New Emerging Applications in Emissions Testing. Dr Caroline Widdowson Material Emission Specialist Markes International

Transcription

1 New Emerging Applications in Emissions Testing Dr Caroline Widdowson Material Emission Specialist Markes International

2 Established applications Construction Product Materials CPR CE Marking ISO Series ASTM D5169, D6119, D7706 US regulations Automotive industry ISO Series VDA US regulations Cleanroom materials VDI Semi-Conductors

3 Emerging Application Areas Spray Polyurethane foam Cultural heritage Space Flavour profiling

4 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

5 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

6 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

7 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: Column flow: Temperature program: Total run time: Based deactivated 5% diphenyl/95% dimethyl polysiloxane, 30 m, 0.25 mm x 0.5 µm 1.5 ml/min, constant flow 40 C (2 min), 20 C/min to 300 C (2 min) 17 minutes

8 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

9 Microchamber preparation: Sample holding time, packaging and storage studies Closed-cell SPF specimen fits tightly into the micro chamber.

10 Sample collection techniques : Sample holding time, packaging and storage studies A. standard TD sorbent tubes B. silica gel with DNPH tube for aldehyde analysis A B C. glass-fiber filter with 1- (2-pyridyl)piperazine (PP) and diethyl phthalate. C C

11 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

12 Spiking of chambers Microchambers Stainless Steel Chamber PTFE Lined Acrylic Chamber

13 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.

14 Cultural Heritage 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. Wiegner K., Farke M., Horn W., Jann O., Hahn O Schadstoffe im Museum richtig einschätzen: BEMMA Bewertung von Emissionen aus Materialien für Museumsaus stattungen. Restauratorenhandbuch 2012/2013, Callwey; ISSN ,

15 Microchamber sampling 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 Wiegner K., Farke M., Horn W., Jann O., Hahn O Schadstoffe im Museum richtig einschätzen: BEMMA Bewertung von Emissionen aus Materialien für Museumsaus stattungen. Restauratorenhandbuch 2012/2013, Callwey; ISSN ,

16 Sampling Method: Microchamber Analytical Methods: ISO /3 Formic and acetic acid/isocyanates Cultural Heritage 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/m 3, b. Σ VOCs<500 μg/m 3 with the exception of sealing materials with Σ VOCs< 2000 μg/m 3 due to significantly smaller application surface, c. Σ SVOCs< 100 μg/m 3 Assessment: If any emission value and limits exceeded, the product fails the BEMMA scheme. Wiegner K., Farke M., Horn W., Jann O., Hahn O Schadstoffe im Museum richtig einschätzen: BEMMA Bewertung von Emissionen aus Materialien für Museumsaus stattungen. Restauratorenhandbuch 2012/2013, Callwey; ISSN ,

17 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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19 VDI Suitable tool for selecting Cleanroom-suitable materials An easy-to-use calculation model gives an estimation of the expected TVOC level regarding the relevant materials. The comprehensive database enables Cleanroom planners and operators a deep insight into the VOC-emission behaviour of tested materials. Test Parameter VOCs Equilibration time range (days) 30 Chamber temperature ( C) Inlet gas flow rate range (ml/min) 100 Gas sampling time (min) 60

20 Flavour Profiling 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 Cheddar Brie Stilton

21 Analysis of the VOC profile of full-fat (extramature) Cheddar

22 Thermal Desorption conditions Flow path temperature 160 C Sorbent Tube Cold Trap Dry Purge Prepurge Primary desorption 1 Primary desorption 2 Pre-Trap Fire Purge Cold trap conditions Overall TD split Tenax TA/ Carbograph 5 TD U-T12ME-2S, Material Emissions Trap 2min, 20ml/min flow to split 1min, 20ml/min flow to split 150 C for 5 min, 50 ml/min trap flow, no split flow 300 C for 5 min, 50 ml/min trap flow, no split flow 2min, 50 ml/min trap flow, 50ml/min split flow 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) 51:1 (high split), 6:1 (low split)

