Reference

NBS

cations

- -

NAT'L INST. OF STAND & TECH

I AlllOb 2b074?

NBSIR 83-2791

An Acute Inhalation Toxicological

Evaluation of Combustion

Products From Fire Retarded and

Non-Fire Retarded Flexible

Polyurethane Foam and Polyester

U S. DEPARTMENT OF COMMERCE

National Bureau of Standards

National Engineering Laboratory

Center for Fire Research

Washington, DC 20234

November 1983

Final Report

Sponsored in part by:

The U.S. Consumer Product Safety Commission

- -1C - - Bethesda, MD 20207

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NBSIR 83-2791

AN ACUTE INHALATION TOXICOLOGICAL

EVALUATION OF COMBUSTION

PRODUCTS FROM FIRE RETARDED AND

NON-FIRE RETARDED FLEXIBLE

POLYURETHANE FOAM AND POLYESTER

Barbara C. Levin, Maya Paabo, Mary Lou Fultz,

Cheryl Bailey, Way Yin, Steven E. Harris

U S. DEPARTMENT OF COMMERCE

National Bureau of Standards

National Engineering Laboratory

Center for Fire Research

Washington, DC 20234

November 1983

Final Report

Sponsored in part by:

The U.S. Consumer Product Safety Commission

Bethesda, MD 20207

U.S. DEPARTMENT OF COMMERCE, Malcolm Baldrige, Secretary

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director

TABLE OF CONTENTS

Page

LIST OF FIGURES iv

LIST OF TABLES vii

Abstract 1

1.0 INTRODUCTION 2

2.0 MATERIALS AND METHODS 4

2.1 Materials 4

2.2 Methods 4

2.2.1 NBS Toxicity Test Method 4

2.2.2 X-ray Fluorescence 7 2.2.3 Combustion Parameters 7 2.2.4 Two-Phase Decomposition of Polyurethane Foam 7

3.0 RESULTS 7

3.1 X-ray Fluorescence .... 7 3.2 Rates of Heat Release and Ignition Times 8

3.3 Autoignition Temperatures 8

3.4 Gas Analysis and Temperature Measurements. . 8

3.4.1 Carbon Dioxide 8

3.4.2 Carbon Monoxide 9

3.4.3 Hydrogen Cyanide 10

3.5 Toxicological Results 11

3.5.1 LC-- Results 11

ou

12

3.5.2 Post-Exposure Weight Effects

3. 5. 2.1 Effect of Restrainer and Head-Only

Exposure 13

3. 5. 2.

2

Correlation of Weight Loss and Amount of

Material Decomposed 13

3. 5. 2. 3 Effect of Flaming or Non-Flaming

Decomposition 14

3. 5. 2. 4 Effect of the Fire Retardants 14

3.5. 2.

5

Weight Profiles Following Exposure to

All the Materials at One Mass Loading 15

3. 5. 2.

6

Weight Data of Individual Animals 16

3.5.3 10-Minute Tests 16

4.0 DISCUSSION 16

5.0 CONCLUSIONS 20

6.0 ACKNOWLEDGEMENT 22

7.0 REFERENCES 22

APPENDIX 57

iii
LIST OF FIGURES

Figure 1.

Figure 2.

Figure 3.

Figure 4.

Figure 5.

Figure 6.

Figure 7.

Figure 8.

Figure 9.

Schematic of NBS gas analysis system 27

Exposure chamber 28

Pyrolysis/combustion furnace 29

Animal restrainer 30

Average 30 minute carbon monoxide concentrations (ppm) as a function of the mass loading/chamber volume (mg/Z).

A. - Non-flaming results. B. - Flaming results 31

Rate of carbon monoxide generation (ppm) during

decomposition of samples 11, 12, 13, 14 and 15 at mass loading/chamber volume of 30 mg/Z. A. - Non-flaming

results. B. - Flaming results 32

Hydrogen cyanide generation from polyurethane foam

charred residues as a function of temperature. The

residues resulted from a 30 minute experiment at the

non-flaming temperature from a mass loading of 20 mg/Z.

Mean weight profiles of control animals normalized to

the initial weight on day of experiment

Mean weight profiles of animals exposed to the non- flaming decomposition products of material #11 at

various mass loadings/chamber volume (mg/Z) ....

33

34

35

Figure 10. Mean weight profiles and standard deviations of

animals exposed to 17.5 mg/Z of material #11 decomposed

in the non-flaming mode and controls who were restrained

and exposed head-only to the chamber atmosphere heated by

setting the furnace at 425°C 36

Figure 11. Profiles of the mean weights of animals exposed to

the non-flaming thermal decomposition products of

sample #12 at various mass loadings /chamber volume

(mg/£) 37

Figure 12. Mean weight profiles of animals exposed to the

non-flaming thermal decomposition products of

sample #13 at various mass loadings /chamber

volume (mg/ Z) 38

Figure 13. Mean weight profiles of animals exposed to the

non-flaming thermal decomposition products from

sample #14 at various mass loadings/chamber

volume (mg/ Z) 39

iv
Page

Figure 14. Mean weight profiles after exposure to the non- flaming decomposition of sample #15 40

Figure 15. Additional animal mean weight profiles after exposure

to the non-flaming decomposition products of material

#15 41

Figure 16. Mean weight profiles after exposure to the flaming

decomposition from samples #11 and 12 at mass loadings/

chamber volume of 20, 30 and 40 mg/5, 42

Figure 17. Mean weight profiles of animals exposed to either the

flaming or non-flaming decomposition products from

sample #13 at mass loadings /chamber volume of 20, 30

and 40 mg/5, 43

Figure 18. Mean weights and standard deviations of animals

exposed to 40 mg/5, of material #13 decomposed in

the flaming and non-flaming modes 44

Figure 19. Mean weight profiles of animals exposed to either

the flaming or non-flaming decomposition products

from sample #14 at mass loadings /chamber volume of

20 and 30 mg/ 5: 45

Figure 20. Profiles of mean animal weights after exposure to the

flaming decomposition products of material #15 46

Figure 21. Mean weights of animals after exposure to either

the flaming or non-flaming decomposition products

from sample #11 at 20 mg/5, (mass loading/ chamber

volume) 47

Figure 22. Mean weights of animals exposed to either the

flaming or non-flaming decomposition products

of sample #12 at different mass loadings /chamber

volume (mg/5,) 48

Figure 23. Mean animal weights after exposure to the flaming

and non-flaming combustion products from material

#14 49

Figure 24. Profiles of mean animal weights after exposure to the

non-flaming thermal decomposition products from

samples #11 and 12 at mass loadings /chamber volume

of 20 and 30 mg/5, 50

Figure 25. Mean weight profiles and standard deviations of

animals exposed to 20 mg/5, of materials #11 and 12

decomposed in the non-flaming mode 51

v
Figure 26. Profiles of mean animal weights after exposure to

the non-flaming thermal decomposition products from

samples #13 and 14 at mass loadings /chamber volume of

20, 30 and 40 mg/2,

Figure 27. Means and standard deviations of the animal weights

after exposure to 40 mg/2, of materials #13 and 14

decomposed in the non-flaming mode

Figure 28. Profiles of mean animal weights after exposure to

the flaming decomposition of samples #13 and 14 at mass loadings /chamber volumes of 20, 30 and

