new emerging applications in emissions testingsample holding time, packaging and storage studies...

New Emerging Applications in Emissions Testing

Dr Caroline Widdowson Material Emission Specialist Markes International

Established applications • Construction Product Materials

– CPR – CE Marking – ISO 16000 Series – ASTM D5169, D6119, D7706 – US regulations

• Automotive industry – ISO 12219 Series – VDA – US regulations

• Cleanroom materials – VDI 2083-17

• Semi-Conductors

Emerging Application Areas

• Spray Polyurethane foam

• Cultural heritage

• Space

• Flavour profiling

Work Item 30960: Standard practice for determination of volatile organic

compounds, diisocyanates, oligomeric isocyanates, and amine catalysts

emitted from spray polyurethane foam insulation (SPFI) products designed

for on-site application in buildings

Standard Practice for Spraying, Sampling, Packaging, and Test

Specimen Preparation of Spray Polyurethane Foam (SPF) Insulation for

Testing of Emissions Using Environmental Chambers

Summary of work carried out so far

•Deciding/Agreeing on a generic formulation to validate method

•Evaluation of Thermal Desorption GC/MS for measuring potential SPF emissions

•Determining Micro-chamber parameters and Sample preparation

•SPF Sample holding time, packaging and storage

studies

•Evaluation of wall effects of SVOCs in test chambers

Generic foam targets

Target Compound Acronym Description

HFC-245fa - Blowing Agent

HFC-134a - Blowing Agent

Tris-(1-chloro-2-propyl) phosphate TCPP Flame Retardant

Bis (2-Dimethylaminoethyl) ether BDMAEE Catalyst

Tetramethyliminobispropylamine TMIBPA Catalyst

N,N,N-Trimethylaminoethylethanolamine TMAEEA Catalyst

Pentamethyldiethylene triamine PMDTA Catalyst

Bis (dimethylaminopropyl) methylamine DAPA Catalyst

Methylene diphenyl diisocyanate MDI Isocyanate

Evaluation of TD-GC/MS Method Instrumentation

TD-100 &

Flow path temperature: 160 °C

Sorbent Tube: Tenax TA and Carbopack X sorbent

tubes (Stainless Steel)

Cold Trap: U-T12ME-2S, Materials Emissions

Trap with Tenax and Carbograph

5TD sorbent

Agilent 7890 GC and 5975 MSD

Column: Based deactivated 5% diphenyl/95%

dimethyl polysiloxane, 30 m, 0.25 mm

x 0.5 µm

Column flow: 1.5 ml/min, constant flow

Temperature program: 40 °C (2 min),

20 °C/min to

300 °C (2 min)

Total run time: 17 minutes

Sample preparation: Sample holding time, packaging and storage studies

Sample substrate consists of cardboard

sheets wrapped with clean aluminum foil.

Five replicate closed-cell SPF

samples are shown in the spray

booth.

Samples stored in polyethylene terephthalate

(PET) layered bags during holding time study

Closed-cell SPF specimen fits tightly into the micro chamber.

Microchamber preparation: Sample holding time, packaging and storage

studies

A B

C C

A. standard TD sorbent

tubes

B. silica gel with DNPH

tube for aldehyde

analysis

C. glass-fiber filter with 1-

(2-pyridyl)piperazine

(PP) and diethyl

phthalate.

Sample collection techniques : Sample holding time, packaging and storage

studies

Determining Wall effects • There is a concern that semi-volatile organic compounds

may adhere to the walls of the environmental test chambers, which could significantly bias the emission results.

• The SVOA compounds of interest were spiked into micro chambers and small-scale stainless steel and PTFE lined chambers to evaluate recoveries.

SVOCs – MDI – Selected amine catalysts – Flame retardant

Microchambers

PTFE Lined Acrylic Chamber Stainless Steel Chamber

Spiking of chambers

MDI:

Spike recoveries were not consistent and a significant

percentage of the spiked MDI adhered to the chamber walls,

regardless of the material and size of the test chamber.

Amine Catalysts: RT,

Microchamber (stainless steal) 81 to 99% recovery

PTFE 10-45% recovery

Stainless steel 4-22% recovery

Flame retardants:

RT, 22% RH (except MCTE) Nitrogen gas, minimal recovery

from any chamber.

When the MCTE was increased to ~35%RH excellent

recovery was observed.

New methods are being developed for

assessment of emissions from materials used in

museums.

What is BEMMA?

Assessment of Emissions from Materials for

Museum Equipment/Bewertung von

Emissionen aus Materialien für

Museumsausstattungen

A new assessment scheme for museum display

case construction materials comprises various

analytical methods.

Cultural Heritage

Wiegner K., Farke M., Horn W., Jann O., Hahn O. 2012 Schadstoffe im Museum richtig einschätzen: BEMMA Bewertung von Emissionen aus Materialien für Museumsausstattungen. Restauratorenhandbuch 2012/2013, Callwey; ISSN 978-3-7667-1962-1, 127-131.


