Volatile Organic Compounds (VOC s)
Christophe Ponce, Automotive Product Manager
(Seating)
Warwick, 16/05/07
Brief summary of the presentation I intend to follow:
Introduction to Huntsman Polyurethanes & the European automotive market
Definitions: How do we describe emissions in an automotive context ?
Description of key VOC test methods
Huntsman investement
Where do emissions come from in a PU context ?
Comparison study : VOC Testing in Car Seats, based on Huntsman systems.
Conclusions
Corporate
Introduction to Huntsman
Polyurethanes and the European
Automotive market
Who is Huntsman?
Differentiated business portfolio
Polyurethanes
MDI
Materials
and Effects
Performance Products
Design &
Composites
Engineering
Performance Specialties
Power &
Electronics
Performance
Intermediates
Pigments
Polyols
PO/MTBE
TPU
Coatings,
Construction
& Adhesives
Textile
Effects
Titanium Dioxide
Maleic Anhydride &
Licensing
Systems
Corporate
Growth rates of the WE & Emerging markets 2002
calculated CAGRs
2021 and
CAGR 3.2%
CAGR 0.75%
CAGR 1.7%
CAGR 0.1%
CAGR -0.9%
CAGR -0.5%
CAGR 11.8%
CAGR 3.1%
CAGR 6.4%
Western Markets
Emerging Markets
Data from JD Powers vehicle build Q4 2006
Corporate
Impact of vehicle growth on total consumption of PU within the European
automotive market
Plastic Families
PP and alloys
PUR
PA and alloys
Other plastics
PE
ABS and alloys
PVC
PBT and PET
PC and alloys
UP
POM
TOTAL
2005
(kg/car)
65.9
19.9
17
13.2
10.7
8.1
4.2
3.3
3.5
2
2.2
150
Car production [mil/y]
(kton)
1440
440
370
290
240
180
90
70
80
40
50
3290
18.9
2010
% (kg/car)
44
73.6
22.1
13
19.4
11
13.7
9
7
11.4
8.6
5
5.1
3
3.9
2
2
3.7
1
2.4
2.3
1
166
(kton)
1765
533
465
328
270
205
125
90
85
55
53
3973
%
44
13
12
8
7
5
3
2
2
1
1
MPV & SUV growth
21.1
Growth in PU:
- More cars, greater share of SUV s & MPV s & more diesel engines
- CAGR PU 2005 2010:
- CAGR vehicle build 2005
2010:
3.9%
3.5%
Diesel engine growth
Corporate
Definitions: How do we describe emissions
in an automotive context ?
Huntsman Polyurethanes CONFIDENTIAL
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
< 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)
BHT (265 ºC)
Di-n-butyl phthalate (340 ºC)
Di-n-ethylhexyl phthalate (390 ºC)
> 400 ºC
Particulate Organic Matter
(POM)
PCB
Corporate
Definitions: In car air quality
terms mean ?
what exactly do the
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
Corporate
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
Corporate
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
Corporate
Description of key VOC test methods
Huntsman Polyurethanes CONFIDENTIAL
Important criteria
Selectivity
Which VOC s can be identified and at which level
=> VOC list
Test capability
How accurate => correctness / sensitivity (ppm, ppb,,.)
How precise => repeatability (one lab, same conditions)
=>reproducability (different labs, same conditions)
In house studies to study these parameters
Corporate
Test methods (1)
1. Daimler Chrysler VDA 278
VOC (90 ºC) - total (ppm)
FOG (120 ºC) -total (ppm)
Sample size ca 20 mg
2. Chamber (1 m³) test GS 97014-3 BMW (headspace µg/m³ ~ ppb)
Based on VDA 276-1
VOC (µg/m³) by GC/MS
Aldehydes after DNP derivatisation (special cartridge) by
HPLC
Conditions
7 days preconditioning (60 to 70 m³/hr purified air flow at 20-25
deg C, no humidity control)
Chamber 65 deg / 5 % rel. humidity / air exchange rate/hr 0.4 ,
residence time: 5 hours (after sampling blank values)
Target product load 0,4 m /m3 (depending on emission intensity)
Corporate
Test methods (2)
3. Huntsman HPLC carbonyl method
Quantifies total (ppm) C1, C2, C3, C4, aldehydes - free and
bounded (acetal)
Principle: ACN extraction (ACN /water: 50/50 for formaldehyde)
+ DNP derivatisation on foam
Sample size: ca 200 mg
4. VDA 277: (PV 3341) VW / Audi method
Not used because poor reproducibility and no identification of
VOC components (result in ppm Carbon )
5. VDA 275: Formaldehyde by colourcomplex
Not used because low reproducibility and influenced by higher
carbonyls.