40 mg/2,

Figure 29. Comparison of mean weights of animals after exposure

to non-flaming thermal decomposition products from

samples #11, 12, 13, 14 and 15 at a mass loading/

chamber volume of 30 mg/2,

Figure 30. Weight loss in individual animals exposed to nonflaming decomposition products from sample #11 at

a mass loading/ chamber volume of 20 mg/2,

52

53

54

55

56

vi
LIST OF TABLES

Page

Table 1. Ignition Times and Rate of Heat Release 25

Table 2. Toxicological and Gas Results from NBS Toxicity

Test Method 26

vii

An Acute Inhalation Toxicological Evaluation of

Combustion Products from Fire Retarded and Non-Fire

Retarded Flexible Polyurethane Foam and Polyester

B. C. Levin, M. Paabo, *M.L. Fultz

C. Bailey, **W. Yin, S.E. Harris

Abstract

The acute inhalation toxicity of the combustion products from selected

upholstered furniture filling materials with and without fire retardants

was evaluated by the toxicity test method developed by the National

Bureau of Standards. The fire materials that were evaluated consisted

of two different formulations of flexible polyurethane foam (each

formulation was supplied in both a fire retarded and non-fire retarded

form) and a polyester fiberfill (not fire retarded). Atmospheric

concentrations of carbon monoxide, carbon dioxide, oxygen, and hydrogen

cyanide in the exposure chamber, were monitored throughout the thermal

decomposition of the materials. In addition, time-to-ignition, rate of

heat release, hydrogen cyanide generation via a two phase decomposition

procedure and x-ray fluorescence measurements were performed. The LC^

(30 minute and 14 day) values did not distinguish any of the materials

as being significantly more toxic than the others. In the worst case,

one of the fire retarded polyurethane foams was only a factor of two

more toxic than its untreated counterpart. Only the fire retarded foams

and the polyester caused deaths of the Fischer 344 rats during the 30

minute exposures. Extensive weight loss and post-exposure deaths

occurred after exposure to the combustion products from all the materials.

Animal deaths during or following exposure to the polyurethane cannot be

attributed to carbon monoxide or hydrogen cyanide alone. Deaths during

exposure to the polyester combustion products appear to be more directly

related to the concentrations of carbon monoxide.

*Dr. Mary Lou Fultz, Forensic Chemist, Bureau of Alcohol, Tobacco and

Firearms, 1401 Research Blvd. , Rockville, MD 20850

**Mr. Way Yin, Columbia University Medical School, New York, NY 10032

1
An Acute Inhalation Toxicological Evaluation of

Combustion Products from Fire Retarded and Non-Fire

Retarded Flexible Polyurethane Foam and Polyester

1 . 0 INTRODUCTION

The largest number of U.S. fire deaths occur in one and two family

residences [1]^. The most frequent cause of residential fires is heating

and cooking, while the major number of fire deaths and injuries stem

from the cigarette ignition of upholstered furniture and bedding [1],

This information has led to much interest in producing fire resistant

and thermally stable materials for upholstered furniture.

Most of the work in the fire retardant field has been directed toward

meeting requirements in flammability regulations and voluntary standards.

In 1974, however, the potential toxicological effects of combustion

products from materials containing fire retardants were dramatically

pointed out by the work of Petajan et al. [2]. Their study showed that

the combustion products from a trimethylolpropane-based rigid urethane

foam containing a reactive phosphate fire retardant caused grand mal

seizures and death in rats. The presence of an obscure toxicant,

4-ethyl-l-phospha-2, 6, 7-trioxabicyclo [2.2.2] octane-l-oxide, was found

to be responsible for the deaths in the above study. As this toxicant,

under ordinary circumstances, would not have been detected by routine

chemical analysis, the need for a biological test system was identified.

In addition, toxicity studies on the combustion products of materials

containing fire retardants was shown to be necessary.

Herpol has reported that four fire retardant treated materials were more

toxic than their untreated counterparts [3], On the other hand, Hilado

showed that the toxicity was reduced in the fire retarded materials that

he tested [4]. Other studies have found that the presence of fire

"''Numbers in brackets refer to the literature references listed at the

end of this report.

2
retardants do not significantly increase the toxicity or toxic combustion

products (e.g., hydrogen cyanide) from materials [5,6,7,8,9,10], These

differing results show that the polymer formulation and the type of fire

retardant will influence the toxicity of materials.

The present study was designed to assess the acute inhalation toxicity

of selected upholstered furniture filling materials with and without

fire retardants using the National Bureau of Standards (NBS) toxicity

test method [11], However, it should be pointed out that it is very

difficult to judge the fire safety of a material by the results of only

a toxicity test. The NBS toxicity test, like other small-scale laboratory

tests, is conducted under specified laboratory conditions*. It was designed to assess the relative intrinsic toxicity of materials under

these specified conditions and not to measure the overall toxic hazard

which might occur in a real fire situation. Some of the parameters

needed to evaluate the toxic hazard to which a material may contribute

in a real fire situation include: the quantity of material present, its

configuration, the proximity of other combustibles, the volume of the

compartments to which the combustion products may spread, the ventilation

conditions, the ignition and combustion properties of the material (s)

present, the presence of ignition sources, the presence of fire protection

systems, and the building occupancy.

In this study, in addition to the NBS toxicity test method data specified

by the contract with the U.S. Consumer Product Safety Commission (CPSC)

,

other fire performance criteria such as time-to-ignition, rate of heat

release, hydrogen cyanide generation under the conditions of the NBS

toxicity test method and via a two phase decomposition procedure were

collected and evaluated. Also, x-ray fluorescence measurements were

performed on all the materials.

*Certain commercial equipment, instruments, or materials are identified

in this paper in order to adequately specify the experimental procedure.

In no case does such identification imply recommendation or endorsement

by the National Bureau of Standards, nor does it imply that the equipment or material identified is necessarily the best available for the

purpose.

3
2.0

MATERIALS AND METHODS

2.1 Materials

The five materials evaluated in this study were supplied by CPSC,

Washington, DC 20207 and identified as FPU #11, 12, 13, 14 and PE #15.

They consisted of two different formulations of flexible polyurethane

foam (hereby specified as A and B) and a polyester fiberfill. Information provided by CPSC indicated that FPU #11 and 12 were formulation A

and FPU #13 and 14 were formulation B. One sample of each formulation

contained a fire retardant. The polyester fiberfill was not fire

retarded. Prior to testing, NBS was not informed which samples were

fire retarded.

2.2 Methods

2.2.1 NBS Toxicity Test Method

The acute inhalation toxicity of the combustion products was assessed by

the NBS toxicity test method [11]. Briefly, the test method consists of

three major components: (1) a combustion system, (2) a chemical analysis

system, and (3) an animal exposure system (Fig. 1). The combustion

system is a closed design in which all the combustion products are generated in a furnace located directly below the 200 liter rectangular

exposure chamber (Fig. 2) and are kept within the chamber except for the

volume which is transferred for chemical analysis and subsequently

returned. The cup furnace is similar to that designed by Potts and

Lederer (Fig. 3) [12]. A material is thermally degraded at a furnace

temperature 25°C above (flaming mode) or 25°C below (nonflaming mode)

its predetermined autoignition temperature. In an actual flaming exposure,

ethanol and/or an electric spark was used to ensure immediate flaming.

Before experiments, all test materials were conditioned for at least 48

hours at 40-50 percent relative humidity and a temperature of 22-24°C.

One piece samples were tested; larger pieces were rolled and bound with

wire.

4
Carbon monoxide (CO) and carbon dioxide (CO^) were measured continuously

by non-dispersive infrared spectroscopy. Oxygen (0^) concentrations

were measured continuously by a galvanic cell. The CO, CO

2

, and 0^ data

were recorded by an on-line computer every 15 seconds as were the

temperature measurements in the quartz beaker of the combustion system

and at animal exposure positions #1, 3, and 6. The hydrogen cyanide

(HCN) generated from the polyurethane foam samples was analyzed approximately every three minutes with a gas chromatograph equipped with a thermionic detector [13].