Sampling VOC (SVOC on to Tenax

tubes analysis by TD-GC/MD

DNPH and other derivitised luer

cartridges for formic and acetic acid,

aldehydes and ketones Derivatisation

at 80 °C for 8 h,

LC-MS, HPLC-DAD

Microchamber

sampling

Sampling Method:

• Microchamber

Analytical Methods:

• ISO 16000-6/3

• Formic and acetic acid/Isocyanates

Criteria (emission values):

1. Substances such as formic acid, acetic acid, formaldehyde must not be

detectable

2. Sum emission values:

a. Σ VVOCs< 100 μg/m3,

b. Σ VOCs<500 μg/m3

with the exception of sealing materials with Σ VOCs< 2000 μg/m3 due

to significantly smaller application surface,

c. Σ SVOCs< 100 μg/m3

Assessment:

If any emission value and limits exceeded, the product fails the BEMMA scheme.

Cultural Heritage


Cleanroom & Space

• Cleanliness of materials and the environments used in the production of

spacecraft has become paramount to obtaining reliable data from missions.

• Determining the source of contaminants from materials and the effect of

the manufacturing environment, as well as determining reliable packaging

and storage techniques can be undertaken using novel technologies.

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VDI2083-17 Suitable tool for selecting

Cleanroom-suitable materials

Test Parameter VOCs

Equilibration time range (days) 30

Chamber temperature (°C) 25-90

Inlet gas flow rate range

(ml/min) 100

Gas sampling time (min) 60

• An easy-to-use calculation model gives an estimation of the expected TVOC

level regarding the relevant materials.

• The comprehensive database www.ipa-csm.com enables Cleanroom

planners and operators a deep insight into the VOC-emission behaviour of

tested materials.

Flavour Profiling

Cheddar Brie Stilton

Micro-Chamber/Thermal Extractor

(6-chamber model, max. 120°C):

Sample: 5 g cheese, grated

Chamber temp: 40°C

Chamber flow: 50 mL/min dry nitrogen

Equilibration time: 20 min

Sampling time: 20 min

Analysis of the VOC profile of full-fat (extra-

mature) Cheddar

Flow path temperature 160°C

Sorbent Tube Tenax TA/ Carbograph 5 TD

Cold Trap U-T12ME-2S, Material Emissions Trap

Dry Purge 2min, 20ml/min flow to split

Prepurge 1min, 20ml/min flow to split

Primary desorption 1 150°C for 5 min, 50 ml/min trap flow, no split flow

Primary desorption 2 300°C for 5 min, 50 ml/min trap flow, no split flow

Pre-Trap Fire Purge 2min, 50 ml/min trap flow, 50ml/min split flow

Cold trap conditions Trap low: 30°C, trap high: 300°C, heating rate: 24degC/s, hold time:

5.0min, split flow 50ml/min (high split), 5ml/min (low split)

Overall TD split 51:1 (high split), 6:1 (low split)

Thermal Desorption

conditions

High/Low analysis

Metadata for sample comparisons Target Compound Chemical

Classifier Cheddar Blue Cheese Emmental Comte Odour descriptor

Acetic Acid Acids 4.74E+08 5.15E+08 1.04E+09 3.53E+08 vinegar, sour Propanoic acid Acids 1.80E+07 1.64E+09 1.67E+08 pungent, rancid, sour Propanoic acid, 2-methyl- Acids 6.91E+07 rancid butter Butanoic acid Acids 2.96E+08 2.81E+09 7.45E+08 1.16E+08 fecal, cheesy Hexanoic acid Acids 9.55E+07 1.21E+09 2.18E+08 4.86E+07 goaty, fatty

Target Compound Chemical Classifier

Cheddar Blue Cheese Emmental Comte Odour descriptor

Isopropyl Alcohol Alcohols 5.30E+07 1.06E+09 8.23E+07 sharp musty odour Ethanol Alcohols 8.33E+07 1.59E+08 8.71E+06 1.00E+08 Dry/dust 2-Butanol Alcohols 4.91E+08 5.60E+07 1.29E+07 sweet, alcohol 1-Propanol Alcohols 1.10E+08 1.88E+07 1.52E+08 sweet 'candy' 1-Propanol, 2-methyl- Alcohols 6.25E+08 plastic 2-Pentanol Alcohols 7.23E+08 musty 1-Butanol Alcohols 1.67E+07 1.38E+08 2.75E+08 8.19E+06 sweetish, putrid 1-Butanol, 3-methyl acetate Alcohols 9.13E+07 pear 1-Butanol, 3-methyl- Alcohols 2.09E+07 2.30E+09 1.89E+08 alcohol, green 3-Buten-1-ol, 3-methyl- Alcohols 8.86E+06 6.85E+06 fruity 1-Pentanol Alcohols 3.07E+06 1.04E+07 fruity balsamic 2-Heptanol Alcohols 5.86E+08 mild alcohol odour 2-Buten-1-ol, 3-methyl- Alcohols 5.01E+06 cheesy fruity green 3-Pentanol, 2-methyl- Alcohols 6.54E+07 green type odour 1-Hexanol Alcohols 2.18E+07 green 2-Butanol Alcohols 3.47E+07 sweet alcohol 2-Octanol Alcohols 8.37E+06 pungent sweet odour



