© 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

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ContentContent

Programme background and objectives

Definitions and standards

Sampling techniques

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© 2006 IARC

Environmental Competence Project Environmental Competence Project - Primary Objectives- 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)

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PARD Programme backgroundPARD 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

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© 2006 IARC

Supplier InteractionSupplier Interaction

Headliner

carpets

facia

trim

Components

(component testing)

Materials

(micro chamber)

Adhesives

Sealants

Assistance to suppliers

Tests, reports, training, material choices

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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

SubstanceConcentration guidelines

µg/m3 Issue

Formaldehyde 100 Potential carcinogen, irritant

Acetaldehyde 48 Irritant 

Toluene 260 Headaches, fatigue 

Xylene 870 Harmful irritant

Ethylbenzene 3800 Toxic agent

Styrene 220 Harmful irritant

Di-n-butyl phthalate 220 Phthalates linked to cancer

Di-n-ethylhexyl phthalate 120 and hormone imbalance

Tetradecane 330  

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VOC: VOC:

Sum of VVOC and VOC which easily evaporate from sample Sum of VVOC and VOC which easily evaporate from sample at test-temperature 25 << 100 at test-temperature 25 << 100 ºC/1barr and with in-car ºC/1barr and with in-car concentration at least > 2 times higher than outsideconcentration at least > 2 times higher than outside

FOG (Windscreen Fogging): FOG (Windscreen Fogging):

Sum of VOC and SVOC which evaporate from sample at test-Sum of VOC and SVOC which evaporate from sample at test-temperature > 90 temperature > 90 ºC/1barrºC/1barr

Odour compounds (OC’s):Odour compounds (OC’s):

Organic chemicals with very high vapour pressure and Organic chemicals with very high vapour pressure and readily evaporating at normal pressures and temperatures readily evaporating at normal pressures and temperatures and quite often not detected as VOC’sand quite often not detected as VOC’s

Definitions: In car air quality – what exactly do Definitions: In car air quality – what exactly do the terms mean ?the terms mean ?

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Boiling pointBoiling point TermTerm ExamplesExamples

< 50 < 50 ºCºC Very Volatile Organic Very Volatile Organic Compounds (VVOC)Compounds (VVOC)

Formaldehyde (- 21 Formaldehyde (- 21 ºC)ºC)

Acetaldehyde (20 ºC)Acetaldehyde (20 ºC)

> 50 > 50 ºCºC

< 260 ºC< 260 ºC

Volatile Organic Compounds Volatile Organic Compounds (VOC)(VOC)

Benzene (80 Benzene (80 ºC)ºC)

Toluene (110 ºC)Toluene (110 ºC)

Styrene (145 ºC)Styrene (145 ºC)

Dabco (175 ºC) Dabco (175 ºC)

> 260 > 260 ºCºC

< 400 ºC< 400 ºC

Semivolatile Organic Semivolatile Organic Compounds (SVOC)Compounds (SVOC)

Di-n-butyl phthalate (340 Di-n-butyl phthalate (340 ºC)ºC)

Di-n-ethylhexyl phthalate (390 ºC)Di-n-ethylhexyl phthalate (390 ºC)

> 400 ºC> 400 ºC Particulate Organic Matter Particulate Organic Matter (POM)(POM)

PCBPCB

Definitions: VOC Classification by the WHODefinitions: VOC Classification by the WHO

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Which VOC substances monitored ?Which VOC substances monitored ?

ESIS: R-phrases ECB IARC EC Nr CAS Nr1 Formaldehyde 23 24 25 34 40 43 Carc. Cat 3 200-001-8 50-00-02 Acetaldehyde 12 36 37 40 Carc. Cat 4 200-836-8 75-07-03 Propionaldehyde 11 36 37 38 204-623-0 123-38-6

4 Benzene 23 24 25 36 38 45 46 48 65Carc. Cat. 1 Mut. Cat 2

200-753-7 71-43-2

5 Toluene 11 20 38 48 63 65 67 Repr. Cat 3 203-625-9 108-88-36 Xylene 10 20 21 38 215-535-7 1330-20-77 Ethylbenzene 11 20 202-849-4 100-41-48 Styrene 10 20 36 38 202-851-5 100-42-59 Chlorobenzene 10 20 51 53 203-628-5 108-90-710 Paradichlorobenzene 36 40 50 53 Carc. Cat 3 Carc. Cat 2B 203-400-5 106-46-711 Dichlorobenzene 246-837-7 25321-22-612 Bromobenzene 203-623-8 108-86-113 Parabromochlorobenzene 203-392-3 106-39-814 Bromochlorobenzene 249-303-1 28906-38-9

15 Nitrobenzene 23 24 25 40 48 51 53 62Carc. Cat 2 Repr. Cat.3

Carc. Cat 2B 202-716-0 98-95-3

16 Phenol 20 21 22 23 24 25 34 48 68 Mut. Cat 3 203-632-7 108-95-217 Benzylchloride 20 51 53 246-698-2 25168-05-218 Dimethylamine 12 20 22 34 Carc. Cat 3 204-697-4 124-40-319 Tetrachloormethane 23 24 25 40 52 53 59 200-262-8 56-23-520 Nitrosodimethylamine 26 27 28 45 6121 Dimethylformamide 20 21 36 61 Repr. Cat 2 200-679-5 68-12-222 Di-n-butyl-phtalate 50 61 62 Repr. Cat 2 & 3 201-557-4 84-74-223 Di-n-ethyl- hexyl- phtalate 60 61 Repr. Cat 2 204-211-0 117-81-7