The animals used for these experiments were Fischer 344 male rats

weighing 200-300 grams. They were obtained from the Harlan SpragueDawley Company (Walkersville, MD) and were allowed to acclimate to our laboratory conditions for at least 10 days prior to experimentation.

Animal care and maintenance were performed in accordance with the

procedures outlined in the National Institutes of Health's "Guide for

the Care and Use of Laboratory Animals" [14]. Each rat was housed

individually in suspended stainless steel cages and provided with food

and water ad libitum. Twelve hours of fluorescent lighting per day were

provided using an automatic timer. All animals were weighed daily from

the day of arrival until the end of the 14 day post-exposure period.

Animals that were still losing weight on day 14 were weighed daily until

they died or recovered as indicated by three days of successive weight

gain. Control animals from the same batch were weighed daily also.

Animals designated for blood analysis of carboxyhemoglobin (COHb)

underwent cannulation 24 hours before experiments. This procedure

involves the surgical insertion of a cannula into the animal's femoral

artery [15] thereby allowing blood samples to be taken during the

exposure. The blood levels of COHb are indicative of the amount of

carbon monoxide inhaled by the animals.

Six animals were exposed in each experiment. Each animal was placed in

a restrainer (Fig. 4) which was then inserted into one of the six port5
holes located along the front of the exposure chamber such that only the

heads of the animals were exposed to the combustion atmosphere. Exposures

were for 30 minutes, during which time blood was taken at 0 time, approximately 15 minutes and just before the end of the experiment from the

cannulated animals (one or two animals were cannulated).

The toxicological endpoint was death. The number of animals that died

at each mass loading of material was plotted to produce a concentrationresponse curve from which an LC,-q (30 minutes and 14 days) was calculated.

The in this case is defined as the mass loading of material per

unit chamber volume (mg/Jl) which caused 50% of the animals to die during

2 the 30 minute exposure plus the 14 day post-exposure observation period . The LCj-q's, their 95 percent confidence limits, and the slopes of the

concentration-response curves and the 95% confidence limits on the

slopes were calculated via the statistical method of Litchfield and

Wilcoxon [16]. According to the NBS toxicity test method, the highest

concentration of material tested was 40 mg/Jl. Therefore, in some cases

the LCc-q is listed as greater than 40 mg/Jl.

If the LC,-q (30 minute and 14 day) values fell between 2 mg/

1

and

30 mg/ i,, the animals were exposed for 10 minutes to a 30 mg/

l

loading.

(The 10 minute test was not performed if a 30 minute test at 30 mg/ 5, produced less than 50% death in the animals during the exposure or postexposure period even though the calculated LC^q was less than 30 mg/S,.)

This 10 minute test was to determine if the material rapidly produces

effective concentrations of toxic combustion products. The 10 minute

exposure test was run twice at the temperature condition (flaming or non-flaming) which gave the lower LC,-q value for 30 minutes and 14 days.

If 50% or more of the animals from both 10 minute exposure tests died

either within the 10 minutes or during a 14 day post-exposure observation

period, the material was considered capable of rapidly producing toxicants.

2 Animals that were still losing weight on day 14 were kept until they

died or recovered as noted above. Animals that died after day 14 were

included in the LC,-q calculation.

6
2.2.2

X-ray Fluorescence

X-ray fluorescence measurements were performed to characterize all the

material samples and to determine the various elements that may have

been added as fire retardants. The X-ray energy dispersive system

consisted of a tungsten tube in conjunction with titanium and molybdenum

secondary emitters and a lithium-drifted silicon detector. This system

detects elements with atomic numbers greater than 11 (sodium) . These

measurements were performed according to the procedure of Pella, et al.

[17] except that the samples were analyzed as received.

2.2.3 Combustion Parameters

Ignition delay times and rates of heat release were determined using an oxygen consumption based technique, the NBS cone calorimeter, which has

been described by Babrauskas [18], Samples of each material (#11-15)

were exposed to three different radiant heat fluxes: 25, 50, and

, 9 75 kW/m . The sample size was 100 x 100 x 50 mm thick.

2.2.4 Two Phase Decomposition of Polyurethane Foam

A 20 mg/£ sample of each polyurethane foam (#11, 12, 13 and 14) was decomposed at 25°C below its autoignition temperature for 30 minutes.

The furnace setting was then increased so that the 30 minute residue was heated at approximately 13°C per minute until the final temperature was

800°C. The time to reach 800°C was 32-34 minutes. These experiments

were performed to measure HCN generation under conditions previously

determined by NBS to produce increased concentrations of HCN [19], No

animals were exposed in these experiments.

3.0 RESULTS

3.1 X-ray Fluorescence

The major elements detected by the energy-dispersive spectra for the

five samples were bromine (sample #11), calcium (sample #12), phosphorus

7
and chlorine (sample //14) , and antimony (sample #15). The bromine,

phosphorus and chlorine are most likely associated with fire retardants

indicating that samples #11 and 14 were the fire retarded samples. The

finding of antimony was not surprising, since it is a catalyst used in

the polymerization of polyesters. Although samples #11 and 12 were supposed to be the same formulation except for the fire retardant, the

detection of a calcium compound in sample #12 was indicative of some differences

.

3.2 Rates of Heat Release and Ignition Times

As shown in Table 1, there is no significant difference in the average

heat release rate among the four polyurethane foam specimens. There is,

however, some difference in ignition times. The two fire retarded

samples (#11 and 14) take longer to ignite than the untreated ones (#12

and 13) especially at the lowest heating flux. The polyester batting

2 (#15) did not ignite at 25 kW/m and burned at substantially lower rates

2 at 50 and 75 kW/m than the polyurethane foam samples.

3.3 Autoignition Temperatures

The temperature of the cup furnace which caused the samples to flame

spontaneously was determined for all five materials. The autoignition

temperature for three polyurethane samples (#11, 12, and 13) was 400°C

and that of polyurethane sample #14 was slightly lower - 375°C. Therefore, the differences in material composition or the presence of fire

retardants did not affect the autoignition temperatures of the polyurethane

foam samples. The non-fire retarded polyester material had a higher

autoignition temperature (525°C) than the polyurethane samples.

3.4 Gas Analysis and Temperature Measurements

3.4.1 Carbon Dioxide

Detailed analysis of the CO^ data was not attempted, since the concen- tration of CO^ is dependent upon both the material combustion and the

animals' respiration rate and the latter changes with the amount and

8
type of irritants present in the combustion atmospheres. A comparison

of the CO

2 values recorded in the analytical (A) and animal (R) experiments in Table A1 (appendix, sample #11) in the non-flaming mode at a mass loading of 20.1 mg/£ and in the flaming mode at a mass loading of

19.8 mg/Jl and Table A2 (sample #12) in the non-flaming mode at a mass

loading of 19.9 mg/£ (analytical-A) and 20.1 mg/£ (animals-R) shows the

differences in CO^ between these experiments with and without animals to

be 970, 700 and 2060 ppm, respectively. These increased amounts of CO^

in the animal experiments are attributed to the animals' respiration.

3.4.2 Carbon Monoxide

The average CO concentrations over the 30 minute exposures at each mass

loading /chamber volume are shown in Tables A1 - A5 in the attached

appendix. These values have been plotted in Figure 5 which shows that a linear relationship fits between the CO concentrations and the mass

loadings /chamber volumes for all the materials when decomposed in either

the flaming mode or the non-flaming mode.

