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# An Evaluation of Airborne Methylene Diphenyl Diisocyanate (MDI)

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Forno Products, Inc. Norton, OH Conducted and Reported by: B.F. Karlovich, Manager- Industrial Hygiene Customer Services, Product Safety & 

### Regulatory Affairs
Date ofEvaluation: February4, 2010 Date ofReport: March 9, 2010 

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The testing and evaluation described in this report have been conducted as a customer service at no additional charge to the Customer. As such, any information contained in this Report has been obtained in accordance with industry standards and is, to the best ofourknowledge, true and accurate, and is based onlyupon the conditions observed at the time ofthe evaluation. The test results, recommendations and/or suggestions contained inthis Report are made only as a courtesy as part ofolll' customer service and Bayermakes no warranty, either expressed o1· implied, with respect to any such test results, recommendations and/or suggestions. Cl;:o ""OfTl 

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### TABLE OF CONTENTS PAGE

SUMMARY .............u .....................................................................................................

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### I. INTRODUCTION..............................................................................................2


### II. PROCESS OBSERVATIONS
..........................................................................2


## m. CRITERIA....................................................................uooooouoooooootoooooooooooOoooooocoo4 

### IV. SAMPLING AND ANALYTICAL TECHNIQUES
.......................................5
V. RESULTS AND DISCUSSION
........................................................................6

VI, RECOMMENDATIONSooo.oooooooooooooootoooooooooooooo•uuuuouooooooooouooooooooouooooooooooouooo7



### TABLE 1 AirborneMDI Concentrations- Personal & 

### AreaSamples
....................8SUMMARY


### On February 4, 2010 air sampling for methylene diphenyl diisocyanate (MDI) was conducted during the production ofone componentpolyurethane foam products, as well as during the test application ofboth one and two componentpolyurethane foam products at Forno Products, Inc., Norton, Ohio. Both personal and area samples were collected. Sample results are summarized in Table 1. Personal Samples Airborne MDI was detected in the two samples collected in thebreathing zone ofthe aerosol line operator. The airborne concentrations were 15 and 2.7 uglm3

, 

### with a corresponding sampling period TWA concentration of8.8 uglm3• 

### This value does not exceed theACGIH 8-hr. TLVTWA of51 uglm3

. 

### Airborne MDI was not detected at or above the analytical quantitation limit in three short-term air samples collected in the breathing zones of 1) the technical trainingrepresentative during the application ofthe E84 Class I Refillable System in the Training Lab hood, using the "I0, 10, 1 0" rule, 2) theproduct manager during the application ofatwo component 205 Disposable Kit in the Spray Lab hood, using the "1 0, 10, 1 0" rule, and 3) the product manager during the application ofone component HandiFoam in the Humidity Chamber. Therefore, the OSHA PEL-C of200 uglm3

### was not exceeded. Airborne MDI was identified at a level of89 uglm3 

### in the one short-term air sample collected in thebreathing zone ofthe product manager during the continuous application ofthe 205 Disposable Kit in the Training Lab hood. However, the OSHA PEL-C of200 uglm3

### was not exceeded. Because the employee wore an air purifYing respirator during this activity, the airborne concentration to which the employee was potentially exposed was likely Jess than the measured concentration. It

### is ofnote that the local exhaust ventilation hood was purposely not operated during this activity. Area Samples Airborne MDI was identified at 3.0 and 1.1 uglm3 

### in the two samples collected near the dispensing heads ofthe aerosol filling station. Airborne MDI was not identified at or above the analytical quantitation limit in the two area samples collected at a distance of 10 feet from spraying activities, or in the two area samples collected beginning one hour following spraying activities in the Training Lab. Recommendations based on results and observations at the time ofthe evaluation appear on Page 7.

### I. 

### INTRODUCTION At the request ofForno Products, Inc., the Bayer MaterialScience (BMS) Product Safety & Regulatory Affairs Department sampled for potential airborne MDI during themanufacture of one and two component lowpressure polyurethane foam systems, as well as the test application ofthese systems. BMS supplies Forno with Mondur MR Light, which contains approximately equal amounts ofmonomeric MDI and polymeric MDI.