Corporate
Huntsman Investments
Huntsman investments
Dedicated resources in the organisation
Full programme started Q1 2006
Structured approach
Create awareness and coordinate
action plans at the production locations
Measure
Analyse
the
results
Action
plans
Corporate
Huntsman investments
Purchase new analytical equipment
1 m³ VOC chamber (including preconditioning chamber)
Upgraded analytical equipment (GC/MS )
Corporate
Everberg Test Chamber
Air sampling point
Inside the test chamber (1 m3)
Sampling for GCMS
analysis (air volume !)
Corporate
VOC test methods
Small scale test methods
Industrial standards (example VDA 278, VDA 277, 275, )
Qualitative and /or Quantitative
Specific methods (Huntsman HPLC carbonyl for aldehydes)
Usually quantification of total available VOC s (ppm, ppb,..)
VDA 278 most commonly applied test in industry (ppm level)
Bigger scale test methods = Chamber tests
Differentiation by test parameters
Furniture, Automotive different conditions
Usually quantification by headspace concentration (µg/m³) =
emitted VOC s (~ ppb level !)
Examples VDA 276, GS 97014-3 BMW
OEM s use their own test methods => need for standardisation
Corporate
GS 97014-3: BMW method
Based on VDA 276-1
Positives;
Can test production samples, eg. Car seats
Evaporation technique: measures VOC s in the headspace :
expressed (µg/m3 air)
Results can be more directly related with full scale vehicle
cabin tests and air quality
Can analyse very low VOC contents because of large sample
size and air collection
More flexibility: control chamber conditions (temperature,
humidity, air collection time, multiple air sample collections in
parallel,
Negatives;
Large investment and running costs: test-chamber - test-room
- sample conditioning
Elaborate test : 7 days pre-conditioning / collecting air
samples / residence time 5 hrs / analysis
Corporate
Test Chamber parameters and variables
Clean air
Test Chamber (x m³)
Test
exhaust
specimen
sampling
analysis
differentiation
Temperature
control
Test specimen
load m²/m³
Air exchange
rate
Humidity control
Test specimen
weight
Corporate
Which methods do we apply ?
VOC measurements
VDA 278 Daimler Chrysler (including FOG) at ppm level
1 m³ Chamber test (including aldehydes) at ppb level
Aldehyde measurements
Huntsman Carbonyl method
on foam and polyol samples
for total carbonyls
at ppm level
Corporate
Conclusions test methods
Chamber test most appropriate for VOC/Aldehyde measurements.
similar precision (value X +/- ca 15 % max) for a better
accuracy (~ppb vs ppm)
=> Bigger sample size
=> Example aldehyde study (doping experiments).
For values close to detection limit lower precision figures.
Better selectivity for VOC
Becomes Industry standard.
=> good investment
Negative is that measurements are highly time consuming
(+ high investment costs).
Corporate
Aldehyde measurements capability
(µg/m³)
emissionchamber
Formaldehyde
Formaldehyde doping test
Measurements by the chamber (µg/m³)
140
120
100
80
60
40
20
0
0
2
4
6
8
10
12
Theoretical value (ppm)
40
(µg/m³)
emission Chamber
Acetaldehyde
Acetaldehyde doping test
Measurements by the chamber (µg/m³)
30
20
10
0
0
1
2
3
4
5
6
7
8
9
10
The ore tical v alue (ppm)
Corporate
We have described what emissions are
where do they come from in a PU context ?
Huntsman Polyurethanes CONFIDENTIAL
Foam sample selection most critical step for
chamber VOC analysis.
The nature of the VOC compound will have an effect on quantitative
and qualitative VOC analysis, depending
on the :
Foam Shape => product load (mentioned in BMW GS 97014-3)
Foam Weight (not linear!)