23 High/Low analysis

24 High/Low analysis

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26 Metadata for sample comparisons Target Compound Chemical Cheddar Blue Cheese Emmental Comte Odour descriptor Classifier Acetic Acid Acids 4.74E E E E+08 vinegar, sour Propanoic acid Acids 1.80E E E+08 pungent, rancid, sour Propanoic acid, 2-methyl- Acids 6.91E+07 rancid butter Butanoic acid Acids 2.96E E E E+08 fecal, cheesy Hexanoic acid Acids 9.55E E E E+07 goaty, fatty Target Compound Chemical Cheddar Blue Cheese Emmental Comte Odour descriptor Classifier Isopropyl Alcohol Alcohols 5.30E E E+07 sharp musty odour Ethanol Alcohols 8.33E E E E+08 Dry/dust 2-Butanol Alcohols 4.91E E E+07 sweet, alcohol 1-Propanol Alcohols 1.10E E E+08 sweet 'candy' 1-Propanol, 2-methyl- Alcohols 6.25E+08 plastic 2-Pentanol Alcohols 7.23E+08 musty 1-Butanol Alcohols 1.67E E E E+06 sweetish, putrid 1-Butanol, 3-methyl acetate Alcohols 9.13E+07 pear 1-Butanol, 3-methyl- Alcohols 2.09E E E+08 alcohol, green 3-Buten-1-ol, 3-methyl- Alcohols 8.86E E+06 fruity 1-Pentanol Alcohols 3.07E E+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

27 Target Compound Chemical Cheddar Blue Cheese Emmental Comte Odour descriptor Classifier Methyl Acetate Esters 2.54E+07 Banana, pear Ethyl Acetate Esters 1.18E E E E+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 E+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 E+07 fruity Target Compound Chemical Cheddar Blue Cheese Emmental Comte Odour descriptor Classifier Propanal Aldehydes 3.44E E+06 fruity sweet scent Butanal Aldehydes 2.73E+06 acrid, fruity, malty Butanal, 3-methyl- Aldehydes 2.80E E+07 Green, malty Hexanal Aldehydes 9.13E E+07 rancid Heptanal Aldehydes 3.43E+06 soapy Nonanal Aldehydes 1.29E+07 green, fatty Benzaldehyde Aldehydes 1.86E E E+07 almond

28 Target Compound Chemical Cheddar Blue Cheese Emmental Comte Odour descriptor Classifier Pentane Alkanes 4.25E E E+07 mild gasoline type odour Hexane Alkanes 7.85E E E E+06 gasoline type odour Heptane Alkanes 1.66E E E E+06 mild gasoline type odour Benzene Alkanes 1.15E E E E+07 sweet aromatic Toluene Alkanes 5.89E E E E+07 sweet pungent Target Compound Chemical Cheddar Blue Cheese Emmental Comte Odour descriptor Classifier Acetone Ketones 6.60E E E E+08 Hay, wood 2-Butanone Ketones 2.74E E E E+07 Butterscotch 2,3-Butanedione (Diacetyl) Ketones 1.49E E E E+08 buttery, caramel, sweet 2-Pentanone Ketones 3.98E E E E+07 sweet, fruity 2-Heptanone Ketones 2.27E E E E+06 blue cheese, green 2-Octanone Ketones 1.39E+07 floral, fruity, sharp, cheesy 2-Butanone, 3-hydroxy- (Acetoin) Ketones 5.50E E E E+09 sour milk 2-Nonanone Ketones 3.50E E+07 malty, fruity Target Compound Chemical Cheddar Blue Cheese Emmental Comte Odour descriptor Classifier Carbon disulfide Sulphur 1.52E E E E+06 sweet 'ether-like' Dimethyl sulfide Sulphur 3.59E E E E+06 cabbage-like, sulphurous Disulfide, dimethyl Sulphur 2.37E+07 Sulphurous Dimethyl trisulfide Sulphur 5.34E+06 cabbage-like, sulphurous Target Compound Chemical Cheddar Blue Cheese Emmental Comte Odour descriptor Classifier o-xylene Misc 2.33E E E E+06 Petroleum p-xylene Misc 3.01E E E E+06 Petroleum

29 Summary Construction Product Materials CPR CE Marking ISO Series ASTM D5169, D6119, D7706 US regulations Automotive industry ISO Series VDA US regulations Cleanroom materials VDI Semi-Conductors New areas Spray Polyurethane foam Cultural heritage Space Flavour profiling

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