1. Dr Peter Hughes Markes International Ltd Material Emissions Specialist
Innovations to improve repeatability and reduce costs when testing (s)VOC emissions / content from car trim materials and In Vehicle Air Quality
Dr Peter Hughes
Markes International Ltd
Material Emissions Specialist

2. Regulatory and Standard Method Developments for Materials Emissions Testing

3. ISO/CEN – ‘Horizontal’ standards
Construction products (and furnishings..) (ISO TC 146, SC6 and CEN TC264 WG7)
ISO – Tenax tube, TD-GCMS(/FID) analysis
EN ISO – small chamber
EN ISO – FLEC cell
EN ISO – selection and preparation of samples
ISO CD – sorptive building materials (Japan)
Proposed new work item: method for SVOC emissions with high temp micro-chamber. Japanese draft submitted - currently being balloted
Includes other parts on formaldehyde, tracer gas ventilation tests, etc
Car cabin air quality and car trim emissions (new work item for ISO TC 146, SC6)
‘Garage-sized’ chamber test
Chamber VOCs
Chamber SVOCs
Emissions screening method (indicative – would follow after above 3)

4. Regulatory and related drivers around the world
Europe (and ROW) – Construction products directive
Europe (and ROW) – REACH
Germany – Flooring certification and the AgBB scheme
US – California, Washington State, etc and the CHPS programme
US EPA ‘Carpet Dialogue’, CRI and the US ‘Greenguard’ label
Japanese labelling schemes for construction products
Japanese regulation of VOCs in car cabin air
Koreans thinking of doing something similar (Dr Mangoo Kim)
Chinese expect to implement controls on car cabin air quality from 2008

5. Japanese Automotive Manufacturers Association (JAMA)
JAMA’s targets are as follows:
“New models of passenger cars to be sold from fiscal 2007 must satisfy the indoor concentration guidelines established for 13 VOCs by the Ministry of Health, Labour and Welfare. Each carmaker must continuously strive to reduce VOC concentration in passenger compartments. Vehicles covered by the guidelines are passenger cars manufactured and sold domestically. An independent program to reduce VOC’s in commercial vehicles, including trucks and buses, is now being worked upon, and is expected to be announced within fiscal 2005.”

6. European Auto Industry
Voluntary program (at the moment) for Auto manufacturers as set up by the European Automotive Industry (VDA)
Similar to JAMA program in that in cabin air quality must adhere to quality guidelines
The list of target compounds and specified concentration limits defined by TÜV (Technischer Überwachungs-Verein Nord)

7. JAMA and TÜV Guidelines
Most European car manufacturers are interested in evaluating
Vehicle Interior Air Quality (VIAQ) / Material emissions

8. Monitoring In Vehicle Air Quality (IVAQ)
Sample air inside vehicle cabin – pumped sampling - retain compounds onto sorbent tube
Tubes analysed using TD-GC/MS
Sampling techniques available include JAMA and CSIRO technique
Both techniques employ Thermal Desorption

9. VDA Techniques available for monitoring Material Emissions from vehicle trim components
VOC’s
Fogging
S-VOC’s
Odour
VDA 270 – Odour
VDA 275- Formaldehyde
VDA 276- VOC, s-VOC Test Chamber
VDA 277- VOC Headspace
VDA 278- VOC, s-VOC Thermal Desorption

10. Analytical Options for Mat Em. Testing
1. Emission Chamber
2. Emission Cell
External - Certification
VOC emission profiles under ‘real-use’ conditions are best obtained using test chambers (VDA276) or cells with sorbent tube sampling and TD-GC(-MS) analysis.
Internal QC - Prevention
Direct thermal desorption / thermal extraction of materials - Measures VOC content as an indication of emission potential (VDA 278)
Create a barrier to prevent emissions contributing to environment- evaluate effectiveness / permeability of barrier
3. Micro-chamber
Overview of the Typical approaches available for mat em testing can be broken up into 2 distinct areas
Evaluating materials emissions under simulated real use conditions or by preventing potential hazourdous or toxic emission sby reducing their presence in the first place ie. reduce initial content or by employing suitable barriers to prevent emissions being released into the environment.
All approaches require thermal desorption analysis
5. Barriers/ Permeation
4. Direct Desorption