Foam surface (skin/no skin)
Open cells (crushing / no crushing )
=> need for a strict standard test protocol in order to allow
comparison
Corporate
Foam samples for Chamber measurements
standard system (1)
Bucket foam samples
(volume ca 12 l, height ca 23 cm)
Buckets heated at 70 - 80
deg C for 15 minutes to
remove contaminants
Controlled Chemicals
One variable at the time to
check for VOC contribution
of that one variable
standard test system
Polyol
water
catalyst (s)
silicone(s)
stabilizer
other additive
Isocyanate (index ca 100)
Corporate
If we look at the processing of PU systems there are a number
of potential sources of VOC materials
quite complex !!.
Primary VOC s
4.
Contaminations
3.
Substances
intentionally
added
2. Impurities
unintentionally
formed
B) PU
Chemistry &
part processing
1.
Impurities
in raw
materials
A) Premature
raw material
degradation
Secondary VOC s
PU part
C) PU degradation
& absorption
PU part : Total Emission
Corporate
Foam samples for Chamber measurements
standard system (2)
Foam preparation
In clean environment to avoid cross
contamination
Mixing 10 s / 3000 rpm (clean mixer
blade)
Foams to meet stability/closed cell
requirements
Final foam weight 500 g +/- 10 g
2 hours after foam preparation
standard test system
Polyol
water
catalyst (s)
silicone(s)
stabilizer
(criticality investigated)
Foams are demoulded with
(clean) gloves
Foams are fully crushed
other additive
Isocyanate (index ca 100)
(consistent manner!)
Packed in PE lined aluminium
foil and sealed off
Corporate
Comparison study :
VOC Testing in Car Seats, based on
Huntsman systems.
Test methods considered
1. Daimler Chrysler VDA 278
2. Chamber (1 m³) test GS 97014-3 BMW
3. VDA 277: (PV 3341) VW / Audi method
4. VDA 275: Formaldehyde by colour-complex
5. Huntsman HPLC carbonyl method
Corporate
Key results summary GS 97014-3 BMW and VDA 278
Foam ID
A
B
µg/m³ ~ ppb
14054
30527
4452
2638
10238
C1
µg/m³ ~ ppb
149
136
66
51
74
C2
µg/m³ ~ ppb
190
195
32
7
35
C3
C4
µg/m³ ~ ppb
µg/m³ ~ ppb
60
31
142
20
10
0
18
3
25
6
Foam weight
Chamber load
VDA 278
VOC
g
m2/m3
1100
0.54
1080
0.47
440
0.35
440
0.35
292
0.13
ppm
174
744
62
54
866
FOG
ppm
13
479
24
29
1030
GS 97014-3
TVOC
C
D
Rubliflex Rubliflex
HR+
HR+
Standard Standard
E
Aldehydes
Corporate
GS 97014-3 BMW: Key Results Summary
Foam ID
A
B
C
D
Rubliflex Rubliflex
Standard
HR+
HR+
30527
4452
2638
E
TVOC
µg/m³ ~ ppb
Standard
14054
Aldehydes
C1
C2
C3
µg/m³ ~ ppb
µg/m³ ~ ppb
µg/m³ ~ ppb
149
190
60
136
195
142
66
32
10
51
7
18
74
35
25
Foam weight
Chamber load
g
m2/m3
1100
0.54
1080
0.47
440
0.35
440
0.35
292
0.13
10238
TVOC:
Low
D / C < E < A << B High
Aldehydes: all samples contain C1, C2 and C3
For C1, C 2 and C 3 : C/D/E << A/B (Rubiflex HR+ provisional
formaldehyde spec = 28 µg/m3
Overall: Rubiflex HR+ systems superior to A,B and D system.