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Which VOC substances monitored? R-phrasesWhich VOC substances monitored? R-phrases

10 Flammable11 Highly flammable12 Extremely flammable20 Harmful by inhalation21 Harmful in contact with skin22 Harmful if swallowed23 Toxic by inhalation 24 Toxic in contact with skin25 Toxic if swallowed26 Very toxic by inhalation27 Very toxic in contact with skin28 Very toxic if swallowed29 Contact with water liberates toxic gas34 Causes burns 36 Irritating to the eyes37 Irritating to the respiratory system 38 Irritating to skin40 Limited evidence of a carcinogenic effect 41 Risk of serious damage to the eyes43 May cause sensitization by skin contact45 May cause cancer 48 Danger of serious damage to health by prolonged exposure50 Very toxic to aquatic organisms51 Toxic to aquatic organisms52 Harmful to aquatic organisms53 May cause long-term adverse effects in the aquatic environment59 Dangerous to the ozon layer60 May impair fertility61 May cause harm to the unborn child62 Risk of impaired fertility63 Possible risk of harm to the unborn child65 Harmful: may cause lung damage if swallowed67 Vapours may cause drowsiness and dizziness

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Evaluation strategy - Equipment and facilitiesEvaluation 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

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Evaluation strategy - Test programmeEvaluation 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

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Test configuration / sampling processTest 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.

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Sampling and test protocolSampling and test protocol

Air sampling conditions - Components

Chamber temp.: 40 0C

Heating time : 4.5hr

Heatercase

Chamber

Fill the heated air

Schematic of 4m3 chamber

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U-cte testing set-upU-cte testing set-up

IARC emission lab set-up:

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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 cm3

Heated air/gas supply

• The µ-CTE contains 6 Chambers in Total

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Evaluation strategy - Equipment and facilitiesEvaluation 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)

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© 2006 IARC

Sampling and test protocolSampling and test protocol

Materials sampling conditions

Microchamber 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)

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1m3 Chamber for VDA276 Testing1m3 Chamber for VDA276 Testing

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1m3 – VDA276 Chamber Specifications1m3 – 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.

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VDA276 expected concentration profile VDA276 expected concentration profile

Steady stateperiod

Nom

inal

cha

mbe

r co

ncen

trat

ion

Time during test

Sample conditioningperiod

VOC levels minusAir exchange

Oven conditioning

sampling

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Other MethodsOther 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.

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Surface Interactions 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 Removalof VOCs

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Important criteriaImportant 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

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GC/MS - Analysis methodGC/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

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GC/MS Analysis of ResultsGC/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.

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Analytical process conditionsAnalytical process conditions

Parameter Value Flow rate (all) 20 ml/min Purge 1 min Tube desorption temperature/time 300 oC/8 mins Trap fire 310 oC/3 mins Total split ratio 46:1

Parameter Value

Column 60 m, 0.25 μm

GC oven (start) 40 oC

GC oven Ramp 1 110 oC @ 6 degs/min

GC oven Ramp 2 315 oC @ 15 degs/min

GC oven hold 315 oC for 10 mins

Total time 35.33 mins

Column flow control Constant velocity mode, 24 cm/sec

Ion source 200 oC

Interface 315 oC

m/z range 35 to 350

GC-MS Parameters:

Unity-Ultra Desorption Parameters:

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Effect of Temperature data: types of VOCEffect of Temperature data: types of VOC

No. of VOC vs Ret time

0

10

20

30

40

50

60

70

80

90

100

0 5 10 15 20 25 30

Ret time

VO

C n

o.

60C

25C

40C

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Effect of Decay DataEffect of Decay Data

Normalised decay

0

20

40

60

80

100

120

1 6 11 16 21

day

no

rmal

ised

em

issi

on

rat

e

Acetone

Phenol

Dodecane

Isooctanal

acetone - start

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VDA276 normalised graphVDA276 normalised graph

Normalised Graph showing TVOC increase with time over test

y = -0.0433x2 + 11.803x - 38.49

0

100

200

300

400

500

600

700

800

900

0 20 40 60 80 100 120 140 160 180 200

time of test / mins

no

rma

lis

ed

TV

OC

Normalised data Poly. (Normalised data)

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VDA276 – Spectrum change with test.VDA276 – Spectrum change with test.

13.75 14.00 14.25 14.50 14.75 15.00 15.25 15.50 15.75

0.5

1.0

1.5

2.0

2.5

3.0

3.5

(x10,000,000)

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© 2006 IARC

© 2006 IARC

Environmental CompetenceEnvironmental Competence ProjectProject

Premium Automotive Premium Automotive

Research and Development ProgrammeResearch and Development Programme