Halogen Free: What, Why and How Presented by : Jim Cronin Environmental Monitoring and Technologies, Inc.
We will discuss What are Halogens and how we interact with them. Why Halogens, within consumer electronics, are of concern to the environment and to human contact How Halogen-Free is defined within various directives & the test methods available to determine halogen content
What are Halogens? Halogens are 5 non-metallic elements found in group VIIA of the periodic table. Fluorine, Chlorine, Bromine, Iodine, Astatine Halogen means salt former and compounds containing halogens are called salts. Halogens exist, at room temperature, in all three states of matter Solid Iodine, Astatine Liquid Bromine Gas Fluorine, Chlorine
Periodic Table : Halogens
Halogens are our friends!
Why Halogen Free? For some applications there is possibility that halogenated flame retardants (HFRs) in plastic materials will release corrosive & toxic gases if ignited in a fire. The corrosive element of these gases has the potential to damage electronics wherever the smoke travels The toxic element can be potentially hazardous to human and animal life.
Why Halogen Free? Recycling of HFRs Certain monomers in plastics will evaporate during shredding/grinding, posing ecotoxicity and human toxicity risks. Plastic is burned during metals recovery Wastewater from plastics recycling processes is often discharged into sewers In landfills, HFR leach from plastics and other materials and can spread Uncontrolled burning in landfills can emit dioxins & furans from halogenated materials.
What determines Halogen-Free? To date, no legislation covering halogen content exists. Lack of legislation results in material of the month behavior driven by environmental groups and/or OEMs striving for a competitive advantage Which of the defined standards that are recognized within the Consumer Electronics Industries do you follow?
Halogen Free Specifications & Standards JPCA-ES-01-1999 Br < 0.09wt% (900 ppm) Cl < 0.09wt% (900 ppm) IEC 61249-2-21 900 ppm maximum Cl 900 ppm maximum Br 1500 ppm total Halogens IPC-4101B 900 ppm maximum Cl 900 ppm maximum Br 1500 ppm total Halogens (These Halogen-Free Standards include Bromine & Chlorine only)
Test Methods for halogen content: Test Method Prep Method Equipment Elements EPA SW-846 5050/9056 Oxygen bomb combustion Ion Chromatograph (IC) Cl, Br, Fl, I EN14582 (Method A) Oxygen bomb combustion IC Cl, Br, Fl, I EN14582 (Method B) Oxygen flask combustion IC Cl, Br, Fl, I JPCA-ES-01-2003 Oxygen flask combustion IC Cl, Br, Fl, I IEC 61189-2 Oxygen flask combustion IC Cl, Br IPC-M-650 Oxygen flask combustion IC Cl, Br ASTM E442-91 Oxygen flask combustion Silver nitrate titration Total (Cl+Br+I) EN50267-2-1, 1999 Oxygen flask combustion Silver nitrate titration Total (Cl+Br+I) EN50267-2-2, 1999 Oxygen flask combustion ph meter, Conductivity degree of acidity NIEA R404.21C Pyrolysis (Tube Furnace) Silver nitrate titration/ic Cl EPA SW-846 9020 (TOX) Pyrolysis (Tube Furnace) Microcoulometric titrator EPA SW-846 9023 (EOX) Pyrolysis (Tube Furnace) Microcoulometric titrator Total organic halogens reported as Chloride Extracted organic halogens reported as Chloride
Our Focus will be on: EPA SW-846 5050/9056 DIN EN 14582 (method A) Sample preparation by: Oxygen Bomb Combustion Analysis by: Ion Chromatography (IC)
Definition: Halogen content: Sums of halogens contained as organic and inorganic compounds that can be converted to halides (fluoride, chloride, bromide, iodide) by combustion and then absorbed or dissolved in an aqueous solution. (DIN EN 14582) Be aware that the above definitions are valid for this empirical EN only and do not comply with scientific definitions of halogen content
EPA SW-846/DIN EN 14582 Oxygen Bomb Combustion Apparatus and Materials (EPA) 1. 1 gram of sample (maximum) 2. Bomb, having a capacity of not less than 300mL, so constructed that it will not leak during the test and that quantitative recovery of the liquids from the bomb may be readily achieved. 3. Sample cup platinum or stainless steel 4. Firing wire platinum or stainless steel 5. Ignition circuit capable of supplying a sufficient current to ignite the sample without melting the wire. Equipment (EN) 1. 0.05 g to 1 gram of sample 2. Calorimetric Bomb, with a capacity of not less than 200mL and equipped with a purging system 3. Sample cup platinum or stainless steel or quartz 4. Firing wire platinum or stainless steel 5. Ignition circuit capable of supplying a sufficient current to ignite the sample without melting the wire