Note: Foam weights are different and it is known that this influences the results but the correlation between foam
weight and emission values has yet to be established (indications that it is not a linear relationship)
Corporate
GS 97014-3 BMW: TVOC details
Rubiflex HR+
GS 97014-3 BMW: TVOC details (µg/m³)
A
B
C
D
E
35000
Low
C / D < A / E << B
high
30000
Majority are amines
25000
Dabco (A/B very high) and
A 99
B/D : high levels of B 16
20000
15000
10000
5000
0
A
B
C
D
E
2 -ethyl- hexanoic acid
98
340
11
9
35
Glycolether
363
3892
197
123
228
alkane and alkene
62
206
Siloxaan
2198
1941
Toluene
48
Amine
13
11272
48
21
39
3553
20344
N,N dimethylamine
derivatives
DMF and dimethylacetamide
B significant nonanone levels
2138
A 99
Dabco
67
B high level of glycolether due
to monol-PO components
A high and C very high load of
toluene
A/B high siloxane levels
E contains
44
87
4762
120
77
72
1790
2321
4978
Corporate
GS 97014-3 BMW: Aldehyde details
Rubiflex HR+
GS 97014-3 BMW: Aldehyde details (µg/m³)
A
B
C
D
E
500
450
A / B strongly inferior to
C/D/E
400
350
300
250
200
All samples contain C1,
C2, C3 and C 4
150
100
50
0
A
B
C
D
E
C4
31
20
0
2.5
6
C3
60
142
10
18
25
C2
190
195
32
7
35
C1
149
136
66
51
74
Corporate
VDA 278 VOC : Details and key
results summary
Rubiflex HR+
A
174
VDA 278 VOC (ppm )
B
744
C
62
D
54
E
866
900
800
Low C/D < A << B/E High
Majority VOC : amines
Amine in B and E is B 16
(hexadecylamine)
B and also A / E contain
volatile siloxanes
700
600
500
400
300
200
100
0
A.
Glycolether
2-ethyl hexanoic
acid
D
E
11
14
47
10
7
38
9
6
12
13
32
3
3
11
500
Amine
Dabco
C
9
Alkane/Alkene
siloxanes
B
140
118
783
50
45
39
Corporate
VDA 278 FOG: Details and key results
summary
VDA 278 FOG (ppm )
A
13
1200
B
479
C
24
D
29
E
1030
1000
low C/D < A << B << E high
High fogging for E/B due to B 16
catalyst (hexadecylamine)
E : fogging by siloxanes
800
600
400
200
0
A
B
C
D
E
3
A lkane/alkene
2
Siloxanes
51
A cridine + derivates
2
2
9
7
8
Glycolether
11
4
15
21
4
1.3
964
A mine
471
Corporate
Conclusions from VDA 278
VDA 278 VOC : results confirm the GS 97014-3 BMW results, but
are less selective in terms of qualification and quantification.
Amine catalysts constitute the majority of the VOC s
Siloxanes and glycolether VOC s follow usually the same trend
VDA 278 FOG: results provide complemetary information to VDA
278-VOC and GS 97014-3 BMW test results
Trace components or low concentration components in VOC are
intensified in FOG
Acridine levels are most likely formed out of MDI at 120 deg C.
Small traces butylated DPA (Irganox 5057) is detected , probably
as contaminant,
Corporate
Huntsman HPLC Carbonyl: Key Results Summary
Rubiflex HR+
Foam ID
C1 free
C1 bonded (acetal)
C1 total
C2 free
C2 bonded (acetal)
C2 total
C3 free
C3 bonded (acetal)
C3 total
A
B
C
D
E
ppm
ppm
ppm
1.3
0.9
2.2
1.2
0.9
2.1
1.7
0.8
2.5
1.5
0.9
2.4
1.7
0.9
2.6
ppm
ppm
10.4
2.6
13
2.6
2.0
4.6
3.3
1.6
4.9
1.3
2.2
3.5
2.3
2.0
4.3
ppm
ppm
312
46
358
178
67
245
304
45
349
242
45
287
257
35
292
Method not as selective as the GC 97014-3 BMW chamber test for
C1 aldehyde.
High C2 aldehyde content only confirmed for sample A , compared to
GC 97014-3 BMW chamber test
But indications that the test capability is limited.
Real value of the results according the Huntsman HPLC Carbonyl test will be further investigated as soon as more data and
comparisons with GS 97014-3 BMW become available.
Corporate
Conclusions
Huntsman Polyurethanes CONFIDENTIAL
Conclusions on Test methods (1)
Based on the experience obtained so far, the GS 97014-3 BMW method produces the
most reliable VOC data, because;
More accurate and reproducible at µg/m³ thus ~ ppb level
Highly selective in terms of qualification and quantification, ie Pictures best
TVOC and individual VOC compounds at very low levels
Best method for aldehydes
Measures real VOC by headspace sampling
Disadvantage of the GS 97014-3 BMW Chamber method are;
High investment costs
Time required per analysis.
