Automotive VOC Testing Overview Presentation by Joe Franklin, Analytical Testing Manager Intertek Automotive Research, San Antonio, Texas October 24, 2013

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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

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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?

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Interior Components – Sources of Emission Ø  Ø  Ø  Ø  Ø 

Plastics, Foams, Carpet, Cloth, Rubber, Leather Sealants, Glue Circuit boards Wire harnesses Stickers, Labels, Tape

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Other Sources of VOC Emission Ø  Ø  Ø  Ø  Ø  Ø  Ø  Ø 

Cleaners Strippers Solvents Lubricants Flame Retardant Waxes Protectant HVAC system intakes

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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

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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.

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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

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Chamber/Bag Method

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Full Vehicle Method Example

Chamber Temp (C)

Chamber Lamps On

AC On

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Sample Cabin

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Pre condition

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Sample Cabin

Sample BG

Closed Mode

Drive Mode www.intertek.com

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.

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European Methods

Ø  German VDA Standards and Procedures •  Referenced or used by VW, BMW, Mercedes, Volvo •  Headspace, Thermal Desorption, Odor, Chamber Ø  BMW •  Chamber and SHED Methods Ø  VW •  Headspace, Odor, Chamber Ø  Mercedes •  Chamber, Thermal Desorption Ø  Volvo •  Headspace, Chamber Ø  TÜV Rhineland Group Standards and procedures •  Full Vehicle interior

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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

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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

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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

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Sampling/Collection Systems Ø  TENAX TD Tubes – collect Aliphatic and Aromatic Hydrocarbons

Ø  DNPH Cartridges – collect Aldehydes and Ketones

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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  Ø  Ø  Ø  Ø  17

GC-TCD FOG Bath IC Dedicated Ovens/Balances TGA www.intertek.com

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.

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GC/MS Sample Run Example

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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

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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.

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… Possibilities for the Future

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Basic Comparison Information

Chamber- Flow through purged

Bag – Static

Simulates cabin air with A/C on, stopped for brief period of soak

Short test duration, introduces potential for bag contribution

Dilutes sample and reduces detection limit

Concentrates emissions for good detection limit

Small sample size limit based on chamber size

Bags are scaleable to part/material size

Many complicated chamber evaluation Bags can be difficult to open and close techniques and reseal.

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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.

Captures VOCs generated/removed by manufacture of the assembly (adhesives/ heated application).

Can be difficult to scale up for predicting total vehicle.

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.

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Thank You! Any Questions?

Joe Franklin Intertek Automotive Research [email protected] 210-523-4671

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