Organised by NMIJ/NIST/BAM in 2003 CCQM-K42 and P34.1: Consitutents of an Aluminium Alloy Organised by BAM in 2004 CCQM-P76: Major and Minor Elements in Copper Alloy Organised by BAM in 2005 CCQM-K64: Analysis of Copper Alloy Organised by BAM in 2007 BAM: Bundesanstalt für Materialforschung und -prüfung All rights reserved Health Sciences Authority 22

Conclusions The qualities of materials are strongly determined by their elemental compositions and/or the levels of contaminants and impurities. Challenges faced in the chemical analysis Low concentrations of the analytes (trace or ultra-trace level) Wide range of possible combinations of raw materials final products with different properties Limited matrix matched standards or CRMs Hence, there is a need for sensitive techniques and analytical methods that are able to compensate for matrix effects, such as IDMS and standard addition techniques. All rights reserved Health Sciences Authority 23

Acknowledgment Colleagues of HSA CML: Dr Lee Tong Kooi, Division Director Dr Teo Tang Lin, Laboratory Director Dr Fransiska Dewi, Analytical Scientist Dr Benny Tong, Analytical Scientist Mr Leung Ho Wah, Senior Laboratory Officer All rights reserved Health Sciences Authority 24