The Huntsman HPLC carbonyl method has much more limited capability;
Specific to carbonyl compounds
It quantifies bonded and free aldehydes/ketones, enabling insight in origin of
aldehyde VOCs which can be a strong benefit
Foam extraction conditions for formaldehyde are being optimized.
It measures total available compounds which is expected to correlate less with
VOCs, as such
Seems less accurate at ppm level than GS 97014-3 BMW at ppb level
Much less elaborate than GS 97014-3 BMW is a strong benefit
The correlation between aldehydes by GS 97014-3 BMW and HPLC carbonyl
method is being studied
Corporate
Conclusions on Test methods (2)
VDA 278 (VOC and FOG) ;
Quick and easy for TVOC and VOC-group fingerprints
Not usable for aldehydes (nor for any very volatile VOC)
Cannot measure very low VOC concentrations
Measures total available compounds thus less representative as chamber VOC
test method
VDA 277: (PV 3341) VW / Audi method
Not used because of poor reproducibility found
No identification of VOC components (result in ppm carbon )
Little use in industry
Will not be used as VOC test method in Everberg
VDA 275: Formaldehyde by colour-complex
Limited to formaldehyde
Found low sensitivity even at 5 10 ppm levels
Low repeatability and reproducibility and results influenced by other carbonyl
compounds.
Will not be used as VOC test method in Everberg
Corporate
Conclusions:
Over the coming years there will be more focus on the
total emission profile within our vehicles
Measurement techniques have developed to such an
extent that ppb levels of materials can be under
discussion
Little work has been be done to compare test methods to
allow clear pictures of automotive specifications to be
developed
Work will be need to be done by all parties in the chain
(raw material supplier / Tier 2 / Tier 1 / OEM) to optimise
emission performance as the raw materials & processing
impact the emission profile
Based on our knowledge we have developped and we are
constiously improving in all application and especially in
the Automotive seating area (see Rubiflex HR+ recent
development with low emission results and improved
comfort and durability properties).
Corporate
A new PU seating system concept to provide simplicity
in meeting a broad range of customer specifications
often seen in an emerging market
Text
Fully formulated system
Excellent flow and stability
Wide range of index
Effective in all mould types
No polymer polyol
EXCEPTIONALLY ROBUST
Fully formulated system
Excellent flow and stability
Wide range of index
Effective in all mould types
Produces low emission foam
No polymer polyol
Enhanced COMFORT
Enhanced DURABILITY
THE KEY MESSAGE THE FORMULATED POLYOL
SYSTEM FOR BOTH TECHNOLOGIES IS THE SAME
Huntsman Polyurethanes CONFIDENTIAL
Corporate
How do the systems perform against standard OEM
specifications ?
Technology
Technology
LOW EMISSION
is designed for mainly VW, RSA, PSA, Fiat and passes all specs at
density from 45-55kg/m³.
Huntsman Polyurethanes CONFIDENTIAL
Corporate
In summary:
Better static comfort
Good static comfort
Improved dynamic comfort
characteristics enabling thinner seats
Good dynamic comfort used for
significant % of FSC in Europe
Better durability
Good durability
Good fatigue properties even with low
emission catalyst packages
Good standard properties even at
low densities
Good mechanical properties across a
very wide range of densities
Good mechanical properties across
a very wide range of density.
Positioning
Designed to improve comfort at
standard thickness or reduce density
to achieve similar performance
Allow to achieve low emission
properties
Positioning
Designed as standard offer for PUR
seating systems capable of meeting
customer needs across a broad
range of densities and hardness.
Can be used to replace TDI for seat
backs / cushions.
Corporate
Thank you for your attention:
My contact details should you have other questions:
Christophe Ponce
Huntsman Polyurethanes
Everberg
Tel: +32 2 758 9353 / Fax : +32 2 758 7353
christophe_ponce@huntsman.com
Information contained herein is based on our present knowledge and experience and does not release the
converter from conducting his own comprehensive tests.
tests. A legally binding guarantee,
guarantee, also regarding possible
rights of third parties,
parties, is expressly denied.
denied. Our products are sold according to our General Terms of Sales and
Delivery.
Corporate