EPA SW-846/DIN EN 14582 Oxygen Bomb Combustion Reagents (epa) Reagent Water Oxygen free from combustible material and halogen compounds. Available at a pressure of 40 atm. Absorption Solution sodium bicarbonate /sodium carbonate Dissolve 2.52 g sodium bicarbonate NaHCO 3 & 2.52 g sodium carbonate Na 2 CO 3 in reagent water and dilute to 1 L. White oil. refined Reagents (en) Water of grade 1 Oxygen free from combustible material, available at a pressure of 30 to 40 atm. Absorption Solution sodium bicarbonate /sodium carbonate Dissolve 2.52 g sodium bicarbonate NaHCO 3 & 2.52 g sodium carbonate Na 2 CO 3 in reagent water and dilute to 1 L. Absorption Solution for Iodine Ascorbicacid solution, (C 6 H 8 O 3 ). w = 1% Combustion enhancer (e.g. paraffin)
EPA SW-846/DIN EN 14582 Oxygen Bomb Combustion Principle (EPA) Sample is oxidized by combustion in a closed system Halogenated compounds are converted to Fluoride (Fl - ), Chloride (Cl - ), Bromide (Br - ) Halide compounds are absorbed or dissolved in an absorption solution Solution analyzed by Ion Chromatograph Principle (EN) Sample is oxidized by combustion in a closed system Halogenated compounds are converted to Fluoride (Fl - ), Chloride (Cl - ), Bromide (Br - ), Iodide (I - ) Halide compounds are absorbed or dissolved in an absorption solution Solution analyzed by Ion Chromatograph Note: Insoluble halides are not completely determined
EPA SW-846/DIN EN 14582 QA/QC EPA MS/MSD should be run Duplicate every 10 samples Blank LCS run to +/- 10% limits EN Grinding sample to 200 microns Blank (suggests in between samples) LCS run to +/- 10% limits Heterogeneous samples to be run in duplicate/triplicate
EPA SW-846 5050 Oxygen Bomb Combustion Calculations (EPA) C com x V com x DF C 0 = W 0 C 0 = concentration of element in sample C com = concentration of element in combustate V com = total volume of combustate, ml DF = dilution factor W 0 = weight of sample combusted, g. Report the concentration of each element detected in the sample in micrograms per gram
DIN EN 14582 Oxygen Bomb Combustion Evaluation (EN) X i = (C i x V)/ 1000 m X i is the element of content in the test sample in grams per kilogram (g/kg) C i is the concentration expressed in mg/l of this element, i is the absorption solution V is the final volume the absorption solution, expressed in ml. m is the mass of the test portion, expressed in grams
EPA SW-846/DIN EN 14582 Analysis by Ion Chromatograph (IC) The combustate collection solution is injected into the IC to flush & fill a constant sample loop. The sample is then injected into a stream of carbonate-bicarbonate eluent of the same strength as the collection solution. The sample is pumped through three different ion exchange columns and into a conductivity detector.
EPA SW-846/DIN EN 14582 Analysis by Ion Chromatograph (IC) A precolumn or guard column and a separator column separate ions into discrete bands. The suppressor column converts the anions in the sample to their corresponding acids. The separated anions in their acid form are measured using an electrical-conductivity cell. Anions are identified based on their retention times compared to known standards. Quantitation is accomplished by measuring the peak height or area and comparing it to a calibration curve generated from known standards.
EPA SW-846/DIN EN 14582 Analysis by Ion Chromatograph (IC) The method detection limit (MDL) is the minimum concentration of a substance that can be measured and reported with 99% confidence that the value is above zero. Varies for anions as a function of sample size and the conductivity scale used. Sample matrix is a determining factor for MDL. Limits may be extended by appropriate dilution.
Method Pros and Cons EPA SW-846/DIN EN 14582 Pros 1. Method can determine Br, Fl, Cl, & I 2. Cost effective because method provides results on Br, Fl, Cl, & I 3. Reduced sample volume 4. Repeatability 5. Attainable MDLs Cons 1. May not be as accurate as methods determining a specific analyte. 2. Insoluble halides are not completely determined
Questions? Jim Cronin 800-246-0663 jcronin@emt.com www.emt.com
Thank you!