The average amount of CO generated from the same mass loading of each

material differed as follows (Fig. 5): material #15 produced significantly more CO in both the flaming mode and the non-flaming mode than

any of the other materials. The lowest average CO above 20 mg/£ for

polyester (#15) was higher than all the data from the polyurethanes,

indicating a statistically significant difference between the two types

of materials [20]. Material #11, which is fire retarded, produced more

CO per mass loading in the non-flaming mode than any of the other

polyurethane materials. Material #14, however, which is also fire

retarded, produced the least amount of CO per mass loading in the nonflaming mode. In the flaming mode, the fire retarded polyurethanes

produced more CO than their non-fire retarded counterparts. The same statistical procedure as above [20] showed that the average amount of CO

generated by material #14 is significantly different from that of

materials #12 and 13.

The generation of CO over time from each of the materials at a mass

loading of 30 mg/£ is shown in Figure 6. The polyester material decomposed

9
in two stages, first producing CO at a rapid generation rate and then at

a slower rate. Unlike the polyurethane materials, the polyester continued

to generate CO for about 13 minutes in the flaming mode and throughout

the 30 minute exposure in the non-flaming mode. The CO from the polyurethane materials leveled off in the first three minutes in the flaming

mode and between 6 and 10 minutes in the non-flaming mode.

The average CO concentrations and carboxyhemoglobin (COHb) values

calculated at the LC^q concentrations for the 30 minute exposure and

14 day post-exposure period are shown in Table 2. For the polyurethane

materials, the CO levels ranged from 750 ppm (#11, non-flaming) to 1400

ppm (#14, flaming). Carboxyhemoglobin (COHb), the molecule which forms

in the blood when the animals are exposed to CO, ranged from 10-66%.

The polyester produced even higher CO and COHb concentrations at the

LC^q; the CO concentrations were 2650 and 3000 ppm in the non-flaming

and flaming mode, respectively; COHb levels were about 85%.

3.4.3 Hydrogen Cyanide

The results in Table 2 show that the levels of HCN generated at the LC,-q

( 30 minutes and 14 day) concentrations for each polyurethane foam in the

non-flaming mode were very low, i.e., less than 10 ppm. The flaming

mode produced slightly higher HCN concentrations (30-70 ppm) . The

highest average value (70 ppm) was observed during the decomposition of

polyurethane foam #14. The decomposition of 35 mg/£ of polyester did not

produce any HCN in either the flaming or non-flaming mode. Therefore, HCN

was not routinely measured during the polyester experiments. The average

HCN concentrations determined for each experiment are given in Tables

A1 - A4 in the appendix.

Other studies conducted at NBS have shown that increased concentrations

of HCN can be generated from flexible polyurethane foam if the material

is decomposed in two phases (procedure is described in Section 2.2.4.

Each of the polyurethane materials in this study was decomposed in this

two phase manner to determine if increased HCN levels would be generated

and the effect of the fire retardants. Heating the charred residues

from the 30 minute non-flaming experiments generated increased HCN

concentrations for all the polyurethane samples (Fig. 7). Polyurethane

10
foam #12 generated the least HCN - 120 ppm. Polyurethane #11, the fire

retarded counterpart to #12, generated 210 ppm HCN, almost double the

amount for sample #12. Non-fire retarded #13 peaked at 180 ppm HCN,

whereas its fire retarded counterpart, #14, peaked at 220 ppm. The fire

retarded materials produced more HCN in this two phase decomposition

procedure than their non-fire retarded counterparts.

3.5 Toxicological Results

3.5.1 LC^q Results

The lowest LC,.q values observed for the polyurethane foams were 17 mg/5,

for #11 (non-flaming conditions) and 28 mg/5, for #14 (flaming conditions).

All the other polyurethane LC^-q values either approached or exceeded

40 mg/5, (Table 2). The LC,-q values of the polyester fiberfill material

#15 in the flaming and non-flaming modes were 28 and 31 mg/5,, respectively.

Based on a comparison of the 95% confidence limits, the LC^-q of material

#11 is significantly different from that of materials #12 and 13, but

not that of #14 or 15. However, these LC,-q values were not considered

toxicologically different from each other based on the classical toxicological

definition which uses a factor of 10 to determine differences in degrees

of toxicity [21]

.

The only within-exposure deaths observed during this study occurred

during the flaming combustion of the fire retarded polyurethane foams,

#11 and #14, and during the non-flaming and flaming combustion of the

polyester fiberfill, #15. The non-fire retarded foams, #12 and #13,

caused no within-exposure deaths.

Deaths were observed during the post-exposure period after the rats were

exposed to the non-flaming decomposition products from materials #11,

12, 13 and 15 and to the flaming decomposition products from the fire

retarded polyurethanes #11 and 14, and from the polyester, #15. Many of

the deaths observed in the post-exposure period occurred after the

animals lost a great amount of weight and after a number of days had

passed. The exceptions were polyurethane foam #14 and polyester #15

decomposed in the flaming mode. In these two cases, all post-exposure

deaths occurred on the same day as the experiments.

11
3.5.2 Post-Exposure Effects

All the animals that survived the exposures and were not cannulated to

provide blood during the exposures were kept and weighed daily for at

least 14 days. The weight profiles provide one indication of the postexposure health of the animals. In this study, the following questions

regarding the post-exposure weights of the animals were addressed:

A. Did placing the animals in restrainers and exposing them to atmospheres

heated by different furnace settings affect the control animals'

weight profiles?

B. Was the weight loss experienced by the experimental animals correlated

with mass loading of material that was thermally decomposed?

C. Which decomposition mode - flaming or non-flaming - produced the

most severe effects on the post-exposure weights of the animals?

D. Did the presence of the fire retardant affect the weight profiles

of the animals?

E. In a comparison of all the materials, what differences were seen in

the animal weight profiles after exposure to the combustion products

from a specified mass loading?

F. How does the individual animals' weight data differ from the mean

weight of the surviving animals in an experiment?

Representative graphs are shown in Figures 8-30. In these graphs, the

weight of the animals on the day of the experiments have been normalized

to 0 to allow a visual comparison of the weight gain or loss due to the

different exposure conditions. Standard deviations of the mean weights

are shown in some cases to indicate the spread of the results. It

should also be noted that occassional rapid increases in the mean

weight may be due to the death of the animal with the lowest weight.

12
3. 5. 2.1 Effect of Restrainer and Head-Only Exposure

Figure 8 shows the weight profiles for four sets of control animals. In

these cases, the furnace temperature was set at 425°C, 550°C, 600°C, and

800°C, and the animals were placed in their restrainers and exposed in

the head-only mode to the atmosphere in the closed exposure chamber. No

materials were burned. Although the furnace was set at the above

temperatures, the average temperatures that the animals experienced

ranged from 28°C to 47°C over the 30 minute exposure period. These four

control groups show that the physical stress of being placed in the

restrainer and being exposed to a non-toxic atmosphere could cause the

animals to lose some weight during the first few days of the postexposure period. The degree of this initial weight loss did not cor- relate with the furnace temperature setting. In the worst case at

425°C, the animals lost 27 grams the first day but were back to their

original weight by day 5.

3. 5. 2. 2 Correlation of Weight Loss and Amount of Material Decomposed

Figure 9 shows the weight loss experenced by the animals following

exposure to various concentrations of material #11 which was decomposed

in the non-flaming mode. The control animals shown are those (also

shown in Fig. 8) which were exposed to an atmosphere where the furnace

temperature was set at 425°C. A concentration-response relationship is

apparent as the animals lose more weight than the controls at the higher

mass loadings (17.5 and 20 mg/£) . At the highest mass loading, 30 mg/£,

all the animals died between day 1 and day 2. Figure 10 shows the

weight profiles and their standard deviations of the controls and the

animals exposed to 17.5 mg/£ (approximately the LC^) of material #11.