### II. PROCESS OBSERVATIONS TheNorton facility blends andpackages various-sized one and two-component low pressure polyurethane foam systems. The one component systems dispense somewhat like a caulking, whereas the two-component systems are spray applied. The aerosol filling operation was evaluated during this investigation. In addition, air sampling was conducted during the test application ofsome ofForno's one and two-component low pressurepolyurethane foam systems. The aerosol line is highly automated and is located in a largeproduction area (greater than I0,000 square feet with ceilings ofapproximately 15 feet). Two lines, 1 and 2, are immediately adjacent to and run parallel with one another. For each line, a conveyor first delivers emptymetal cans· (typically 12 or 24 ounce) to the aerosol filling station, where two heads dispense MDI under low pressure into the tops oftwo cans for a period ofabout 1 to 2 seconds. Following this, the cans proceed a short distance down the line, and two additional heads dispense polyol blend into the tops ofthe cans, also for a period ofabout I to 2 seconds. Heads that dispense other additives are also present and are used for certainproducts. Following the addition ofproduct, valves are then automatically added to the tops ofthe cans. The cans thenproceed to the "Gas House" where propellant is injected. Following the Gas House, the conveyor delivers the cans to a station where collars are added (forproducts that use a gun attachment), and then to the shaker (I0 to 15 shakes per can). The cans are then submerged in a "hotbath" to increase the temperature to about 120 degrees Fahrenheit, and then proceed through a cold bath. The cans then move to the "Blower House" to be dried with fast moving

### air. The cans then proceed along to the labeler, capper, and adapter placer, before being fitted with an outer thin plastic sleeve, which is thenheated viaheat gun, and then followed up by a heat tunnel. The cans are then boxed up manually. From here, the boxes ofcans proceed to thepalletizer. Thepallet with boxes ofproductis then shrink wrapped, at which pointit is ready for shipment. On the day of the evaluation, theproducts produced included 24-ounce Window and Door, 12-ounce Straw Foam, and 12-ounceWindow and Door. Approximately cans wereproduced in total. The aerosol filling station is equipped with a canopyhood; the dimensions ofthe hood face are approximately 4 feet by4 feet. The face ofthe hood is located about 6 feet above the floor. Smoke 

### gun testingindicated that air was moving slowing into thehood. Forno has implemented a "10, 10, I0"policy where two component spray polyurethane foam systems are being demonstrated for customers, or where customers are beingtrained. The policy is reportedlyused atboththe Forno facility as well as at customerlocations. Thepolicy is as 2follows. Sprayingis permitted for no more than 10 seconds at a time; observers must be at least 10 feet awayfrom the applicator; and there is a minimum 10-minute waitingperiodbetween spraying events. Onthe day ofthe evaluation, test application ofvarious Forno products were conducted in the TrainingLab, Spray Lab, and Humidity Chamber. The Training Lab is approximately 24 feet by 19 feet by 12 feet high. Two supply air diffusers are located in the ceiling. A local exhaust ventilation hood with the dimensions ofapproximately 6 feet wide, by 3 feet deep, by 6 feet high is located in the far comer ofthe room. Two component foam kits are applied into simulated wall cavities or onto other substrates in the hood. The hood is reportedly operated during spraying; however, Forno chose to not operate the hood onthe day ofthe evaluation in order to represent worst case conditions. The room thathouses the SprayLab is approximately 45 feetby 20 feet by 18 feet high. One supply air diffuser was observed in overhead ductwork. A local exhaust ventilationhood with the dimensions ofapproximately 10 feet wideby 5 feet deep is present in the SprayLab. Similar to the hood inthe Training Lab, two component foam kits are applied into simulated wall cavities or onto other substrates in the hood. Thehood is reportedly operated during spraying; however, similarto the Training Lab hood, Forno chose to not operate the hood onthe day ofthe evaluation in order to represent worst case conditions. The Humidity Chamber is approximately 8 feet by 16 feetby 8 feet high. One supply air diffuser was observedin the ceiling. Theroom is reportedly kept at a relative humidity ofapproximately 50 percent for the purpose oftesting single-component foam products. Three employees weremonitored during this investigation, an aerosol line operator, a technical training representative, and a productmanager. The aerosol line operator worked atboth Lines 1 and 2. His primary tasks were to restock the conveyor lines with empty cans and valves, and to weigh the aerosol cans at different stages ofthe process for quality control purposes. He wore boots, pants, a short sleeved work shirt, safety glasses with side shields, disposable latex gloves, and earplugs. The technical training representative demonstrated the "10, 10, 10" rule in the hood ofthe Training Lab. He applied a two component "E84 Class I Refillable System" to a cardboardlined, simulated wall assembly (2"by4" framing) in the hood. The E84 Class I Refillable System was equipped with a 1 0-inch HandiGun with a disvosabJe tip and a Magnum hose heater (80 degrees F). Dynamic pressure at the 

