Volatile Organic Compounds (VOC s)

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

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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

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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

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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

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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 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

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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

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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

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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

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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.

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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

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Huntsman investments

Purchase new analytical equipment

1 m³ VOC chamber (including preconditioning chamber) Upgraded analytical equipment (GC/MS )

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Everberg Test Chamber

Air sampling point

Inside the test chamber (1 m3)

Sampling for GCMS analysis (air volume !)

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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

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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).

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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)

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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

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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)

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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

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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

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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