1. © 2006 IARC 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. 2 © 2006 IARC Content  Programme background and objectives  Definitions and standards  Sampling techniques 

3. 3 © 2006 IARC 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. 4 © 2006 IARC 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. 5 © 2006 IARC Supplier Interaction Headliner carpets facia trim Components (component testing) Materials (micro chamber) Adhesives Sealants Assistance to suppliers Tests, reports, training, material choices

6. 6 © 2006 IARC 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 Substance Concentration guidelines µg/m 3 Issue Formaldehyde100Potential carcinogen, irritant Acetaldehyde48Irritant Toluene260Headaches, fatigue Xylene870Harmful irritant Ethylbenzene3800Toxic agent Styrene220Harmful irritant Di-n-butyl phthalate220Phthalates linked to cancer Di-n-ethylhexyl phthalate120and hormone imbalance Tetradecane330

7. 7 © 2006 IARC VOC:  Sum of VVOC and VOC which easily evaporate from sample at test-temperature 25 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 Definitions: In car air quality – what exactly do the terms mean ?

8. 8 © 2006 IARC Boiling point TermExamples < 50 ºC Very Volatile Organic Compounds (VVOC) Formaldehyde (- 21 ºC) Acetaldehyde (20 ºC) > 50 ºC < 260 ºC Volatile Organic Compounds (VOC) Benzene (80 ºC) Toluene (110 ºC) Styrene (145 ºC) Dabco (175 ºC) > 260 ºC < 400 ºC Semivolatile Organic Compounds (SVOC) Di-n-butyl phthalate (340 ºC) Di-n-ethylhexyl phthalate (390 ºC) > 400 ºC Particulate Organic Matter (POM) PCB Definitions: VOC Classification by the WHO

9. 9 © 2006 IARC Which VOC substances monitored ?

10. 10 © 2006 IARC Which VOC substances monitored? R-phrases

11. 11 © 2006 IARC 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. 12 © 2006 IARC 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

13. 13 © 2006 IARC

14. 14 © 2006 IARC Test configuration / sampling process Air flow rate / sampling time very closely controlled to give consistency of results. Results in micrograms per m 3 These must be below values given in regulations. Will effect: health toxicity, odour and fogging.

15. 15 © 2006 IARC Sampling and test protocol  Air sampling conditions - Components  Chamber temp.: 40 0 C  Heating time:4.5hr Heater case Chamber Fill the heated air Schematic of 4m 3 chamber

16. 16 © 2006 IARC U-cte testing set-up IARC emission lab set-up:

17. 17 © 2006 IARC Single µ- CTE Chamber Assembly Sample tube Flow controlling device 10 – 500 ml/min Air/gas manifold supplying all 6 μ-Chambers Heated block Temps. up to 120°C Micro-chamber Diameter 45 mm Depth 28 mm Volume ~45 cm 3 Heated air/gas supply The µ-CTE contains 6 Chambers in Total

18. 18 © 2006 IARC 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. 19 © 2006 IARC Sampling and test protocol Materials sampling conditions Microchamber Parameters:  Micro-cell mode (planar sample, Ø40mm disc)  VOC-free compressed air  40 0 C  30 minutes  21 ml/min flow rate  TENAX TA packed steel tubes (200mg)

20. 20 © 2006 IARC 1m3 Chamber for VDA276 Testing

21. 21 © 2006 IARC 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. 22 © 2006 IARC VDA276 expected concentration profile Steady state period Nominal chamber concentration Time during test Sample conditioning period VOC levels minus Air exchange Oven conditioning sampling

23. 23 © 2006 IARC 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. 24 © 2006 IARC Surface Interactions Still air: surface boundary layer - area / topography Bulk Material: - Density - Surface area -VOC Molecular weights -Layered Structures - foams - adhesives Surface air flow Bulk diffusion Air Diffusion Rapid Removal of VOCs

25. 25 © 2006 IARC 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. 26 © 2006 IARC 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. 27 © 2006 IARC 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. 28 © 2006 IARC Analytical process conditions ParameterValue Column60 m, 0.25 μm GC oven (start)40 o C GC oven Ramp 1110 o C @ 6 degs/min GC oven Ramp 2315 o C @ 15 degs/min GC oven hold315 o C for 10 mins Total time35.33 mins Column flow controlConstant velocity mode, 24 cm/sec Ion source200 o C Interface315 o C m/z range35 to 350 GC-MS Parameters: Unity-Ultra Desorption Parameters:

29. 29 © 2006 IARC Effect of Temperature data: types of VOC

30. 30 © 2006 IARC Effect of Decay Data

31. 31 © 2006 IARC VDA276 normalised graph

32. 32 © 2006 IARC VDA276 – Spectrum change with test.

33. 33 © 2006 IARC

34. Environmental Competence Project Premium Automotive Research and Development Programme