### gun was reported to be.approximately75 pounds per square inch. The product was applied for 10 seconds, and then applied for another 10 seconds 10 minutes later. The total length ofthe activitywas 15 minutes. When not spraying, the employee stood at approximatelythe same location as when spraying. As previously stated, the ventilation hood was not operated. The door to the Training Lab was closed during the sampling period. The employee woreboots,jeans, a short sleeved shirt, safety glasses with side shields, Duraskin disposable nitrile gloves, and disposable plastic sleeves to cover the forearms.

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### The product manager conducted three separate tasks. The first task was the application ofatwo component "205 Disposable Kit" into cardboard boxes on the floor inthe hood in the Training Lab. One entire kit was dispensed over a period ofapproximately 15 minutes. The ventilation hood was not operated, and the door to the room was closed. The product manager wore shoes, pants, fabric lab coat, halfmask air purifying respirator with organic vapor cartridges, disposable nitrile gloves, and safety glasses with side shields during this activity. The product manager's second task was to apply a one component "HandiFoam" with attached straw dispenser to plastic covered cardboard sheets in the Humidity Chamber. The cardboard sheets were located on a desktop about 3 feet above the floor. The foam was nearly continuously applied in abead width ofabout 3/8-inch. Approximately one and one halfcans were used over a IS-minute period. The door was closed during this activity. The employee wore shoes, pants, fabric lab coat, High Five disposable latex gloves, and safety glasses with side shields during this activity. The product manager's third task was to demonstrate the "1 0, I0, I0" rule in the hood ofthe Spray Lab. She applied the two component "205 Disposable Kit" to apiece ofcardboard on the back wall ofthe hood at aheight ofabout 3 to 4 feet above the floor. The product was applied for I0 seconds, and then applied for another 10 seconds 1 0 minutes later. The total length ofthe activity was IS minutes. When not spraying, she stood at approximately the same location as during spraying. As previously stated, the ventilation hood was not operated. She wore shoes, pants, fabric lab coat, Duraskin disposable latex gloves, and safety glasses with side shields during this activity.
III. CRITERIA MDI The American Conference ofGovernmental Industrial Hygienists (ACGIH) has adopted a Threshold Limit Value- Time Weighted Average (TLV-1WA) for 4,4'-methylene bisphenyl isocyanate (MDI) of0.005 parts per million (ppm) (i.e., 5parts perbillion, ppb) or 51 micrograms per cubic meter ofair (ug!m'). This is an airborne concentration for a normalS-hour workday and a40-hour workweek and represents conditions under which nearly all workers can be exposed without adverse effect. In 

### addition, the federal Occupational Safety illld Health Administration (OSHA) has established a Permissible Exposure Limit (PEL) for 4,4'-MDI of 0.02 ppm or 200 ug/m3 

### as a Ceiling (C) limit. The Ceiling limit is a concentration that should not be exceeded during any part ofthe day. At present, neither an ACGIH TLV nor a federal OSHA PEL has been established for2,4'-MDI or polymeric MDL However, Bayer MaterialScience recommends that the exposure limits for 4,4'-MDI be used for the 2,4'- MDI isomer. The United States Environmental Protection Agency (EPA) has established a Reference Concentration (RfC) for 4,4'-MDI of0.06 ppb (0.6 ug/m3). 

