Combustion Ion Chromatography Beyond the horizon – the world of combustion Dr. Christian Emmenegger Metrohm International Headquarters

Combustion IC Topics Why Combustion IC? – Regulations Different combustion methods The Mitsubishi Combustion System Applications USP Combustion Ion Chromatography

Regulations Why do we need “halogen-free” products? Address the fast and global increase of consumer electronics waste Reduce damage to people and environment Restriction for the use of hazardous materials mostly in various electronic and electrical equipment: Europe: Waste Electrical and Electronic Equipment Directive (WEEE) 2002/96/EC Restriction of Hazardous Substances Directive (RoHS) 2002/95/EC (polybrominated biphenyls PBB, polybrominated diphenyl ether PBDE, Pb, Hg, Cd, Cr (VI)) PBB and PBDE are flame retardants (AW IN6-0837-062008) Improvement also for staff in production Plasticizers RoHS CrVI in coatings AW IN6-0848-042008 Combustion Ion Chromatography

www.ipc.org www.iec.ch www.jpca.net www.halogenfree.org Regulations Halogen-free Definition JPCA (Japan Printed Circuit Association): JPCA-ES-01-2003 Br < 900ppm Cl < 900ppm IEC (International Electrotechnical Commission): IEC 60502-1 Total halogens < 1500ppm IPC (Association Connecting Electronic Industries): IEC 61249-2-21 Other VIIA group halogens are not included in the definition (F, I) www.ipc.org www.iec.ch www.jpca.net www.halogenfree.org Combustion Ion Chromatography

Regulations Regulations Apple (069-1857-A) Br<900ppm Cl<900ppm Total halogens<1500ppm Sony Ericsson 2/034 01-LXE 108 239 Uen Samsung Electronics Combustion Ion Chromatography

Regulations Various Test Methods EPA Method 9056A Determination of inorganic anions by IC (for drinking water, wastewwater, aques extracts of solids and the bomb combustion samples) DIN 41727 Determination of Chlorine in different types of Coal (German Norm) with Oven at 1250°C ASTM D 7359 –08 Standard Test Method for Total Fluorine, Chlorine and Sulfur in Aromatic Hydrocarbons and Their Mixtures by Oxidative Pyrohydrolytic Combustion followed by Ion Chromatoghraphy Detection Combustion Ion Chromatography

Regulations Fuel and Petrol Industry Low sulfur contents reduce air pollutants in the air Low sulfur contents increase performance of emissions cleaning systemes in automobiles European Union, Japan… continously reduced sulfur content DIN EN 228 for automobile max. 10 ppm Sulfur Continously reduced to presently 10 mg/kg S Combustion Ion Chromatography

Application Fields Which industries are applicable to CIC? Environmentally relevant oil, plastic waste, acitvated substances: carbon … Electronic components: printed circuit boards, resins, cables, insulating materials … Fuels: gasoline, kerosene, crude oil, heating oil, coal, catalysts … Plastics: polymers such as polyethylene, polypropylene … Dyestuffs: pigments, paints … Pharmaceutical products: raw substances, intermediates, finished products Combustion Ion Chromatography

Potentional Customers Who does not use electronical parts? Combustion Ion Chromatography

Potentional Customers Who does not use electronical parts? Combustion Ion Chromatography

Sample Combustion Methods Typical Combustion Setups Offline: Schöniger Flask Wickbold - Apparatus Parr-Bomb with Na2O2 Oxygen-Bomb Microwave-induced combustion Online: Mitsubishi AQF Combustion Ion Chromatography

Schöniger Flask Combustion by Kurt Schöniger Closed system to determine halogens and sulfur in organic compounds: Closed system Compounds on a filter are burned in a flask filled with oxygen and adsorbed. Die mikroanalytische Schnellbestimmung von Elementen wie Halogenen und Schwefel in organischen Verbindungen mittels des sogenannten "Schoeniger Kolbens" wurde von Schoeniger 1955, 1956 und 1958 beschrieben. Zitat: "Das Prinzip der Methode ist folgendes: Die zu untersuchende Substanz wird in einem Stück aschefreiem Filterpapier in einem mit Sauerstoff gefülltem Erlenmeyerkolben verbrannt, die Verbrennungsprodukte absorbiert und der Gehalt des zu bestimmenden Elementes massanalytisch erfasst. Der ursprünglich verwendete Platindraht zur Befestigung des Filterpapiers wurde, wegen rascher Versprödung, durch ein Platinnetzchen mit einer Drahtstärke von 0.5 - 0.8 mm ersetzt." Combustion Ion Chromatography

