Automotive VOC Testing Overview Presentation by Joe Franklin, Analytical Testing Manager Intertek Automotive Research, San Antonio, Texas October 24, 2013 1
Content Ø History of VOC testing Ø Common Sources of VOC s in vehicle Interiors Ø VOC Test Types Overview Ø Review of Many Current Automotive VOC Test Methods Ø European Ø Japanese Ø US Ø Analysis requirements Ø Collection & Analysis techniques Ø Possibilities for the future Ø Basic comparison of techniques 2
History of Concern with VOC Emissions Ø Home interiors testing Sick Building Syndrome Ø School computer labs Ø Office buildings Ø Vehicles Ø Japan Automobile Manufacturers Association adopts voluntary Japanese Health Ministry guidelines for air quality in homes Ø US and European Auto manufacturers begin to work toward lower interior VOC s Ø China and Korea signal intent to regulate vehicle VOC s Ø Future needs, Government Regulation to come? 3
Interior Components Sources of Emission Ø Plastics, Foams, Carpet, Cloth, Rubber, Leather Ø Sealants, Glue Ø Circuit boards Ø Wire harnesses Ø Stickers, Labels, Tape 4
Other Sources of VOC Emission Ø Cleaners Ø Strippers Ø Solvents Ø Lubricants Ø Flame Retardant Ø Waxes Ø Protectant Ø HVAC system intakes 5
VOC Test Type Overview Ø Headspace Material test material is placed in a small vial, heated and read directly by GC or GCMS. Ø Thermal desorption Material test material is packed in desorption tube, heated and analyzed. VOC, SVOC/Fog Ø Chamber Test sample is housed in a temperature controlled chamber where clean air is passed through the chamber and the exhaust is sampled. Ø Bag Test sample is sealed in a bag, baked for some period of time, and then the bag atmosphere is sampled. Ø Vehicle Entire vehicle is placed in a chamber. Sniffer probes are placed in various places inside the vehicle. High intensity lights are used to heat the interior of the vehicle. The sniffer probes are sampled after some amount of soak time. Ø Content testing Chemical breakdown of the material (usually liquid or aerosol) is done and compounds of interest are quantified. More typical for consumer products or paints and coatings. 6
Headspace Methods Ø Test material placed within vile. Ø Vile is heated and a sample of the atmosphere within the vile is sent directly to the GC/MS. 7
Thermal Desorption - Direct Ø Test material placed within tube. Ø Heated gas is passed through the tube and sent to the GC/MS. Ø 90ºC VOC, 120ºC SVOC 8
Chamber/Bag Method 9
Full Vehicle Method Example Chamber Lamps On AC On Chamber Temp (C) 40 23 Sample Cabin Sample Cabin Sample BG Sample BG Pre condition Closed Mode Drive Mode 10
Emission Sampling Variables Ø Temperature Anywhere from 20ºC to 120ºC Ø Sample flow rate 0.1 L/min to 1 L/min Ø Sample duration 10 minutes to a few hours Ø Purge media Nitrogen, humidified clean air, shop air Ø Background sample Background to be subtracted from the final results. 11
European Methods Ø German VDA Standards and Procedures Referenced or used by VW, BMW, Mercedes, Volvo Headspace, Thermal Desorption, Odor, Chamber Ø BMW Ø VW Chamber and SHED Methods Headspace, Odor, Chamber Ø Mercedes Chamber, Thermal Desorption Ø Volvo Headspace, Chamber Ø TÜV Rhineland Group Standards and procedures Full Vehicle interior 12
Japanese/Korean Auto OEM Methods Ø Nissan Bag Method Ø Toyota Bag Method Ø Honda Bag Method, No Background Ø Mazda Chamber Method Ø Isuzu Bag Method Ø Hyundai/Kia Bag Method Ø Mitsubishi Bag Method 13
US Auto OEM Methods Ø GM Headspace (Old specification) Direct Thermal Desorption Bottle analysis for Aldehydes and Ketones with HPLC Full Vehicle VOC and SVOC Ø Ford Fog, References SAE Odor, References SAE Headspace VOC Bottle analysis for Aldehydes and Ketones with HPLC 14
Collection/Conditioning Chambers Ø Range from canisters and chambers to large tedlar bags for parts Ø To full vehicle chambers designed to control temperature and air flow 15
Sampling/Collection Systems Ø TENAX TD Tubes collect Aliphatic and Aromatic Hydrocarbons Ø DNPH Cartridges collect Aldehydes and Ketones 16
Analysis Equipment Ø GC/MS Gas Chromatograph with fully integrated Mass Spectrometer detection system, headspace and Thermal desorption sample station. Ø HPLC High performance liquid chromatograph with UV detection system. Ø Additional equipment utilized in evaluating VOC Ø GC-TCD Ø FOG Bath Ø IC Ø Dedicated Ovens/Balances Ø TGA 17
Analysis Types Ø GC/MS calibrated with compounds of interest. Any compound of interest is calibrated with that compound. Peaks of those compounds are identified, integrated and quantified. Ø Total VOC For peaks other than compounds of interest, the toluene response factor is used to quantify TVOC. Normally between Hexane C6 and Hexadecane C16. Ø HPLC calibrated with compounds of interest. Aldehydes & Ketones. 18
GC/MS Sample Run Example 19
Testing Issues Ø Age of test part VOC s decay exponentially, some procedures call out part age. Ø Sealing, UV protection Seal test parts to prevent cross contamination. UV can release VOC s or create different compounds. Ø No tape, paint, stickers Almost anything placed on test part to identify the part will contribute to total VOC. Ø Shipping methods 20
Trends in US Automotive Ø Japanese, European and US OEMs are putting stronger requirements on their suppliers to report VOC/SVOC emission. Ø More and more details are being required for Substances of Concern (SoC) Ø Each OEM has now well established the methods used for evaluation of materials for VOC/SVOC emission. Ø New requirements for SoC is an area that needs more clarification and detail for many OEM requirements. 21 Possibilities for the Future
Basic Comparison Information Chamber- Flow through purged Simulates cabin air with A/C on, stopped for brief period of soak Dilutes sample and reduces detection limit Small sample size limit based on chamber size Many complicated chamber evaluation techniques Bag Static Short test duration, introduces potential for bag contribution Concentrates emissions for good detection limit Bags are scaleable to part/material size Bags can be difficult to open and close and reseal. 22
Comparison information continued Direct Material Analysis Assembly analysis Maximum Surface area exposed for emission. Closer to real surface area exposure. Can be scaled down to minimum quantity for testing, reducing cost of testing. Can be difficult to scale up for predicting total vehicle. Captures VOCs generated/removed by manufacture of the assembly (adhesives/ heated application). Less difficult to scale up for predicting total vehicle. Simple to ship and work with in the lab. Assemblies can be large and difficult to ship and work with in the lab. 23
Thank You! Any Questions? Joe Franklin Intertek Automotive Research Joe.franklin@intertek.com 210-523-4671 24