After day 5, there is no overlap of the standard deviations indicating

the divergence of the two curves.

A similar correlation between weight loss and concentration of combustion

products was apparent from the non-flaming weight results from material

#12 (Fig. 11). This relationship between weight loss and mass loading/

chamber volume was not apparent for materials #13 and 14 in the non- flaming mode, although in both cases, the exposed animals lost more

13
weight than the untreated controls (Fig. 12 and 13). The polyester

material //15 also showed a correlation between weight loss and concen- tration of combustion products in the non-flaming mode (Fig. 14 and 15).

In the flaming mode, the correlation between weight loss and mass loading

was not evident for any of the materials. The flaming data for materials

//ll and 12 are shown in Figure 16, and that for materials #13, 14 and 15 are in Figures 17, 19, and 20, respectively.

3. 5. 2. 3 Effect of Flaming or NonFlaming Decomposition

Regardless of the material tested, the combustion products from the non- flaming mode produced greater effects on the weight profiles of the

animals than those from the flaming mode. This is most clearly illustrated

in Figure 17 which shows the obvious difference in weight loss after the

animals were exposed to either the flaming or non-flaming combustion

products from material #13. In the non-flaming mode, the animals lost

approximately 30 grams in the first two days following exposure regardless of the concentration of material decomposed. In the flaming mode,

the greatest weight loss was 5.5 grams on day 2. The mean weights and

their standard deviations of the animals after exposure to 40 mg/2. of

material #13 showed no overlap of the standard deviations only on day 2 when the animals exposed in the non-flaming mode lost the most weight

(Fig. 18). This indicates that once the animals start to recover, there

is no significant difference between the experimental and controls.

Results following exposure to the other materials are shown in Figures

19 (material #14) , 21 (material #11) , 22 (material #12) , and 23 (material

#15).

3. 5. 2.4 Effect of the Fire Retardants

Figure 24 compares samples #11 and #12 at comparable concentrations

after decomposition in the non-flaming mode. Material #11, the fire

retarded material, produced a greater toxicological effect on both postexposure weights and deaths than #12, the corresponding untreated foam.

For example, none of the animals exposed to these concentrations of

material #12 died during the post-exposure period. However, all the

14
animals exposed to these concentrations from material #11 did die during

the post-exposure period. The higher the concentration, the sooner the

deaths occurred. Comparison of mean weights and standard deviations of

animals exposed to 20 mg/Jl of materials #11 and 12 decomposed in the

non-flaming mode showed no overlap of the standard deviations between

material #11 and the control data (Fig. 25). Material #12 did overlap

with the control.

Although the LC,-q values in Table 2 were the same, the weight profiles

of the animals after exposure to samples #11 and #12 in the flaming mode

indicate that exposure to material #11 was generally more severe than

exposure to #12 (Fig. 16). The differences are not as obvious as in the

non-flaming mode.

Figure 26 compares the non-flaming results for materials #13 (non-fire

retarded) and #14 (fire retarded) . Both materials show the same initial

weight loss. The animals exposed to material #13 show an attempt to

recover about days 5 and 6 and then again lose weight, after which some recovery is seen. The higher concentrations of material #14 appear to cause the animals to recover more slowly than seen with material #13;

however, this may be an artifact due to no data at the time the recovery

would have occurred. These results at the highest mass loading/chamber

volume tested (40 mg/£) were plotted along with their standard deviations

(Fig. 27). The control data is incomplete between days 4-6 but the

remaining results indicate that no overlap of the standard deviations

occurs on days 2 and 3 following the exposure and that by day 7, there

is no difference between the exposed and control animals. The flaming

results from materials #13 and #14 did not show any significant differences

(Fig. 28).

3. 5. 2.

5

Weight Profiles Following Exposure to All the Materials

at One Mass Loading

Figure 29 compares the non-flaming results for materials #11, 12, 13,

14, and 15 at 30 mg/&. The decomposition products from #11 caused all

the animals to die on day 1. The other materials all caused about the same initial weight loss for the first two days, after which a period of

15
recovery is noted (except #14) for three days. The animals then either

continue to recover (#15) or experienced additional weight losses before

starting to gain weight. The only material other than #11 to cause deaths in these illustrated experiments was #13 which caused one death

on day 11.

3. 5. 2.

6

Weight Data of Individual Animals

In each experiment, six animals were exposed to the combustion products

and all surviving animals, which were not sacrificed for blood, were weighed daily. In all the above cases, the mean weights of the remaining

animals were calculated and plotted. However, since individual animals

died at various times, Figure 30 illustrates each individual animal’s

weight loss and day of death after exposure to 20 mg/2 of material #11.

All the animals reacted in a similar way, i.e., they initially lost

weight for two days, appeared to recover through day 6 or 7, and then

started losing weight again until they died. In this experiment, the

greatest weight loss was 91 grams.

3.5.3 10-Minute Tests

Ten minute tests were performed for polyurethane #11 in the non-flaming

mode where the LC^-q was 17 mg/2, and for polyurethane #14 in the flaming

mode where the LC,.q was 28 mg/Jl. In both cases, no animals died either

during the exposure or during the 14 day post-exposure period. The LC^

for the polyester fiberfill in the non-flaming mode was 28 mg/2,, but

since 30 minute experiments had been carried out with this material at

30 mg/2, and 32 mg/2, and less than 50% of the animals had died either

within or post-exposure, it was concluded that a 10 minute exposure to

30 mg/2 would also not produce 50% deaths.

4.0 DISCUSSION

The purpose of this study was to compare upholstered furniture filling

materials, in particular two different formulations of flexible polyurethane foam and a polyester fiberfill. Each formulation of polyurethane

16
foam was supplied as two samples, one of which contained a fire retardant.

Therefore, a total of five samples were evaluated. These samples were

coded as polyurethane #11, 12, 13, and 14 and polyester #15.

The time-to-ignition was examined under three heat fluxes, 25, 50, and

2

75 kW/m , and the results indicated that the two fire retarded polyurethane foam specimens (#11 and 14) take longer to ignite than the

untreated ones (#12 and 13), expecially at the lowest heating flux.

This also suggests that over a certain range of heating fluxes, the

flame spread might be slower over the fire retarded samples than over

the untreated samples. This advantage would diminish at higher fluxes.

At the lowest heat flux tested, the polyester fiberfill did not ignite

and the times-to-ignition were longer at the higher heat fluxes than

those noted for any of the polyurethane foams.

The rate of heat release data showed no significant differences among

the four polyurethane samples. In other words, once ignited, the

burning rates of these samples are almost identical. The polyester

fiber fill's rate of heat release was lower than any of the polyurethane

samples at any given heat flux. However, it should be noted that the

actual packing density of a fiberfill can vary widely and the density of

the polyester packing would affect the heat release rate. Nonetheless,

it is clear that, in comparison to these polyurethane samples, this

polyester is less ignitable and has a lower heat release rate.

The autoignition temperatures which were determined as part of the NBS

toxicity test method (400°C for polyurethane foams #11, 12 and 13, 375°C

for polyurethane foam #14 and 525°C for the polyester) indicated that

the autoignition temperatures were not affected by the presence of the

flame retardants. This value is determined under different conditions

than the ignition time. The autoignition temperature is found by placing

the sample in a quartz cup which has been preheated to different temperatures and determining the temperature which causes the material to

flame. The ignition time is determined by exposing a sample to different

heat fluxes and measuring the time at which it ignites. Since the autoignition temperatures were similar and little difference was observed in

times-to-ignition at high heat fluxes, the cup furnace exposure appears

comparable to the higher heat fluxes used in the ignition time tests.