### The RfC is for chronic inhalation 4exposure, and represents the airborne exposure to the human population (including sensitive subgroups) thatis likelyto be without an appreciablerisk ofdeleterious effects during a lifetime.


### IV. SAMPLINGAND ANALYTICAL TECHNIQUES Where spraying activities were conducted, samples ofairborne MDIwere collected using glass impingers containing 15 milliliters ofa solution oftoluene and 1-(2-pyridyl)piperazine, backed upbycoated 13mm glass fiber filters mounted in Swinnex holders, and connected to A.P. Buck Basic 5 air samplingpumps. The impinger/filter sampling trains were either attached to the workers' lapels (i.e., personal samples) orplaced inthe surrounding work area (i.e., area samples). All pumps were calibrated before sample collection to a sampling rate of approximately 1Lpm using a Bios DryCal® DC-Lite Primary Air Flow Meter. The samplingrate was reconfirmed after the sampling event, withthe average valueused inthe sample volume calculation. Prior to mounting the filter to the Swinnex holder, each filter was coated with 2 mg of 1-(2-pyridyl)piperazine and diethyl phthalate. Immediately upon completion ofsampling, the impinger solution was transferred to samplebottles, and the filters wereremoved from the Swinnex holders and desorbed in 2 ml ofacetonitrile/dimethyl sulfoxide (90:I0 v/v) solution. When airborne MDI is drawn through the impinger solution (and treated filter) it is converted to a stableurea derivative, which is quantitatively analyzed byHPLC using BayerMaterialScience Method 1.20.0. The 13mm filters were analyzed according to Bayer MaterialScienceMethod 1.7.7. Where spraying activities were not conducted, samples ofairborne MDIwere collected using 1- (2-pyridyl)piperazine and diethyl phthalate-coated 13mm glass fiber filters mounted in Swinnex holders, and connected to SKC Airchek 52 air sampling pumps. The filters were either attached to the workers' lapels (i.e., personal samples) orplaced inthe surrounding work area (i.e., area samples). The 13mmfilters were analyzed according to Bayer MaterialScience Method 1.7.7. All samples collected were analyzed atthe BayerMaterialScience Industrial Hygiene Laboratory, which is accredited bythe AIHA. · Airflow Airmovementinthe aerosol filling station area was assessed with a Te!Tru1M Borozin A.C. Gun (i.e., smoke gun) that uses 100% Air Test GradeZinc Stearate as thetesting powder.

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### V. RESULTS AND DISCUSSION The analytical results are presented in Table 1. Notethat the reported MDI values for the samples collected during/following spraying activities represent MDI found in the impinger solution only, as MDI was not identified in any ofthe back-up l3mm filters. 

### Personal Samples Airborne MDI was detected in the two samples collected in the breathing zone ofthe aerosol line operator. The airborne concentrations were 15 and 2.7 ug/m3
, with a corresponding TWA concentration of8.8 ug/m3

. This value does not exceed the ACGIH 8-hr TLV-TWA of51 uglm3 Airborne MDI was not detected at or above the analytical quantitation limit in the one short-teffil sample collected in the breathing zone ofthe technical training representative during the application ofthe E84 Class I Refillable System in the Training Lab hood, using the "10, 10, 10" rule. Therefore, the OSHAPEL-C of200 ug/m3 was not exceeded. Airborne MDI was not detected at or above the analytical quantitation limitintheone short-temJ sample collected in the breathing zone ofthe product manager during the application ofthe two component 205 Disposable Kit in the Spray Lab hood, using the "10, 10, 10"rule. Similarly, airborne MDIwas also not detected at or above the analytical quantitation limit in the short-temJ sample collected during the application ofthe one component HandiFoam in the Humidity Chamber. Therefore, the OSHAPEL-C of200 ug/m3was not exceeded for either ofthese samples. Airborne MDIwas identified at a level of89 ug/m3 inthe one short-tenn sample collected in the breathing zone ofthe product manager during the application ofthe two component 205 Disposable Kitin the Training Lab hood. However, the OSHAPEL-C of200 ug/m3was not exceeded. Becausethe employee wore a halfmask air purifYingrespirator during this activity, the airborne concentration to which the employee was potentially exposed was likely less than the measured concentration. 