Wickbold Combustion Apparatus Oxyhydrogen Gas Blowpipe Combustion Open system mainly for sulfur and chlorine analysis in petroleum products: Substance is evaporated in oxygen stream Burned in a cooled quartztube in oxyhydrogengas Absorption in solution Oxyhydrogen gas = knallgas Burning in flame and cooling with Wickbold Combustion Ion Chromatography

Parr-Bomb – Oxygen Bomb Classical Methodolgy Closed system for combustion in a sealed, pressure-stable environment: Parr Bomb: Oxydation e.g. by Na2O2 at elevated temperatures thermal excitation (slow, hours) Microwave-induced Combustion (fast, several minutes) Oxygen Bomb: @ 25 - 40 bar O2 the sample is ingnited by electrodes Na2O2 = sodium peroxide AW UK6-0226-052008 Calirimetric Bomb by Customer Mervyn Barggott, OSS Group AW UK6-0226-052008 Determination of F -, Cl -, PO42- and SO42- combusted oil sample oxygen bomb Combustion Ion Chromatography

Mitsubishi Combustion System Complete Prep Station for Ion Chromatography Open system for fast halogen and sulfur analysis: Sample is automatically inserted into furnace and incrementally burned in oxygen/argon gas stream Absorption in H2O2 solution Combustion Ion Chromatography

Which Ions are measured? Combustion and Absorption Principles Sulfur and halogen compounds are combusted under Ar/O2 gas and oxidized by H2O2 Sample in combustion gas in absorption solvent S SO2, SO3 SO42- X (F, Cl, Br, I) HX, X2 X- N/A for the following compounds: N NO, NO2 (bad recovery) P P2O5 (non-volatile) M (Metal) MO (metal oxides are non-volatile) Internal standard (e.g. Phosphate, Tartaric Acid, Citric Acid…) is added to the absorption solvent to correct for the absorption volume Combustion Ion Chromatography

Specifications for Samples Important numbers for Mitsubishi Combustion IC Solid and Non-Aqueous Liquid Samples Solid sample 1-100 mg (typically 20-30 mg) Liquid Sample 5-100 mL (typically 30-50 mL) Absorbent Volume 3-10 mL (extendable up to 20 mL) Furnace Temperature max 1100°C Combustion Time about 3-7 minutes Combustion Ion Chromatography

Sample Preparation Is sample preparation required? Inhomogenous, bulky and large samples need sample preparation: Smaller size by scissors, cutter Dissolve in solvent Powdering by grinder, mill Freeze milling Combustion Ion Chromatography

Flowpath Combustion IC Common Conditions: Inlet Temperature: 900°C Outlet Temperature: 1000 °C Ar/O2 flow: 200 mL/min O2 flow: 450 mL/min WS-100 Ar flow: 150 mL/min Schematic of the CIC system Gas Reinheiten minimum:99.98 % Argon 99.7 Oxygen Combustion Ion Chromatography

Burn Process Multistage Combustion Process (gradually) The combustion process is divided into the following steps for the sample boat: 4. 3rd position 6. Cooling position End position (oxydation) 7. Home position (Absorption Time) 2. 1st position (preheating) 3. 2nd position Home Positon (Prepare Sample) Combustion Ion Chromatography

Combustion Program Sample combustion and absorption programs Combustion must be optimized for each sample for a slow pyrolysis process! Otherwise incomplete combustion! Combustion Ion Chromatography

Time Program Efficient Time Schedule for Combustion and IC The analysis time schedule is optimized and synchronized: Remote Signal für IC Start Cleaning Combustion Ion Chromatography 3 min 5 min 15 min 1st sample 2nd sample 3rd sample Cleaning Combustion 3 min 5 min Combustion Ion Chromatography

Multiple Combustion Sample Accumulation with multiple combustion Multiple Combustion time schedule for low concentrations: Cleaning Combustion Combustion Combustion Ion Chromatography 3 min 5 min 5 min 5 min 15 min Sample to show multiple injection is Bleifrei 95 (lead-free) aus AW CH6-0959-092008 Sulphate and Chloride concentration in absorption solvent correlate well Combustion Ion Chromatography

