Environmental Competences: VIAQ Training Day Dr. G.J.Williams, Dr.M.W.Pharaoh, P.Madden, Warwick Manufacturing Group,

1. Environmental Competences: VIAQ Training Day Dr. G.J.Williams, Dr.M.W.Pharaoh, P.Madden, Warwick Manufacturing Group, University of Warwick M.Griffin JLR

2. Content • Programme background and objectives • Definitions and standards • Sampling techniques

3. Environmental Competence Project - Primary Objectives • Understand the issues and provide clear direction for the project partners to ensure an effective response to the Integrated Product Policy (IPP). • Develop capability within the supply base to satisfy the emerging requirements for vehicle interior air quality (VIAQ)

4. PARD Programme background • The Premium Automotive Research and Development (PARD) Programme consists of a portfolio of research and development projects. • Programme set up in 2003, project activity to be completed by end 2006 and deliverables achieved by 2010 • It is aimed at enhancing the manufacturing and design capabilities of automotive supplier companies, particularly in the West Midlands. • The programme is supported by the Regional Development Agency, Advantage West Midlands together with numerous partner companies, including a lead partner, Jaguar & Land Rover. • The International Automotive Research Centre was set up in the University’s Warwick Manufacturing Group to host the programme

5. Supplier Interaction Components (component testing) facia Headliner Materials (micro chamber) trim Assistance to suppliers carpets Adhesives Sealants Tests, reports, training, material choices

6. JAMA Guidelines Overview • Substances emitted from vehicle interior may be harmful • Japan (JAMA) are the first country to have released voluntary vehicle interior air quality guidelines– seen as potential future legislation. FULL LIST IN HANDOUTS. • Guideline limits are for 9 compounds including formaldehyde, acetaldehyde and toluene tested at 40°C

7. Definitions: In car air quality – what exactly do the terms mean ? • VOC: • Sum of VVOC and VOC which easily evaporate from sample at test-temperature 25 << 100 ºC/1barr and with in-car concentration at least > 2 times higher than outside • FOG (Windscreen Fogging): • Sum of VOC and SVOC which evaporate from sample at test-temperature > 90 ºC/1barr • Odour compounds (OC’s): • Organic chemicals with very high vapour pressure and readily evaporating at normal pressures and temperatures and quite often not detected as VOC’s

8. Definitions: VOC Classification by the WHO

9. Which VOC substances monitored ?

10. Which VOC substances monitored? R-phrases

11. Evaluation strategy - Equipment and facilities • Vehicle Testing: performed at Gaydon • Volumetric test: ug/m3 • 1m3 chamber testing • Volumetric test: ug/m3 • Micro-chamber testing • Emission rate test: ug/m2/hr • Thermal desorption – GC/MS • HPLC – being installed later this week

12. Evaluation strategy - Test programme • Vehicle testing: - Complete vehicle testing performed in line with Japanese Automotive Manufacturers Association (JAMA) voluntary guidelines on a range of new vehicles • Component testing: - Complete car set being tested in chamber - Correlation tests being done to VDA 276 • Material testing being done using micro-chamber: - production material - component material

14. Test configuration / sampling process Air flow rate / sampling time very closely controlled to give consistency of results. Results in micrograms per m3 These must be below values given in regulations. Will effect: health toxicity, odour and fogging.

15. Chamber Heater case Fill the heated air Schematic of 4m3 chamber Sampling and test protocol • Air sampling conditions - Components • Chamber temp.: 40 0C • Heating time : 4.5hr

16. U-cte testing set-up • IARC emission lab set-up:

17. Single µ- CTEChamber Assembly Sample tube • Micro-chamber • Diameter 45 mm • Depth 28 mm • Volume ~45 cm3 • The µ-CTE contains 6 Chambers in Total Heated air/gas supply • Heated block • Temps. up to 120°C • Flow controlling device • 10 – 500 ml/min Air/gas manifold supplying all 6 μ-Chambers

18. Evaluation strategy - Equipment and facilities • Micro-chamber benefits: • Can collect air samples from up to 6 material samples simultaneously • Highly repeatable and controllable • Can carry out sampling from ambient to 120 degs C • Need only small quantities of sample material (~∅40mm discs) • Rapid sample turnaround (based on 30mins sampling time)

19. Sampling and test protocol • Materials sampling conditionsMicrochamber Parameters: • Micro-cell mode (planar sample, Ø40mm disc) • VOC-free compressed air • 40 0C • 30 minutes • 21 ml/min flow rate • TENAX TA packed steel tubes (200mg)

20. 1m3 Chamber for VDA276 Testing

21. 1m3 – VDA276 Chamber Specifications • Treated stainless steel for best cleanliness. • Cleaning protocol, plus air samples taken before each test to confirm cleanliness results. • Testing: Chamber conditioning phase 75C followed by sampling regime of 65C. VDA test is at 120mins after sample has been inserted. • Our testing takes air samples (15mins) immediately the test material is inserted and continues for 220mins.

22. sampling VOC levels minus Air exchange Nominal chamber concentration Oven conditioning Sample conditioning period Steady state period Time during test VDA276 expected concentration profile

23. Other Methods • Tedlar bag, used by Honda and Nissan • Component placed in a tedlar bag which is filled with clean air. Left in the bag for the duration of the test. Air sampled onto a tube at the end of the test period • Direct desorption techniques • Direct pyrolosis of the material in to the MS. • Heating the material in the thermal desorber which follows the usual GC/MS path. • We have been reluctant to do these are they can cause contamination and increase background levels.

24. Surface air flow Rapid Removal of VOCs Air Diffusion Still air: surface boundary layer - area / topography Bulk diffusion • Bulk Material: • - Density • - Surface area • VOC Molecular weights • Layered Structures • foams • adhesives Surface Interactions

25. Important criteria • Selectivity • Which VOCs can be identified and at which level => VOC list • Test capability • How accurate => correctness / sensitivity (ppm, ppb,,.) • How precise => repeatability (one lab, same conditions) => reproducibility (different labs, same conditions) • In house studies to study these parameters

26. GC/MS - Analysis method • Run (Desorb & GC-MS): • 1 blank (clean) VOC tube • 1 pre-loaded calibration ‘standard’, contains 1ug each of target analytes (16 total) • Collected sample tubes • Process: • Calibrate detector response according to 1ug ‘standard’ • Detect and integrate peaks from chromatogram • Analyse mass spectra within those detected peaks • Mass ratios within mass spectrum allow identification of compound • Quantified target compounds & qualitative unknowns

27. GC/MS Analysis of Results • U-cte: run a minimum if 3 chambers, check flow at beginning and end of sampling. • Quantitative results: those compounds run in the standard can be quantified with respect to their response in the standard. • All others are determined with respect to toluene response in the standard using the relative areas; semi-quant results.

28. Analytical process conditions Unity-Ultra Desorption Parameters: GC-MS Parameters:

29. Effect of Temperature data: types of VOC

30. Effect of Decay Data

31. VDA276 normalised graph

32. VDA276 – Spectrum change with test.

34. Premium Automotive Research and Development Programme Environmental CompetenceProject