17
The polyester fiberfill, which was the least ignitable at the high heat

flux exposures, had the highest autoignition temperature.

Pure gas studies performed at NBS have shown that the LC,-q for a 30

minute CO exposure is 5000 ppm (when the animals are exposed gradually,

i.e., the CO is introduced into the exposure chamber over a 5 minute

period) or 4600 ppm (when the animals are exposed immediately) . Carboxyhemoglobin, the molecule that forms in the blood when the animals are exposed to CO, will reach 87-89% before the animals die. For these

polyurethanes, the CO concentrations at the LC,.q ranged from 750 ppm to

1400 ppm and for this polyester, the CO concentrations were 2650 ppm and

3000 ppm at the LC^q’s in the non-flaming and flaming modes, respectively.

The highest COHb levels noted in this study ranged from 10% to 66% for

the polyurethane materials and about 85% for the polyester. These

results indicate that the CO and COHb levels generated at the LCj.q (30

minutes and 14 day) concentrations of the polyurethane foam were not

sufficient to account for the deaths of the animals. Although the CO

levels generated at the LC,^ value for the polyester were lower than the

lethal levels seen in the pure gas studies, the COHb levels were high

enough (85%) to consider CO as the primary toxicant.

Another factor to consider is that most of the deaths observed in this

study occurred post-exposure. (Exceptions were polyurethane #14 in the

flaming mode in which half the animals died the same day of the experiment

and polyester #15 in which most of the deaths occurred during the exposure.)

The NBS pure CO studies have shown that if the animals survive the

exposure, they will not succumb during the post-exposure period. Therefore, the post-exposure deaths should not be attributed to CO.

HCN can be generated during the thermal decomposition of any nitrogencontaining polymer. Therefore, HCN concentrations were measured during

the decomposition of the polyurethane samples, but not the polyester

material. Pure gas studies at NBS have indicated that approximately

160 ppm of HCN for 30 minutes are necessary to kill 50% of the animals

during exposure to the NBS toxicity test method conditions. Examination

of the HCN results presented in Table 2 shows that the HCN levels ranged

from less than 10 ppm to 70 ppm and therefore were never high enough to

18
account for the within-exposure deaths. Although CO and HCN are probably

contributing to the within-exposure deaths of the animals exposed to

polyurethane combustion products, there appear to be additional factors or toxic gases which are not yet understood. Also the reasons for the

post-exposure deaths are still unclear.

This study also has shown that increased amounts of HCN can be generated

from the polyurethane samples if they are decomposed according to a two

phase procedure developed at NBS. This two phase decomposition procedure

simulates a real fire scenario, namely, that of a polyurethane upholstered

chair which smolders for some unspecified time forming a char and eventually

ignites. These results indicated that the fire retarded samples produced

more HCN than the untreated specimens. Although no animals were exposed

in this series of experiments, it is clear that the LC^_q (30 min) levels

of pure HCN were reached in the case of materials #11, 13, and 14.

The materials examined in this study should not be rank ordered based on

the calculated LC,_q values. Toxicologically , the LC^'s should differ

by a factor of 10 before any one is considered significantly more toxic

than another [21], In this study, the LC^q's were not found to be

toxicologically different. However, it is interesting to note that the

non-fire retarded polyurethane foams (#12 and 13) produced only postexposure deaths and those only in the non-flaming mode. The fire

retarded foams (#11 and 14) produced within-exposure deaths but only in

the flaming mode. The post-exposure deaths that resulted from the fire

retarded foams were in the non-flaming mode (#11) and flaming mode (#11

and 14). The production of within-exposure deaths from the fire retarded

foams only is indicative of a rapidly acting toxicant (within 30 minutes)

being generated by the flaming combustion.

The 10 minute tests designed to determine whether these materials

rapidly produced effective concentrations of toxicants were performed

for the two materials not previously tested for 30 minutes at 30 mg/S,.

These materials did not rapidly produce (within 10 minutes) lethal

levels of toxicants at those concentrations.

The weight profiles of the animals after exposure to the combustion

products of the materials were also evaluated in this study. The greater

19
toxicological effects on the animals by the fire retarded material #11 was reflected by increased weight loss and less rapid recovery than seen with material #12 which was untreated. The combustion products from

materials #13 and #14 appeared to have about equal effects on the postexposure weights of the animals.

In addition, the weight profiles indicated that the non-flaming conditions

caused greater post-exposure effects than the flaming conditions. After

exposure to the non-flaming conditions, the animals lost weight in the

first few days, appeared to stabilize or recover slightly and then,

about day 5-7, began to lose weight again. Material #15, the polyester,

did not produce the second weight loss. It was during this second

period of weight loss that most of the deaths from the polyurethanes

occurred. The deaths that did occur during the first few days are probably directly related to the insult caused by the toxic exposure.

Some of the control data indicates that, in some cases, the initial

weight loss may be due to the physical stress of being restrained and

not the chemical stress of the toxicants. The weight loss and deaths

that occur later, however, are most likely related to the toxic insult

which caused physiological damage or increased susceptibility to secondary

infection.

5.0 CONCLUSIONS

As a result of this study, the following conclusions can be stated:

o The LC^q (30 minute and 14 day) values did not distinguish any of

the test materials as being toxicologically different from the

the others. The worst case fire retarded material #11 was only a factor of two more toxic than its untreated counterpart.

o The fire retarded polyurethane foam decomposition products

caused within-exposure deaths. No such deaths were observed when

the non-fire retarded polyurethane samples were burned.

o Exposure to the combustion products of these materials caused

extensive weight loss of the animals during the post-exposure

20
period and, in many cases, death. The non-flaming mode produced

greater weight losses than the flaming mode. The effect of stress

on the animal weights during the early post-exposure period cannot

be clearly separated from the effect of the toxicants.

o The physiological explanation for the late-occurring post-exposure

deaths is not known.

o The animal deaths from exposure to the combustion products from

the polyurethane foams tested cannot be attributed to CO or HCN

alone.

o Animal deaths due to the combustion products of the polyester

were generally within-exposure and appear to be more directly

related to the CO concentrations.

o The greatest concentration of CO was generated by the polyester

regardless of the combustion mode (flaming or non-flaming). The

fire retarded polyurethanes generated more CO in the flaming mode

than the non-fire retarded polyurethanes. This difference was not

observed in the non-flaming mode.

o Increased concentrations of HCN can be generated from the polyurethane foams by a two phase decomposition procedure. The fire

retarded materials produced even more HCN than the untreated

samples

.

o The rate of heat release for the polyurethane materials increased

with increased heat flux and was comparable for all the foams at a given heat flux. The polyester burned at lower rates when compared

to the polyurethane foams at a given heat flux.

o The autoignition temperatures of the polyurethane foams #11 (fire

retarded), 12, and 13 were the same. Number 14 (fire retarded) was

25°C lower than the other polyurethane foams. Therefore, fire

21
retardants did not affect the temperature at which the samples

flamed. The polyester was 125°C higher indicating lower ignitability

.

o The fire retarded polyurethane samples had longer times-to-ignition

than the untreated samples at the lowest heat flux tested. At

higher heat fluxes, the times were comparable. The polyester had

the longest time-to-ignition at all heat fluxes tested.