Combustion Temperatures Temperatures for ideal combustion Typical combustion temperatures for following compound types: Organic 900/1000 °C Organic with inorganic 1000/1100 °C Inorganic 1100/1100 °C Combustion Ion Chromatography

Combustion Improver Protects equipment and increases recovery Recovery is low when target is inorganic salt or sample matrix has inorganics Also effective against corrosion of quartz glass Typical improvers are: tungsten oxide (effective for alkaline/alkaline earth metal: Na, Ca, …) copper oxide (halogen analysis in silica compound, glass) iron oxide (halogen analysis in silica compound, glass) Cannot prevent corrosion by fluorine Combustion Ion Chromatography

Combustion Improver Effect Effect of Combustion Improver Prevent corrosion of quartz glass CaO + H2O Ca(OH)2 deteriorates tube CaO + H2O + WO3 CaWO4 + H2O lightens deterioration Improves e.g. sulfur recovery: CaSO4 + WO3 Ca WO4 + SO3 Na2SO4 + WO3 Na2WO4 + SO3 Combustion Ion Chromatography

Sample Boat Types Several kinds of boats are available Boat for ABC quartz boat Boat for ABC quartz boat: organic sample without residual ceramic disposable boat: with improver or sample has residue which cannot be cleaned out Boat for auto sampler ceramic boat: organic sample without residual. nickel inner disposable boat: with improver or residue which cannot be cleaned out. Only for halogen (sulfur has low recovery) Quartz boat can deteriorate by fluorine, alkaline metal, elkaline earth metal. Frequently washing helps to elongate life. ceramic disposable boat ceramic boat nickel inner disposable boat Combustion Ion Chromatography

Pyrolysis Tube Handling and Use Quartz tube can be deteriorated by fluorine, alkaline and alkaline earth metal. Frequently washing necessary. (deteriorating samples are: sodium sulfonic acid, sodium sulfate, barium sulfate, sodium salt, potassium salt, alakline earth metal. High fluorine) Alternative: ceramic inner tube Combustion Ion Chromatography

Mitsubishi System Configurations I Combinations for AQF-100 Basic Units necessary: GA-100 (gas absorption unit) AQF-100 (furnace) WS-100 (water supplier) Absorption Parts: Absorption Tube for Low Concentration (10 mL) Absorption Tube for High Concentration (20 mL, 20 und 5 mL Sampling Loops, Trap Column) Sample Injectors for combustion: for liquids: ABC-100 or combo ABC-100 + ASC150L for solids: ABC-100 or ASC-120S Also available: ceramic inner pyrolysis tube for high concentration fluoride analysis Combustion Ion Chromatography

Mitsubishi System Configurations II Combinations for AQF-100 Basic Units necessary: GA-100 (gas absorption unit) AQF-100 (furnace) WS-100 (water supplier) Absorption Parts: Absorption Tube for Low Concentration (10 mL) Absorption Tube for High Concentration (20 mL, 20 und 5 mL Sampling Loops, Trap Column) Sample Injectors for combustion: for liquids: ABC-100 or combo ABC-100 + ASC150L for solids: ABC-100 or ASC-120S Also available: ceramic inner pyrolysis tube for high concentration fluoride analysis Combustion Ion Chromatography

Mitsubishi System Configurations III Combinations for AQF-100 Basic Units necessary: GA-100 (gas absorption unit) AQF-100 (furnace) WS-100 (water supplier) Absorption Parts: Absorption Tube for Low Concentration (10 mL) Absorption Tube for High Concentration (20 mL, 20 und 5 mL Sampling Loops, Trap Column) Sample Injectors for combustion: for liquids: ABC-100 or combo ABC-100 + ASC150L for solids: ABC-100 or ASC-120S Also available: ceramic inner pyrolysis tube for high concentration fluoride analysis ASC150L 50 samples ASC-120S 20 samples ABC-100 Combustion Ion Chromatography

