ML19211A174

Evaluation of Matls Used in Fire Resistant Phenolic Foam

ML19211A174
Person / Time
Site:	07109009
Issue date:	03/01/1978
From:	Daugherty C, Harris G, Wright R UNION CARBIDE CORP.
To:
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ML19211A172	List: ML19211A171 ML19211A174
References
14791, NUDOCS 7912170144
Download: ML19211A174 (15)

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{{#Wiki_filter:. 1 K/TL 729 EVALUATION OF MATERIALS USED IN FIRE. RESISTANT PHENOLIC FOAM C. E. Daugherty G. E. Harris R. R. Wright Special Services Department K.25 Technical Services Division March 1,1978 & i.~i g L ~.. ;..,~ %:.T:.a k Q. s.L. 7,.;. ; '.+ L ~Cght ic. ', uw.J w ca: '.::;',L W.:. - c. N@g@QM$f%M n:Kh %:n-~ :'*?'. x. b r ~ $ ' ^? XM. tau $'w$j%Y"[ [. -j UNION MTh Ea.w,. A. rt s %. - m*.^..,.,. '.;. - :.-a :,~ s, 1 CARBlDE w&. a,, y -~. re - .--.__..f\\. ... _ _= ,1 _ _ ~ _ a prepared for the U.S. DEPARTMENT OF ENERGY under U.S. GOVERNMENT Contract W.7405 eng 26 1594 193 1 g. v m g o 14?s1 79121 70

'I This report was prepared as an account of work sponsored by en agency of the United States Government. Neither the Umted States Government or any agency thereof, nor ar') of their employees, nor any of their contractors, wt> contractors. or their employees, makes any warranty, empress or wnpsied, nor assumes any legal liabdity or responsabstity for any third party's use or the reWts of such use of any information, apparatus, pro &ct or process disclosed in this report, nor represents that its use by mch third party would not infringe privatety owned rights. 594 194

1 3 ABSTRACT Materials to be used in the fire-resistant phenclic foam are outlined in the U. S. Atomic Energy Co= mission (Department of Energy) Material and Equipment Specification SP-9. Many of the specified materials are no longer available, or are difficult to obtain, due to specified vendor, grade, or =esh size. Cc=patibility evaluations of =aterials that are nov being substituted for those cutlined in the specification have been =ade, and the results are presented in this report. A number of tests were run on the substituted materials, including mesh evaluation, ther?.al gravimetric analyses, free-foam density, fire tests, and moisture tests. The tests indicated that the substituted =aterials did not affect the quality of the final foes product. It is recc= mended that the required properties of the final foam product be detailed in the =aterial specification, along with suggested component materials that are known to yield an acceptable foa=. Specification of component =aterials to be used should be avoided because material availability, =aterial varia-tions between venders or between lots frem the sa=e vendor, and cther dif-ferences vould necessitate obtaining formal deviations frem the specifi-cation or issuing frequent specification revisiens. 1594193

e + 5 CONTEITS Page INTRODUCTION.... 7 EIFERIMENTAL... 8 CONCLUSIONS 16 1594 196

7 EVALUATION OF MATERIALS USED IN FIRE-RESISTANT PHENOLIC FOAM IUTRbDUCTION Many of the materials outlined in the U. S. Atomic Energy Cc= mission (Department of Energy (DOE)} Material and Equipment Specification SP-9 for fire-resistant phenolic foam are no lenger available, and in some cases, the specific grade, =esh size, and/or vendor have pre.nented purchasing problems to contractors. As a result, other materials have been substituted for the originals. The original specification contained the folleving materials: Ccmponent Weight Per 100 lb of

Material, Material Vander - Trade Name Ib Licuid Comnonents:

1. Phenolic Resin 3RL-2760 UCC Plastics Division 65.8 0.2 2. Surfactant UCC Plastics Division 2.0 0.1 Silicene Surfactant L-530; Dev Corning Surfactant No. 202, or equal 3 Refrigerant-113 DuPont Freen 113, or equal 6.6 0.1 Povder Cc=ponents: h. Boric Anhydride (3 0 ) Var-Lac-OiD Chemical Company k.1 : 0.1 23 -100 +200 Mesh Scric Anhydride (3 0 ) Var-Lac-OiD Chemical Company h.1 t 0.1 23 -200 Mesh 5 Oxalic Acid, H C 0g, Baker and Adamson 3.2 2 0.1 2 Anhydrous Povder, No. 1135, er equal Reagent Grade Reinforcing Ccmoonent: 6. Fiberglas Rovings No. Owens-Corning Fiberglas 9.6 : 0.h 805 (HSI) 1/h-in. Corporation Chopped Lengths ( Materials 2 and 6 are no longer available frem the manufacturers. Union Carbide Corporation (UCC) Y-6663 has been substituted for UCC L-530 and Owens-Corning Fiberglas No. 833 has been substituted for Fiberglas No. 305 Both of these substitutions were made based on recc=mendations frem the manufacturers. Because it is difficult to obtain, practical grade borie 1594 197

E 8 anhydride PO-2685 from East =an has been substituted for the compound manu-factured by V,tr-Lac-OiD. Since reagent-grade anhydrous oxalic acid is also difficult to obtain, technical grade has been substituted for Material 5 Materials 1 and 3 are still available and re=ain unchanged. Tests have been run on the substituted boric anhydride and oxalic acid to ensure that the properties of the final phenolic foam are ecmparable to the foam produced according to the specifications. EXPERIMENTAL The materials analysed are listed in Table 1. Table 1 MATERIAL ANALYZED Boric Anhydride Reagent grade, -100 +200 mesh, (3 0 ) Var-Lac-OiD Chemical Company 23 Practical grade, -100 mesh, PO-2685, East =an Chemical Ccmpany Oxalic Acid Hydrated,(a) reagent grade, (H C 0g) Baker and Ada= son 22 Anhydrous, technical grade, Browning Chemical Ccmpany (a)This compound was previously thought to be the anhydrous form, as indicated in the specificatien, but was later determined to contain two vaters of hydration (H C 0g + 22 2H O). 2 Thermal analyses, mesh evaluation, and free-foam tests were run on the ec=peunds. Thermal gravimetric and differential thermal analyses were run on the ecmpcunds which indicated no significant differences in che:11-cal properties, except for the oxalic acid from Baker and Adamsen which was found to be hydrated. The two ecmpounds of toric anhydride vere sieved to evaluate the difference in mesh size. The results are given in Table 2. 1594 198

9 Table 2 EVALUATION OF MESH SIZES FCR BORIC A7 HYDRIDE CCMPOUNDS B 0, Practical Orade, B 0, Reagent Orade, 23 2 3 Sieve Var-Lac-OiD -100 +200 Mesh East =an PO-2685 -100 Mesh No. (% Retained) (5 Retained) 40 0.h1 0.25 70 0.75 62.30 100 1h.12 18.h8 <100 8k.72 18.97 The difference in mesh size did not affect mixing or reaction rate during the foam tests described in the following paragraphs. Free-fcan tests were run on mixtures of the chemicals to evaluate reaction properties. Figure 1 is a diagram of the foaming apparatus. The tests were performed in a round, 95-liter (25-gal) galvanized steel container which was approxi=ately 60 cm (2k in.) high and h2 cm (16-1/2 in) in diamet er. Affixed to a vertical aluminum rod in the center of the con-tainer were three ther=occuples which =easured the temperature of the components during the foaming process. A fourth thermocouple was sus-pended approxi=ately 5, em (2 in.) above the top of the foam layer and was moved upward, to =aintain this 5-cm position constant as the foam expanded. A fifth thermocouple recorded rocs temperature during the process. The container had 3.5-cm (3/15-in. ) veep holes spaced 7.5-10 cm (3 h in.) apart. The container was heated at a constant rate during the foaming process, with the temperature at the beginning of the process recorded at h0*C. ?eo tests were run, using approximately h.5 kg (10 lb) of material in each. In the first test, the materials used were: 1. Phenolic resin BRL-2760, UCC Plastics Division. 2. Surfactant Y-663, UCC Plastics Division. 3. Freon 113, DuPont. h. Soric anhydride, reagent grade, -100 +200 mesh, Var-Lac-OiD Chemical Ccmpany. 1594 199