6 . 0 ACKNOWLEDGEMENT

The authors gratefully acknowledge the help of the Materials Fire

Properties Group, Center for Fire Research, Dr. V. Babrauskas , Head, who

performed and interpreted the rate of heat release and time-to-ignition

experiments. We also thank Mr. E. Braun, who wrote the computer program

for storing and graphing the post-exposure animal weights and

Ms. M. Diephaus and Ms. A. Durham who skillfully used these computer

programs to prepare many of the figures. The statistical guidance of

Dr. Hsien H. Ku, Statistical Engineering Division, Center for Applied

Mathematics, NBS, is also appreciated greatly. Dr. M.L. Fultz,

Mr. S.E. Harris and Mr. W. Yin were guest workers from the University of

Pittsburgh. Our appreciation is also expressed to Mrs. E. Granger for

her timely and expert typing of this manuscript.

This experimental work was performed under Contract CPSC-IAG-74-75 , Task

Order 82-1 from the U.S. Consumer Product Safety Commission, Dr. Rita Orzel,

Project Representative. The opinions expressed herein are those of the

authors and not those of CPSC.

7 . 0 REFERENCES

1. Federal Emergency Management Agency, Fire in the United States,

2nd Edition, FEMA-22 , July 1982.

2. Petajan, J.H. , Voorhees, K. J.

,

Packham, S.C.

,

Baldwin, R.C.,

Einhorn, I.N., Grunnet, M.L.

,

Dinger, B.G.

,

and Birky, M.M.

,

Extreme toxicity from combustion products of a fire-retarded

polyurethane foam. Science 187 : 742-744 (1974).

22
3. Herpol, C. , Toxicity of products of pyrolysis and combustion of

the fire retardant and untreated woods and synthetic polymers.

In "Fire Retardants: Proceedings of 1st European Conference

on Flammability and Fire Retardants," Ed. by V.M. Bhatnagar,

Technomic Publishing Co. Inc., Westport, CT. p. 64-74 (1977).

4. Hilado, C.J. , Relative toxicity of pyrolysis products of some

foams and fabrics. J. Comb. Tox. _3: 32-60 (1976).

5. Weil, E.D. , and Aaronson, A.M. , Phosphorus flame retardants - meeting new requirements. In "Fire Retardants: Proceedings of

1st European Conference on Flammability and Fire Retardants,"

Ed. by V.M. Bhatnager. Technomic Publishing Co. Inc., Westport,

CT. p. 163-180 (1977).

6. Ashida, K. , Yamauchi, F. , Katoh, M. , and Harada, T. , HCN generation

from urethane and isocyanurate foams. J. Cell. Plastics, 10 : 181-185 (1975).

7. Benisek, L. , The effect of the Zirpro flame-resistant treatments

on flame retardance, smoke emission and toxicity of combustion

products (NBS Developmental Test), J. Comb. Tox. 8_: 233-241 (1981).

8. Alarie, Y.C., Wilson, E. , Civic, T. , Magill, J.J., Funt, J.M.,

Barrow, C. , and Frohliger, J. , Sensory irritation evoked by

polyurethane decomposition products. JFF/Comb. Tox. 2: 139-150

(1975).

9. Hilado, C.J. and Furst, A., Relative toxicity of pyrolysis products

of some materials used in home furnishings. J. Comb. Tox. 3^: 425-464 (1976).

10. Keller, J.G. , Herrera, W.R. , Johnston, B.E. , An investigation of

potential inhalation toxicity of smoke from rigid polyurethane

foams and polyester fabrics containing antiblaze 19 flame

retardant additive. J. Comb. Tox. 3^: 296-304 (1976).

11. Levin, B.C., Fowell, A.J., Birky, M.M. , Paabo, M. , Stolte, A.,

and Malek, D. , Further development of a test method for the assess ment of the acute inhalation toxicity of combustion products.

Nat. Bur. Stand. (U.S.) NBSIR 82-2532, June 1982, 143 p.

12. Potts, W.J., and Lederer, T.S., A method for comparative testing

of smoke toxicity. J. Comb. Tox 4^: 114-162 (1977).

13. Paabo, M. , Birky, M.M. , and Womble, S.E. , Analysis of hydrogen

cyanide in fire environments. J. Comb. Tox. 6^: 99-108 (1979).

14. Committee on Care and Use of Laboratory Animals, Guide for the care and use of laboratory animals. DHEW publication No. (NIH)

78-23. U.S. Dept, of HEW, Public Health Service, National

Institutes of Health (1978).

23
15. Packham, S.C., Frens, D.B., McCandless, J.B., Patajan, J.H., and

Blrky, M.M. , A chronic intra-arterial cannula and rapid technique

for carboxyhemoglobin determination. J. Comb. Tox. 3^ 471-478

(1976).

16. Litchfield, J.T., Jr., and Wilcoxon, F., A simplified method of

evaluating dose-effect experiments. J. Pharmacol, and Exp.

Therapeut. 9j6: 99-113 (1949).

17. Pella, P.A., Lorber, K.E., and Heinrich, K.F. J. , Energy-dispersive

X-ray spectrometric analysis of environmental samples after borate

fusion. Anal. Chem. 50: 1268-1271 (1978).

18. Babrauskas, V. , Development of the cone calorimeter - a bench-scale

heat release rate apparatus based on oxygen consumption. Nat. Bur.

Stand. (U.S.), NBSIR 82-2611, Nov. 1982, 84 p.

19. NBS results, to be published.

20. Tukey, J.W. , A quick compact, two-sample test to Duckworth’s

specifications. Technometrics 2^:31-48 (1959).

21. Klaassen, C.D. and Doull, J. , Evaluation of safety: toxicological

evaluation. In "Casarett and Doull’s Toxicology" Ed. by Doull, J.,

Klaassen, C.D. and Amdur, M.O. 2nd Edition, Chapter 2, p. 12.

Macmillan Publ. Co., Inc. New York, Toronto, and London. 1980.

24
Table 1

Ignition Times and Rate of Heat Release

Material

Heating

Flux

(kW/m )

Ignition

Time

(sec)

Peak Heat

Release

(kW/ni )

60 sec. Average

Heat Release

(kW/m2

)

11 25 39.2 438 276

50 4.1 1029 456

75 2.7 1429 545

12 25 5.5 433 278

50 3.3 1059 443

75 1.3 1773 501

13 25 5.2 466 272

50 3.3 876 470

75 NA 1810 646

14 25 15.0 467 230

50 4.1 844 428

75 2.9 1862 561

15 25 00 0 0

50 10.2 247 149

75 9.2 259 129

25
Toxicological

and

Gas

Results

from

NBS

Toxicity

Test

Method

a*O H U

0) Of P 4J

4-» P P P

0)M

U

W 3 H Cfl CO 5n h O O »H £* £<§ U Pd

00

C/3

4-i

C

O *H Z £ O * Z PM9

03 5n O rH e-<§ w

as o O *H

4-»

C

p co i OOhU

C0 4-» hJ u c

CU 0) > u < co 5 l

he

a

4-» s

co o a o a

*h

B

0)

03 03 P a 0 a a p

03 5^ T3

a)

m

pe: C7N m-4 1 c P o O CJ pU 0) 4J a p o

03 rH U C/3 Po

CJ

03>%

CO 0) T3 UP 03 <r 03 4-» Hin-o -h .ON -H B + UH *H P X P o

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w oma

hJH o M o < w

gggg

g

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CO

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vO

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<4-omo o-O' AOo

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rHO

00

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Uh «H

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p P P 4J 4J 'O 0 rH o O *H Z fa Z Z *P

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03 03 T3 03

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p 0 (0 P •H u UH p P p u •H T3

4J P P B P P o 3 c 4J u •H o* p p 4J co u s

Ql P P p 4J E •H u 4J H3

00O

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4J

a

•H JS 5 ^ OOOO »o

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co

p 03 P *H *H & *2 ts oS 03 l/VH rH O P OH hJ 4J e

men co •H O P u 0 p P

rH P P P P O

u hJ rH

C £ P P P P P P 4-1 u <D P OO •H P P P P P p > 4J P UH •H O U 1 x 1 X 1 X 1 X | H c CJ < P P M X z P 4J rH pn u CM Sn 4J cn Jn 4-J 'd' Sn P m 4-> rH P rH rH P rH rH P rH rH P rH rH 4J rH P O U O M O H O H O CO • • • • z fa 3 fa P fa P fa P fa P *** rH Csl cn <» m

26
0.5^/min.