Methyl Acetate Esters 2.54E+07 Banana, pear Ethyl Acetate Esters 1.18E+07 3.76E+07 1.20E+08 6.45E+06 pleasant, fruity Acetic acid, 1-methylethyl ester Esters 4.23E+06 fruity pungent odour Propanoic acid, ethyl ester Esters 4.19E+06 fruity, pineapple Methyl Butanoate2.61E+08fruity Esters Acetic acid, 2-methylpropyl ester Esters 9.01E+06 fruity, floral Butanoic acid, ethyl ester Esters 2.03E+07 3.13E+08 fruity 'bubble-gum' Acetic acid, butyl ester Esters 3.91E+06 sweet banana, apple Butanoic acid, 2-methylpropyl ester Esters 1.44E+08 fruity, pear Hexanoic acid, ethyl ester Esters 6.92E+06 fruity malty Butanoic acid, 1-methylbutyl ester Esters 1.60E+07 fruity, apple Butanoic acid, butyl ester Esters 1.54E+07 fruity Hexanoic acid, 1-methylethyl ester Esters 8.83E+06 fruity Hexanoic acid, ethyl ester Esters 2.34E+08 fruity Butanoic acid, 3-methylbutyl ester Esters 8.37E+08 fruity Hexanoic acid, 2-methylpropyl ester Esters 3.27E+07 fruity Octanoic acid, methyl ester Esters 4.64E+07 fruity Hexanoic acid, butyl ester Esters 8.70E+06 intensive fruity Octanoic acid, ethyl ester Esters 3.22E+07 floral, fruity, sweet, waxy Isopentyl hexanoate Esters 4.50E+08 fruity, apple Decanoic acid, methyl ester Esters 2.71E+07 fermented, fatty Butanoic acid, methyl ester Esters 2.53E+08 7.86E+07 fruity



Propanal Aldehydes 3.44E+06 4.01E+06 fruity sweet scent Butanal Aldehydes 2.73E+06 acrid, fruity, malty Butanal, 3-methyl- Aldehydes 2.80E+07 2.27E+07 Green, malty Hexanal Aldehydes 9.13E+07 1.63E+07 rancid Heptanal Aldehydes 3.43E+06 soapy Nonanal Aldehydes 1.29E+07 green, fatty Benzaldehyde Aldehydes 1.86E+07 3.49E+07 2.45E+07 almond



Pentane Alkanes 4.25E+07 1.14E+07 3.19E+07 mild gasoline type odour Hexane Alkanes 7.85E+06 1.27E+07 1.28E+07 5.11E+06 gasoline type odour Heptane Alkanes 1.66E+07 4.89E+06 8.46E+06 3.38E+06 mild gasoline type odour Benzene Alkanes 1.15E+07 1.13E+07 1.40E+07 1.16E+07 sweet aromatic Toluene Alkanes 5.89E+07 1.16E+07 2.82E+07 1.61E+07 sweet pungent



Acetone Ketones 6.60E+08 8.21E+08 6.80E+08 4.44E+08 Hay, wood 2-Butanone Ketones 2.74E+09 7.13E+07 8.11E+07 4.01E+07 Butterscotch 2,3-Butanedione (Diacetyl) Ketones 1.49E+07 1.87E+06 1.48E+07 2.33E+08 buttery, caramel, sweet 2-Pentanone Ketones 3.98E+07 1.21E+09 3.19E+07 1.56E+07 sweet, fruity 2-Heptanone Ketones 2.27E+07 1.04E+09 3.81E+07 7.07E+06 blue cheese, green 2-Octanone Ketones 1.39E+07 floral, fruity, sharp, cheesy 2-Butanone, 3-hydroxy- (Acetoin) Ketones 5.50E+07 1.09E+07 3.24E+08 1.48E+09 sour milk 2-Nonanone Ketones 3.50E+08 1.01E+07 malty, fruity



Carbon disulfide Sulphur 1.52E+07 1.10E+07 1.07E+07 2.68E+06 sweet 'ether-like' Dimethyl sulfide Sulphur 3.59E+06 1.83E+07 1.47E+07 2.08E+06 cabbage-like, sulphurous Disulfide, dimethyl Sulphur 2.37E+07 Sulphurous Dimethyl trisulfide Sulphur 5.34E+06 cabbage-like, sulphurous



o-xylene Misc 2.33E+06 2.43E+06 5.23E+06 4.66E+06 Petroleum p-Xylene Misc 3.01E+06 4.35E+06 6.97E+06 7.31E+06 Petroleum

Summary

• Construction Product Materials – CPR – CE Marking – ISO 16000 Series – ASTM D5169, D6119,

D7706 – US regulations

• Automotive industry – ISO 12219 Series – VDA – US regulations

• Cleanroom materials – VDI 2083-17

• Semi-Conductors

New areas • Spray Polyurethane

foam • Cultural heritage • Space • Flavour profiling

www.markes.com

[email protected]

http://www.markes.com/

new emerging applications in emissions testingsample holding time, packaging and storage studies...

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