The Metrohm-Mitsubishi Combination Setup with IC Net Combination with Compact 761/861 Compact IC 761 need to have an analog output 771 synchronizes the two systems MagIC Net can be added to such a system (database features) There is a package available for the 771 and MagIC Net (2.771.0110). Part No. Description Use 6.2134.140 Cable 771 (analog) – 819 Connection of analog and start signals to 771 2.771.0010 IC Compact Interface Receives and records the analog signal of the IC system. Further it receives the contact closure signal of the Mitsubishi instrument and starts the IC instrument. Combustion Ion Chromatography

The Metrohm-Mitsubishi Combination Setup with MagIC Net Compact IC pro 881 Scan for a contact closure signal on input line 2 ( *****1** ) Part No. Description Use 6.2148.010 Remote Box MSB Connect to MSB port of IC instrument. 6.2141.140 Cable 766/788/813/838 - 817 Connect to the Mitsubishi contact closure output with the open ends and with the 21 pin connector to the Remote box Combustion Ion Chromatography

Applications Performance check upon installation: S-Benzylthiuroniumsulfate Check solution S-Benzylthiuroniumsulfate 25mg/25mL Ethanol Absorbent 30 ppm H2O2, 1 ppm Phosphate Calibrate IC System Measure 30 mL check solution Judgment: within 92-108 % of theoretical value 97-100.5 % Recovery for Cl and S in AW 953 AW CH6-0953-082008 Combustion Ion Chromatography

ERM-EC681k Low density Polyethylene pellet Certified Reference Material A Supp 5 –150 H2O2 30 ppm, 1 ppm Phosphate AW CH6-0954-082008 Combustion Ion Chromatography

Fuel Sulfur in Fuel Available Reference Material by ERM: Various Fuel Measurements A Supp 5 –150 50 mL injections Simultaneous Chloride determination H2O2 30 ppm, 1 ppm Phosphate Alternativ mit AW DE8-0550-042008 Fluoride, Acetate, Formiate and Chloride in Fuel with Matrix Elimination PO4 1 ppm, H2O2 30 ppm Sample Chloride [ppm] RSD [%] Sulfur [ppm] Bleifrei 95 (lead free) 7.9 2.3 10.8 1.0 Diesel 4.5 9.1 1.3 1.1 Migrol Greenlife Biodiesel 5.0 1.2 10.4 Rapeseedmethylester (RME) 4.9 3.1 3.8 1.5 AW CH6-0959-082008 Combustion Ion Chromatography

Highly viscous oil samples Determination of Chloride Crude oil with high content of Sulfur A Supp 5 –150 100 mL injections H2O2 300 ppm, 1 ppm Phosphate 50 ppb Cl was the lowest calibration point. Sample Chloride [ppm] RSD [%] Waxy distillate 36.5 4.3 HCR-Feed < LOQ 9.1 Migrol Greenlife Biodiesel 5.0 1.2 Rapeseedmethylester (RME) 4.9 3.1 AW CH6-0980-012009 Combustion Ion Chromatography

Residual solvents Matrix Elimination of H2O2 (no disturbance for F) Determination of F, Cl,Br, S A Supp 5 –150 10 or 100 mL injections H2O2 900 ppm, 20 ppm Phosphate for high concentrated samples H2O2 90 ppm, 1 ppm Phosphate for low concentrated samples 1P12497E THF/Toluene 150P760 Diversolvent A PCC HC, Dosino, No. S [%] Cl [%] Br [%] F [%] 1 n.d. 8.16 13.80 2 8.03 13.59 3 8.56 14.58 Avg - 8.25 13.99 RSD % 1.2 3.7 No. S [ppm] Cl [ppm] Br [ppm] F [ppm] 1 2.4 14.8 20.6 n.d. 2 2.5 14.7 20.7 3 3.3 20.9 Avg 2.7 - RSD % 0.3 0.6 AW CH6-0984-022009 Combustion Ion Chromatography

Parameters are adjustable Adjustable parameters e.g. for lower concentration Increase amount of sample for combustion Decrease absorbent volume Multiple combustion into one absorbent volume Increase injection loop Combustion Ion Chromatography

USP Advantages by Combustion IC Full Automation with Mitsubishi setup Reduced analysis time Fast Sample throughput Simultaneous determination of sulfur and halogen compounds Halogens are speciated individually Analysis of solids and viscous substances! Analysis within the ppm range New application fields for IC Combustion Ion Chromatography

Combustion Ion Chromatography Beyond the horizon – the world of combustion sampling H2O2 zeigt Störung bei F -> Matrix Elimination