27

Figure

1.

Schematic

of

NBS

gas

analysis

system.
oo
1000

ml

QUARTZ

BEAKER

92

mm

O.D.

15

cm

high

GO

29

HEATING

ELEMENT

IN

BOTTOM
30

Figure

4.

Animal

restrainer
AVERAGE

CO

CpprrO

AVERAGE

CO

CppnO

Figure 5. MASS LOADING/CHAMBER VOLUME Cmg/15

Average 30 minute carbon monoxide concentrations (ppm) as unction of the mass loading/chamber volume (mg/£)

A. - Non-flaming results. B. - Flaming results.

a

31
CO

(ppm)

CO

(ppm)

TIME (seconds)

Figure 6. Rate of carbon monoxide generation (ppm) during decomposition

of samples 11, 12, 13, 14 and 15 at mass loading /chamber

volume of 30 mg/£. A - Non-flaming results. B - Flaming

results

.

32
250

(Wdd) NOH

4-1O

60 c c O *H

•H £

4-1 CO U t—l G 4-1 3 I 4-1 Co

co c

CO CU

co

X4-1 co

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•H 4J

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>-i S

CO6od

60

CU

<0 jC

X)

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CO • CU CU Odd3 3 C 4J 4J

<U cO CO 60 (H O CU CU vj a a

XI E E

>1 (U H) K *J 4

fH.

CU

>H3

60

•H

33

FURNACE

TEMPERATURE

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Figure

8.

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profiles

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weight

on

day

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Figure

10.

Mean

weight

profiles

and

standard

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of

animals

exposed

to

17.5

mg/£

of

material

//ll

decomposed

in

the

non-flaming

mode

and

controls

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were

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Figure

11.

Profiles

of

the

mean

weights

of

animals

exposed

to

the

non-flaming

thermal

decomposition

products

of

sample

#12

at

various

mass

loadings

/chamber

volume

(mg/£).
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Figure

12.

Mean

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profiles

of

animals

exposed

to

the

non-flaming

thermal

decomposition

products

of

sample

#13

at

various

mass

loadings

/chamber

volume

(mg/£)

.
39

Figure

13.

Mean

weight

profiles

of

animals

exposed

to

the

non-flaming

thermal

decomposition

products

from

sample

#14

at

various

mass

loadings/chamber

volume

(mg/£).
(suudjB) 1H913M NI 30NVM0

40

Figure

14.

Mean

weight

profiles

after

exposure

to

the

non-flaming

decomposition

of

sample

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Figure

15.

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mean

weight

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after

exposure

to

the

non-flaming

dacomposi

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products

of

material

//

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43

Figure

17.

Mean

weight

profiles

of

animals

exposed

to

either

the

flaming

or

non-flaming

decomposition

products

from

sample

//

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mass

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and

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18.

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and

standard

deviations

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animals

exposed

to

40

mg

/£

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//

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in

the

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and

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Figure

19.

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of

animals

exposed

to

either

the

flaming

or

non-flaming

decomposition

products

from

sample

#14

at

mass

loadings

/chamber

volume

of

20

and

30

mg/£.
(SIAlVdO) 1H9I3M NI 30NVH0

46

Figure

20.

Profiles

of

mean

animal

weights

after

exposure

to

the

flaming

decomposition

products

of

material

#15.
(sujdjB) 1M0I3M NI 30NVH0

47

Figure

21.

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animals

after

exposure

to

either

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sample

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22.

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23.

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exposure

to

the

non-flaming

thermal

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products

from

samples

//

11

and

12

at

mass

loadings/chamber

volume

of

20

and

30

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(suudjB) 1H0I3M NI 39NVH0

51

Figure

25.

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and

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animals

exposed

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20

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materials

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to

the

non-flaming

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from

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#13

and

14

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mass

loadings

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after

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to

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14

at

mass

loadings

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20,

30

and

40

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Figure

29.

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of

mean

weights

of

animals

after

exposure

to

non-flaming

thermal

decomposition

products

from

samples

#11,

12,

13,

14

and

15

at

a

mass

loading

/chamber

volume

of

30

mg/£.
(SWVa9)lH9I3M N1 39NVH0

56

Figure

30.

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in

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animals

exposed

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non-flaming

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a

mass

loading

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20

mg

/£.
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62 i
NBS.r, IA (REV. 2-80

U.3. DEPT. OF COMM.

BIBLIOGRAPHIC DATA

SHEET (See instructions)

4. TITLE AND SUBTITLE

1. PUBLICATION OR

REPORT NO.

NBSIR 83-2791

2. Performing Organ. Report No^ 3. Publication Date

November 19bj

An Acute Inhalation Toxicological Evaluation of Combustion Products from Fire Retarded

and Non-Fire Retarded Flexible Polyurethane Foam and Polyester

5. author(S) Barbara C. Levin, Maya Paabo, Mary Lou Fultz,

Cheryl Bailey, Way Yin, and Steven E. Harris

6. PERFORMING ORGANIZATION (If joint or other than NBS, see instructions)

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

9.

SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (Street. City. State, ZIP)

7. Contract/Grant No. CPSC-1AG-74-25

S. Type of Report & Period Covered

Consumer Product Safety Commission

5401 Westbard Avenue

Bethesda, MD 20207

10.

SUPPLEMENTARY NOTES

I | Document describes a computer program; SF-185, FIPS Software Summary, is attached.

11. ABSTRACT (A 200-word or less factual summary of most significant information. If document includes a significant

bibliography or literature survey, mention it here)

The acute inhalation toxicity of the combustion products from selected upholstered

furniture filling materials with and without fire retardants was evaluated by the

toxicity test method developed by the National Bureau of Standards. The five materials

that were evaluated consisted of two different formulations of flexible polyurethane

foam (each formulation was supplied in both a fire retarded and non-fire retarded form)

and a polyester fiberfill (not fire retarded). Atmospheric concentrations of carbon

monoxide, carbon dioxide, oxygen, and hydrogen cyanide in the exposure chamber were

monitored throughout the thermal decomposition of the materials. In addition, time-toignition, rate of heat release, hydrogen cyanide generation via a two phase decomposition procedure and x-ray fluorescence measurements were performed. The LC50 (30 minute

and 14 day) values did not distinguish any of the materials as being significantly more

toxic than the others. In the worst case, one of the fire retarded polyurethane foams was only a factor of two more toxic than its untreated counterpart. Only the fire

retarded foams and the polyester caused deaths of the Fischer 344 rats during the

30 minute exposures. Extensive weight loss and post-exposure deaths occurred after

exposure to the combustion products from all the materials. Animal deaths during or following exposure to the polyurethane cannot be attributed to carbon monoxide or hydrogen cyanide alone. Deaths during exposure to the polyester combustion products

appear to be more directly related to the concentrations of carbon monoxide.

12. KEY WORDS (Six to twelve entries; alphabetical order; capitalize only proper names; and separate key words by semicolons

Carbon monoxide; combustion products; fire retardants; heat release; hydrogen

cyanide; inhalation; polyester; polyurethane foams; toxicology; weight loss

13.

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