Environmental Competences:
VIAQ Training Day
Dr. G.J.Williams, Dr.M.W.Pharaoh, P.Madden,
Warwick Manufacturing Group, University of Warwick
M.Griffin
JLR
© 2006 IARC
Content

Programme background and objectives

Definitions and standards

Sampling techniques

© 2006 IARC
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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)
© 2006 IARC
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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
© 2006 IARC
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Supplier Interaction
Components
(component testing)
facia
Headliner
Materials
(micro chamber)
Assistance to suppliers
Tests, reports, training, material choices
trim
carpets
Adhesives
Sealants
© 2006 IARC
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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
Substance
© 2006 IARC
Concentration 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
6
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 testtemperature > 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
© 2006 IARC
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Definitions: VOC Classification by the WHO
Boiling point
Term
Examples
< 50 ºC
Very Volatile Organic
Compounds (VVOC)
Formaldehyde (- 21 ºC)
Acetaldehyde (20 ºC)
> 50 ºC
Volatile Organic Compounds
(VOC)
< 260 ºC
Benzene (80 ºC)
Toluene (110 ºC)
Styrene (145 ºC)
Dabco (175 ºC)
> 260 ºC
Semivolatile Organic
Compounds (SVOC)
< 400 ºC
> 400 ºC
Di-n-butyl phthalate (340 ºC)
Di-n-ethylhexyl phthalate (390 ºC)
Particulate Organic Matter
(POM)
PCB
© 2006 IARC
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Which VOC substances monitored ?
1
2
3
Formaldehyde
Acetaldehyde
Propionaldehyde
ESIS: R-phrases
23 24 25 34 40 43
12 36 37 40
11 36 37 38
4
Benzene
23 24 25 36 38 45 46 48 65
5
6
7
8
9
10
11
12
13
14
Toluene
Xylene
Ethylbenzene
Styrene
Chlorobenzene
Paradichlorobenzene
Dichlorobenzene
Bromobenzene
Parabromochlorobenzene
Bromochlorobenzene
11
10
11
10
10
36
20
20
20
20
20
40
38 48 63 65 67
21 38
36 38
51 53
50 53
ECB
Carc. Cat 3
Carc. Cat 4
IARC
Carc. Cat. 1
Mut. Cat 2
Repr. Cat 3
Carc. Cat 3
EC Nr
200-001-8
200-836-8
204-623-0
CAS Nr
50-00-0
75-07-0
123-38-6
200-753-7 71-43-2
Carc. Cat 2B
Carc. Cat 2
Carc. Cat 2B
Repr. Cat.3
22 23 24 25 34 48 68 Mut. Cat 3
53
22 34
Carc. Cat 3
25 40 52 53 59
28 45 61
36 61
Repr. Cat 2
Repr. Cat 2 & 3
62
Repr. Cat 2
203-625-9
215-535-7
202-849-4
202-851-5
203-628-5
203-400-5
246-837-7
203-623-8
203-392-3
249-303-1
108-88-3
1330-20-7
100-41-4
100-42-5
108-90-7
106-46-7
25321-22-6
108-86-1
106-39-8
28906-38-9
15 Nitrobenzene
23 24 25 40 48 51 53 62
202-716-0 98-95-3
16
17
18
19
20
21
22
23
20
20
12
23
26
20
50
60
203-632-7
246-698-2
204-697-4
200-262-8
Phenol
Benzylchloride
Dimethylamine
Tetrachloormethane
Nitrosodimethylamine
Dimethylformamide
Di-n-butyl-phtalate
Di-n-ethyl- hexyl- phtalate
21
51
20
24
27
21
61
61
108-95-2
25168-05-2
124-40-3
56-23-5
200-679-5 68-12-2
201-557-4 84-74-2
204-211-0 117-81-7
© 2006 IARC
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Which VOC substances monitored? R-phrases
10
11
12
20
21
22
23
24
25
26
27
28
29
34
36
37
38
40
41
43
45
48
50
51
52
53
59
60
61
62
63
65
67
Flammable
Highly flammable
Extremely flammable
Harmful by inhalation
Harmful in contact with skin
Harmful if swallowed
Toxic by inhalation
Toxic in contact with skin
Toxic if swallowed
Very toxic by inhalation
Very toxic in contact with skin
Very toxic if swallowed
Contact with water liberates toxic gas
Causes burns
Irritating to the eyes
Irritating to the respiratory system
Irritating to skin
Limited evidence of a carcinogenic effect
Risk of serious damage to the eyes
May cause sensitization by skin contact
May cause cancer
Danger of serious damage to health by prolonged exposure
Very toxic to aquatic organisms
Toxic to aquatic organisms
Harmful to aquatic organisms
May cause long-term adverse effects in the aquatic environment
Dangerous to the ozon layer
May impair fertility
May cause harm to the unborn child
Risk of impaired fertility
Possible risk of harm to the unborn child
Harmful: may cause lung damage if swallowed
Vapours may cause drowsiness and dizziness
© 2006 IARC
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Evaluation strategy - Equipment and facilities

