Ellen England

Comparison of Sampling Methods for Monomer and Polyisocyanates of 1,6-Hexamethylene Diisocyanate During Spray Finishing Operations

A comparison study of isocyanate sampling methods for 1,6-hexamethylene diisocyanate (HDI) monomer and HDI-based polyisocyanates was conducted in spray painting environments. This study compared the performance of the Iso-chek sampler against existing and proposed National Institute of Occupational Safety and Health (NIOSH) and Occupational Safety and Health Administration (OSHA) monitoring methods for HDI-based isocyanates. Six methods for monitoring HDI monomer and polyisocyanate levels were compared. Fifty-eight sampling sets were collected during spray painting of aircraft and aircraft parts at four U.S. Air Force bases. Impinger and cassette samplers were mounted side-by-side on a mannequin located in paint overspray areas. For HDI monomer sampling results, there were no significant differences between NIOSH 5521, NIOSH 5522, OSHA 42, MAP (the proposed NIOSH method), and the Iso-Chek. For HDI-based polyisocyanates, NIOSH 5522, NIOSH 5521, Iso-Chek, and the Total Aerosol Mass Method (TAMM) were significantly different from one another. There was no significant difference between MAP and the NIOSH 5522 polyisocyanate sampling results. This study suggests the Iso-Chek and MAP sampling methods compare favorably with established methods for monitoring in HDI spray painting environments and the Total Aerosol Mass Method provides a reasonable upper boundary for estimating HDI polyisocyanate concentrations. The results also reemphasize aerosol sampling physics and sampler geometries must be carefully considered and appropriate samplers used when measuring exposures in spray paint environments where particulates are of the inhalable size.

Exposures to 1,6-hexamethylene diisocyanate during polyurethane spray painting in the U.S. Air Force.

1,6-Hexamethylene diisocyanate (HDI) exposures were measured during polyurethane enamel spray painting at four Air Force bases. Breathing zone samples were collected for HDI monomer and polyisocyanates (oligomers) using three sampling methods: NIOSH Method 5521, the Iso-Chek sampler, and the total aerosol mass method (TAMM). Exposures to HDI monomer are low when compared to current occupational exposure limits; the highest 8-hr time-weighted average (TWA) exposure found was 3.5 micrograms/m3, below the American Conference of Governmental Industrial Hygienists (ACGIH) threshold limit value (TLV) of 34 micrograms/m3. HDI oligomer levels were higher; mean task exposures indicated by either the Iso-Chek sampler or TAMM are above the Oregon ceiling limit of 1 mg/m3. Eight-hour TWA exposures, however, were much lower, with only one exceeding the Oregon standard of 0.5 mg/m3. Poor worker practices commonly observed during this study included: standing in downwind positions so paint overspray passed through breathing zones; spraying toward other painters; and using excessive paint spray gun air cap pressures. Workers should stand in upwind orientation relative to the aircraft being painted, causing overspray to move away from the painters breathing zone; adjust their position to prevent spraying other painters or limit paint application to one worker at a time; and use air cap pressure gauges prior to spraying to limit spray gun air cap pressures and reduce paint overspray generation rates. These improved techniques will result in reduced worker exposures to isocyanates.

A Comparison of Solid Sampler Methods for the Determination of Hexamethylene-Based Isocyanates in Spray-Painting Operations

A polyurethane foam sponge impregnated with 1-(2-methoxyphenyl) piperazine in dimethylsulfoxide was mounted in both cassette and inhalable organic monitor samplers and these were then compared with a dual-filter cassette. The samplers were used for the collection of hexamethylene diisocyanate (HDI) monomer and oligomers during actual spray-painting operations. The dual filter cassettes were positioned on a mannequin. The polyurethane foam cassette (PUF CAS) and polyurethane foam inhalable organic monitor (PUF IOM) samplers were positioned on a cart in the same maximum overspray area. Data from this pilot study suggest that there is no significant difference (P < 0.05, n = 6) in the amount of HDI monomer obtained with the PUF IOM sampler when compared with the amount obtained from the dual filter cassette. The data also suggest that the PUF IOM sampler yields a higher amount of HDI oligomer than either the dual filter cassette or the PUF CAS sampler, neither of which exhibited a significant difference (P < 0.05, n = 6) from each other.

Determination of hexamethylene diisocyanate-based isocyanates in spray-painting operationsPart 2.† Comparison of high performance liquid chromatography with capillary zone electrophoresis

A capillary zone electrophoresis (CZE) approach was developed for the determination of hexamethylene diisocyanate (HDI) monomer and HDI-based oligomers. A comparison of CZE with high performance liquid chromatography (HPLC) indicates that the CZE separation completely isolates isocyanates from excess solvent, derivatizing reagent and pigment while offering a fivefold increase in sensitivity. The CZE approach allows for the quantification of HDI monomer and oligomer within a 1 min time window under the run conditions selected. For the determination of HDI-based oligomer, provided that the relative response with respect to HDI monomer is calculated, there is no significant difference (p < 0.05, n = 10) in the isocyanate air concentration when using either HPLC or CZE. The results are significant because they indicate that CZE has advantages for the determination of both HDI-based oligomer and HDI monomer generated during spray-painting operations.