Www.markes.com Innovations to improve repeatability and reduce costs when testing (s)VOC emissions / content from car trim materials and In Vehicle Air.

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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

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Regulatory and Standard Method Developments for Materials Emissions Testing

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ISO/CEN – ‘Horizontal’ standards

• Construction products (and furnishings..) (ISO TC 146, SC6 and CEN TC264 WG7)

– ISO 16000-6 – Tenax tube, TD-GCMS(/FID) analysis– EN ISO 16000-9 – small chamber– EN ISO 16000-10 – FLEC cell– EN ISO 16000-11 – selection and preparation of samples– ISO CD 16000-24 – 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)

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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 12-13 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

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Japanese Automotive Manufacturers Association Japanese Automotive Manufacturers Association (JAMA)(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.”

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European Auto IndustryEuropean 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)

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JAMA and TJAMA and TÜÜV GuidelinesV Guidelines

Most European car manufacturers are interested in evaluating Vehicle Interior Air Quality (VIAQ) / Material emissions

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Monitoring In Vehicle Air Quality (IVAQ)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

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VDA Techniques available for monitoring Material VDA Techniques available for monitoring Material Emissions from vehicle trim componentsEmissions from vehicle trim components

VDA 270 – OdourVDA 275- Formaldehyde

VDA 276- VOC, s-VOC Test ChamberVDA 277- VOC Headspace

VDA 278- VOC, s-VOC Thermal Desorption

Odour

VOC’s

Fogging S-VOC’s

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Analytical Options for Mat Em. Testing

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.

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

External - Certification

Internal QC - Prevention

1. Emission Chamber 2. Emission Cell

3. Micro-chamber

4. Direct Desorption5. Barriers/ Permeation

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VDA 276- Test Chamber MethodVDA 276- Test Chamber Method

LineTime[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 70 Maximum 10.4/4.0 Prepare test chamber if needed

Test

3 0:00 65 0.40 10.4/5.0 First conditioning phase

4 2:00 65 0.40 10.4/5.0 Start air sampling:BTXE/S-aromaticsaldehydes and ketonessurvey analysisany other sampling

56

4:308:00

100100

0.440.44

??

Second conditioning phasestart fogging samplingend fogging sampling

[1] dew point temperature or relative humidity at 65°C and 1.013 x 105 Pa

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Direct Thermal Desorption-VDA 278Direct 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

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VDA 278 – VOC and sVOC content testingVDA 278 – VOC and sVOC content testingDirect Thermal DesorptionDirect 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

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Internal QC-Internal QC-Direct Desorption (VDA 278)Direct Desorption (VDA 278)

To GC

1. Valve Configuration 1- off line to GC2. Sample tube Heated

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Secondary Desorption (VDA 278)Secondary Desorption (VDA 278)

GC/MS/FID

To GC

1. Valve Configuration 2- on line to GC

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Results- PVC Foam sheet VOC content analysis by VDA 278

Desorbing for 30 minutes at 90°C VOC’s up to n-C20

Compound 1. 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)

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Results- Artificial leather Fogging Compounds by VDA 278

Desorbing for 30 minutes at 90°C followed by 60 minutes at 120°CSVOC n-C16 to n-C32

Compound 1. 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)

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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

Detergent

Natural oil

Discoloured Portion

Control Portion

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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.