Vehicle Testing: performed at Gaydon
 Volumetric

1m3 chamber testing
 Volumetric

test: ug/m3
test: ug/m3
Micro-chamber testing
 Emission
rate test: ug/m2/hr

Thermal desorption – GC/MS

HPLC – being installed later this week
© 2006 IARC
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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
© 2006 IARC
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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.
© 2006 IARC
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Sampling and test protocol

Air sampling conditions - Components

Chamber temp.:
40 0C

Heating time :
4.5hr
Chamber
Heater
case
Fill the heated air
Schematic of 4m3 chamber
© 2006 IARC
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U-cte testing set-up
IARC emission lab set-up:
© 2006 IARC
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Single µ- CTE Chamber Assembly
Sample tube
Micro-chamber
•Diameter 45 mm
•Depth 28 mm
•Volume ~45 cm3
Heated block
• The µ-CTE contains 6 Chambers in Total
Heated
air/gas supply
•Temps. up to 120°C
Air/gas manifold
supplying all 6
μ-Chambers
Flow controlling device
•10 – 500 ml/min
© 2006 IARC
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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)
© 2006 IARC
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Sampling 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)
© 2006 IARC
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1m3 Chamber for VDA276 Testing
© 2006 IARC
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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.
© 2006 IARC
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Nominal chamber concentration
VDA276 expected concentration profile
VOC levels minus
Air exchange
Oven
conditioning
© 2006 IARC
Sample conditioning
period
sampling
Steady state
period
Time during test
22
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.
© 2006 IARC
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Surface Interactions
Surface air flow
Rapid Removal
of VOCs
Air Diffusion
Bulk diffusion
Still air: surface boundary layer
- area / topography
Bulk Material:
- Density
- Surface area
-VOC Molecular weights
-Layered Structures
- foams
- adhesives
© 2006 IARC
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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
© 2006 IARC
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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
© 2006 IARC
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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.
© 2006 IARC
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Analytical process conditions
Unity-Ultra Desorption Parameters:
Value
20 ml/min
1 min
300 oC/8 mins
310 oC/3 mins
46:1
Parameter
Flow rate (all)
Purge
Tube desorption temperature/time
Trap fire
Total split ratio
GC-MS Parameters:
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
© 2006 IARC
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Effect of Temperature data: types of VOC
No. of VOC vs Ret time
100
90
60C
80
25C
70
40C
VOC no.
60
50
40
30
20
10
0
0
5
10
15
20
25
30
Ret tim e
© 2006 IARC
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Effect of Decay Data
Normalised decay
120
100
Acetone
normalised emission rate
Phenol
Dodecane
80
Isooctanal
acetone - start
60
40
20
0
1
6
11
16
21
day
© 2006 IARC
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VDA276 normalised graph
Normalised Graph showing TVOC increase with time over test
900
800
700
y = -0.0433x2 + 11.803x - 38.49
normalised TVOC
600
500
400
300
200
100
0
0
20
40
60
80
100
120
140
160
180
200
time of test / mins
© 2006 IARC
Normalised data
Poly. (Normalised data)
31
VDA276 – Spectrum change with test.
© 2006 IARC
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© 2006 IARC
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Premium Automotive
Research and Development Programme
Environmental Competence
Project
© 2006 IARC