11. VDA 276- Test Chamber Method
Line
Time
[h:min]
Temp.
Target [oC]
Air Change
[1/h]
Air-in humidity [oC/ %rh][1]
Procedure
Pre-conditioning 1 70
Maximum
10.4/4.0 2
-0:30
Prepare test chamber if needed
Test 3
0:00 65
0.40
10.4/5.0
First conditioning phase 4
2:00
Start air sampling:
BTXE/S-aromatics
aldehydes and ketones
survey analysis
any other sampling 5 6
4:30
8:00
100
0.44 ?
Second conditioning phase
start fogging sampling
end fogging sampling
[1] dew point temperature or relative humidity at 65°C and x 105 Pa

12. Direct Thermal Desorption-VDA 278
A number of voluntary labelling schemes which promote ‘Low VOC’ products actually rely on product content testing rather than emissions testing in order to comply with the scheme (e.g. using US EPA Method 311 for paint).
The European automotive industry, adopts a similar approach to testing emissions from car trim components. Their Method VDA 278 specifies direct desorption of materials, at elevated temperatures, to assess both VOCs and SVOCs (fogging) components.
Residual Solvent analysis- pharmaceutical companies

13. VDA 278 – VOC and sVOC content testing Direct Thermal Desorption
Used to minimise the risk from emissions by ensuring that materials do not contain significant concentrations of toxic / odorous compounds in the first place.
Small section of material placed inside of empty sorbent tube and content thermally extracted
Desorbing for 30 minutes at 90°C - VOC’s up to n-C20
followed by 60 minutes at 120°C - SVOC n-C16 to n-C32

14. Internal QC- Direct Desorption (VDA 278)
Valve Configuration 1- off line to GC
Sample tube Heated
To GC

15. Secondary Desorption (VDA 278)
Valve Configuration 2- on line to GC
GC/MS/FID
To GC

16. Results- PVC Foam sheet VOC content analysis by VDA 278
Desorbing for 30 minutes at 90°C VOC’s up to n-C20
Compound
toluene
(C7H8)
2. 1-methoxy-2 propylacetate
(C6H12O3)
3. 2-ethyl-1-hexanol (C8H18O)
4. 1-methyl-2-pyrrolidinone (C5H9NO)
5. 2-(butoxyethoxy)-ethanol (C10H20O4)
6. 1-decanol (C10H22O)
7. butylated hydroxytoluene
(C15 H24 O)

17. Results- Artificial leather Fogging Compounds by VDA 278
Desorbing for 30 minutes at 90°C followed by 60 minutes at 120°C
SVOC n-C16 to n-C32
Compound
2,6-di-tert-butyl-4-sec-butyl phenol
(C16H350)
2. decanedioic acid, dimethyl ester (C12H2204)
3. 2-hexyl-1-decanol (C16H340)
4. bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (C25H56N204)
5. di-i-decyl phthalate (C28H4604)
6. di-n-decyl phthalate
(C28H4604)

18. Direct Thermal Desorption for Troubleshooting (Example: Discoloration of Leather)
White leather upholstery discoloured (turned yellow) in patches
Direct desorption of the discoloured sample (top) showed high concentration of natural oils
Direct desorption of a sample of white (control) leather (bottom) shows high concentrations of detergent.
The leather upholstery had not been adequately treated with detergent
Discoloured Portion
Natural oil
Detergent
Control Portion

19. Direct Desorption (VDA 278) Summary
Compatible with many materials
Can be used for complete (quantitative) extraction
Can provide a representative profile of the (S) VOC content of a material
VOC/SVOC simultaneous analysis is readily achieved
Limitations- small sample size might not be representative of the whole sample
Direct correlation between conventional emissions testing difficult- due to bulk desorb’n rather than surface, elevated temps., and small sample size.