### Area Samples AirborneMDI was identified at 3.0 and 1.1 ug/m 3 in the two samples collected near the dispensing heads ofthe aerosol filling station. Airborne 

### MDI was not identified at or above the analytical quantitation limit inthe two area samples collected at a distance of 10feet from spraying activities, one for the E84 Class I Refillable System, and one for the 205 Disposable Kit. Airborne MDI was also not identified in the two area samples collected beginning one hour following continuous 205 Disposable Kit spraying activities in the Training Lab.

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### TABLE! AIRBORNE METHYLENE DIPHENYL DIISOCYANATE (MDI) CONCENTRATIONS Personal & 

### Area Samples

- Forno Products, Inc. Norton, Ohio- February4, 2010 Sample Name/ Sampling Sample 2,4'-MDI 4,4'-MDI Total MDI TWA' Number Job Description/Location Period Volume (ugim3) (ug/ru3) (ugim3 ) (ugim3) (liters) PERSONAL SAMPLES LONG TERM 006-1 I Aaron Runyon, Aerosol Line Operator I 7:04-11:08 I 251.3 I 1.5I I 13.1 

### J 15 I 8.8 006-2 I I Il:08-15:03 I 242.I I ND' I 2.73 I 2.7 

### I PERSONAL SAMPLES- SHORT TERM 308-1 Derrick**Hyde~** 8:I8-8:33 15.7 ND ND ND


### -- Technical Training Representative, Applies E84 Class IRefillable System inTrainingLabHood{HIO, 10 10") 308-2 Sandy GumpJ, Product Manager, 8:50-9:05 15.3 I7.0 71.9 89 30 Applies 205Disposable Kit in Training Lab Hood 308-4 Sandy Gump, Product Manager, I0:41-10:56 15.5 ND ND ND Applies 205 Disposable Kit in Spray Lab Hood ("10, 10, 10") 442-1 Sandy Gump, Product Manager, 9:15-9:30 15.4 ND ND ND Applies One ComponentHandiFoam in Humidity C'hamber AREA SAMPLES 900-1 Aerosol Filling Station, Between Lines 7:00-11:09 264.7 0.60 2.46 3.0 

# -- 900-2 1 and 2, immediately upline of 11:09-15:03 248.7 0.40 0.68 l.l


### -- dispensing heads, about 5 feet above floor 531-1 On cart, I 0 feet from Training Lab 8:18-8:33 15.3 ND ND ND 

## -- hood> 3 feet above floor, during E84 Class JRefillable System application ("10, 10, 10; 1) 308-3 On cart
.. 10 feet fi·om Training Lab 10:05-10:20 15.8 ND ND ND 

## -- hood, 3feet above floor, one hour following end of IS-minute application of205Disposable Kit 531-2 On cart, 10 feet from Training Lab 10:05-13:05 178.2 ND ND ND 

# -- hood, 3feet above floor, started at one (<0.56 (<0.56 hourfollowing end of**lS~minute** ug/m') uglm3) application of205DisposableKit 309-1 On desk top, 10 feet from Spray Lab 10:41-10:56 15.5 ND ND ND 

# -- hood, 3 feet above floor, during application of205Disposable Kit (;'10, 10, 10") 1. Time Weighted Average (TWA) based on the combined samples. 2. ND (Non-detectable)- concentration was less than the analytical Limit ofQuantitation (LOQ) ofO.! !lg/sample. Forsarnples that were 15 minutes in duration, the corresponding total MDI concentration is ofapproximately <13 ug/m3

. 3. Employee wore ahalfmask air purifying respirator during this activity. Therefore, the airborne concentration to which the employee was potentially exposed was likely less than the concentration shown.

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