voc reduction: a pathway to environmentally friendly...

VOC Reduction: A Pathway to Environmentally Friendly Interiors Bruce Mulholland

© Celanese

VOC Reduction:

A Pathway to Environmentally Friendly Interiors

Component Supply Chain Eliminate Paint VOCs (and Plating)

Vehicle Interior Reduce overall cabin VOCs

End of Life Recycle un-painted and un-chromed parts

Key is to eliminate the paint process

Painting/Plating Elimination

►Provides “Green” solution ‒ Eliminate VOC’s from paint process

‒ Eliminate chemical handling/disposal for painting and plating operations

‒ Ability to recycle molded-in-color resins

►Lower part cost (“Green”) versus painting or plating ‒ Typical savings: $1/part

‒ Eliminate secondary operation

‒ Eliminate warranty claims

‒ Eliminate multiple tools/materials required for trim level differentiation

Celanese Appearance Resins provide the solution for both drivers

Get “Green” Without Paint

►Historically, interior design features were painted to achieve:

‒ A desired color

‒ A desired level of UV performance

‒ A desired level of gloss (i.e., low gloss)

‒ A desired appearance effect (i.e., metallic)

VOC Reduction:





Colorability

UV Stability

Low Gloss

Metallics

Key is to eliminate the paint process

Boiling Point Classification Examples and boiling points of VOC

< 50°C Very Volatile Organic

Compounds (VVOC)

Methane (-161°C), formaldehyde (-21°C),

methylmercaptan (6°C), acetaldehyde (20°C),

dichloromethane (40°C)

50°C < 260°C Volatile Organic

Compounds (VOC)

Ethyl acetate (77°C), ethanol (78°C), benzene (80°C),

methyl ethyl ketone (80°C), toluene (110°C), xylene

(140°C)

260°C < 400°C Semi-volatile Organic

Compounds (SVOC)

Chlorpyrifos (290°C), di-n-butyl phthalate (340°C), di-

n-ethyl hexyl phthalate (390°C)

> 400°C Particulate Organic

Matter

PCB, benzopyrene

Vehicle Interior Air Quality – Low VOC Materials

►OEMs moving to reduce VOC (Volatile Organic Compounds) emissions in the cabin ‒ No internationally agreed definition of VOCs

►World Health Organization offers a classification based on boiling point:

OEM definitions generally overlap VVOC & VOC classifications


►Concern began in Europe over 15 years ago

►Driver appears to be elimination of “new car smell”

►Evident by adoption of test method VDA 270

Qualitative Smell Test


►Quantifying air quality in living spaces gained momentum in Japan over the last 10 years

►Ministry of Health, Labour and Welfare formulated indoor concentration guidelines for 13 VOCs due to “sick building syndrome”

“There have been numerous reports on residents of newly built or recently renovated houses and buildings suffering from physical disorders, due to the increased air tightness of houses and the use of building materials and interior finishing materials containing chemical substances which evaporate and contaminate the air in the rooms. While this phenomenon involves diverse symptoms, as well as the mechanisms such as the onset are largely unknown and the factors are many and complex, such symptoms are generically called sick building syndrome.”

“Sick Building Syndrome”


►Japan Automobile Manufacturers Association (JAMA) viewed passenger compartments in cars as living spaces

Voluntarily worked on defining and reducing cabin VOCs

Voluntary action began with the 2007 model year

►Other Asian countries followed including China and Korea

►US OEMs are evaluating as requirements expand to vehicles exported to those regions

►Sources of cabin VOCs include plastic parts, carpet, seat coverings, foams, adhesives, leather, wood, insulation, etc

Not just a plastics issue!


►Many compounds being targeted by OEMs

Compound Target Range (μg/m3)

Ethylbenzene < 4,000

Xylene < 900

Tetradecane < 350

Toluene < 270

Styrene < 250

Dibutylphthalate < 240

Diethylhexylphthalate < 130

Formaldehyde < 100

Acetaldehyde < 50

Each OEM or region may have own target compounds and levels

VOC Emission Limits for Total Vehicle Air Quality

Compound Japan

JAMA (μg/m3)

China

SEPA (μg/m3)

South Korea

MOCT (μg/m3)

Ethylbenzene 3,800 No Limit 1,600

Xylene 870 200 870

Tetradecane 330 No Limit No Limit

Toluene 260 200 1,000

Styrene 220 No Limit 300

p-Dichlorobenzene 240 No Limit No Limit

Benzene No Limit 110 30

Dibutylphthalate 220 No Limit No Limit

Diethylhexylphthalate 120 No Limit No Limit

Formaldehyde 100 100 250

Acetaldehyde 48 200 No Limit



►VOC testing is a three tiered process

Test Vehicle

Full vehicle testing –

addressed by JAMA

Component Testing –

responsibility of Tier 1

Material Testing


►JAMA full vehicle method Sample at ambient temperature

Doors open for 30 minutes

Heat vehicle to 40°C, hold for 4.5 hours, then sample

Open driver door for 1 minute, set A/C to 23°C, then sample

Photos courtesy of Ford Motor Company


►Component or part level testing Asian OEMs favor bag method testing

Components up to 100cm2 placed inside 10L Tedlar bag

Bag with a sampling tube is sealed with tape and placed inside an oven

Bag is heated at 65°C for 2 hours

Headspace air sampled twice:

Tenax tube (absorbent: 2,6-diphenylene oxide polymer)

» Tube analyzed using GC-MS for total VOCs

DNPH cartridge (dinitrophenyl hydrazine)

» Cartridge analyzed using HPLC for aldehydes

Blank bag must be tested to determine baseline

Typical method is JASO M902


►Component or part level testing Asian OEMs favor bag method testing


►Component or part level testing European and US OEMs favor chamber method

Components placed inside a 1m3 airtight stainless steel or glass-lined

chamber

Chamber heated at 65°C and 11% RH for 2 hours

Headspace air sampled twice:

Tenax tube (absorbent: 2,6-diphenylene oxide polymer)

» Tube analyzed using GC-MS for total VOCs

DNPH cartridge (dinitrophenyl hydrazine)

» Cartridge analyzed using HPLC for aldehydes

Typical method is VDA 276


►Material level testing VDA 277

VOC by headspace GC

VDA 278

VOC by thermal desorption

Others specific to VOC in question

VDA 275 for formaldehyde





Xylene < 900

Tetradecane < 350

Toluene < 270

Styrene < 250



Formaldehyde < 100

Acetaldehyde < 50






Xylene < 900

Tetradecane < 350

Toluene < 270

Styrene < 250



Formaldehyde < 100

Acetaldehyde < 50

Last two important for acetal

VOC Testing: Material Level

►VDA 275 to target formaldehyde

80 x 50 x 1 mm

50 ml Water

60mm

Teflon ring

1 Qt jar with PE lid and SS hook

2 POM plaques suspended over water

In oven for 3 hrs at 60oC

Water analyzed for HCHO by lutidine method

Reported as mg HCHO/kg part (ppm)

80 x 50 x 1 mm

50 ml Water

60mm

Teflon ring

VDA 275 reports formaldehyde emission in ppm

Emission range

1999

Em

issio

ns b

y V

DA

275 (

pp

m)

10

5

0

Manufacturing

process

optimized

Europe Target


New Target

Next Gen

stabilization

package

Nominally < 3 ppm

Reaction to market trends for low emission products


►Typical acetal copolymer natural grades may contain:

‒ Primary antioxidant

‒ Secondary antioxidant

‒ Acid scavenger

‒ Formaldehyde scavenger

‒ Nucleant

‒ Lubricant

►Second generation low emission stabilization package developed to balance low emission with other performance criteria


Product Examples – Acetal Copolymer

Type Example Low

VOC?

VDA 275

(ppm)

General Purpose Natural C 9021 or M90® No > 10 ppm

C 9021 XAP2TM Yes < 2 ppm

Low VOC emission natural grades can be achieved


Product Examples – Acetal Copolymer

Type Example Low

VOC?

VDA 275

(ppm)

General Purpose Natural C 9021 or M90 No > 10 ppm

C 9021 XAP2 Yes < 2 ppm

Impact Modified S 9243 No > 20 ppm

S 9364 XAP2 Yes < 5 ppm

Low wear, low noise C 9021 AW No > 20 ppm

C 9021 AW XAP2 Yes < 5 ppm

Colored grades C 9021 No > 50 ppm


UV Stabilized colors UV90Z No > 50 ppm

UV90Z XAP2 Yes < 5 ppm

UV stabilized colors meet low emission and UV requirements


Type Example Low

VOC?

VDA 275

(ppm)











Metallic, UV colors LX90Z No > 30 ppm

LX90Z XAP2 Yes < 5 ppm

Metallic UV colors meet low emission and UV requirements


Type Example Low

VOC?

VDA 275

(ppm)











Metallic, UV colors LX90Z No > 30 ppm

LX90Z XAP2 Yes < 5 ppm

Low Gloss, UV colors UV140LG No > 30 ppm

UV140LG XAP Yes < 10 ppm

VOC Reduction:





Colorability

UV Stability

Low Gloss

Metallics

Colorable, UV Stabilized, Low Emission POM provides the pathway for

Environmentally Friendly Interiors

Copyright © 2014 Celanese or its affiliates. All rights reserved.

This publication was presented on May 21, 2014 based on Celanese’s

present state of knowledge, and Celanese undertakes no obligation to

update it. Because conditions of product use are outside Celanese’s

control, Celanese makes no warranties, express or implied, and assumes

no liability in connection with any use of this information. Nothing herein is

intended as a license to operate under or a recommendation to infringe any

patents.

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