10 owe. No. sos-t es tul 0 50 100 M.V. TEMPERATURE RECORDER <poo ip<> ONE IRON-CONSTANTAN T.C. (ROOM TEMPER ATURE) BLOWER - n CONDENSATE ^ OUT RCULATING STEAM IN 0 AIR ' O STEAM LINES l9 FOAM g m f C THERMOCOUPl. Eli 0 N 'o[ SUPPORT e. j ~ O o '6 j - o lO : A ~ u

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t; - 95 LITER / FOAM O ^ CONTAINER c O u m - o r s-O u = = FOUR COPPER-CONSTANTAN 200 LITER S.S. DRUM THERMOCOUPLES 1594 200 7,,, 1 DIAGRAM OF FOAMING AFFARATJS

11 5 Hydrated oxalic acid (H C 0g = 2H O), reagent grade, Baker and 22 2 Adamson. 6. Fiberglas Rovings No. 883, 0.63 cm (1/h in. ) lengths, ovens-Corning Fiberglas Corporatica. The same materials were used in the second test, except for Items k and 5 for which vere substituted: k. Boric anhydride, practical grade, -100 mesh, PO-2685. F.:ast=an Chemical Company. Anhydrous oxalic acid (H C 0g), technical grade, Browning Chemical 5 22 Cc=pany. It should be noted that no effort was =ade to ecmpensate for the addf tional vater present in the hydrated oxalic acid. The same weights of hydrated and anhydrous oxalic acid were used in both tests. For each test, the ingredients were mixed in the sa=e manner. The resin, surfactant, and refrigerant were mixed until homogeneous. Fiberglass was added separately and mixed, followed by addition of the exalic acid and boric anhydride. After a total mix time of 5 min, the mixture was poured into the container and allowed to free-foam. Heats of reaction during the foaming process for each test are shown in Figures 2 and 3 No significant difference was determined between the two exothermic reactions. Cross sections of the fcems after 2h hr are shown in Figure k. Except for a slight difference in color, the two samples were similar. Both samples reached a height of 50 cm (20 in.) with a team density of 0.05 g/cm3 (3.2 lb/ft3). The irregular shape of the sample frem the second test was a result of uneven distribution of the =aterial before foaming. To ecmpare their properties after burning, the samples were exposed to a 10-min fire test at 760 C. Cross sections of sanples after burning are pictured in Figure 5 The sa=ples behaved in the same manner; there was no reducticn in size after burning, and the insulating properties adjudged by the depth of charring appeared to be equal. Portions of each of the two sa=ples were soaked in vater for 72 hr to evaluate the absorbent properties of the foam. The pH of each solution was measured after the 72-hr period to give seme indication of the corro-sive nature of vet, uncoated foam. The results are given below: Test No. Water Absorbed Solution pH 1 3.1 x sample vt 2.5 2 k.6 x sample vt 2.h 1594 201

12 owo. no. o-n ise s tus 100 C 3 S 3 90 ? 80 0 70 U e g80 m THERMOCOUPLE LOCATION m G BOTTOM 4 ENTER OF FOAM A MICDLE4 ENTER OF FOAM $50 0 TOP 4 ENTER OF FOAM 0 TOP 4 ENTER ABOVE FOAM X OUTSIDE THE CONTAINER-ROOM TEMPERATURE 40 30 X X X X X -w 20 I I I I I I I 10 O 10 20 30 40 50 60 70 TIME, MI.N Figure 2 "'EST 1: HEAT OF REACTION DURI'IG FOAMING FRCCESS 1594 202

DWS. NO. G-77 1942 lup 100 M3 90 O 80 0 A O 70 g80 E-I O w g 50 THERMOCOUPLE LOCATION 0 BOTTOM 4 ENTER OF FOAM 40 A MIDDLE CENTER OF FOAM O TOP 4 ENTER OF FOAM O TOP 4 ENTER ABOVE FOAM X OUTSIDE THE CONTAINER-ROOM TEMPERATURE 30 20 10 l I I I I I I O 10 20 30 40 50 60 70 TIMES MIN Figure 3 TEST 2: HEAT OF REACTION DURING E0AMDG FROCESS 1594 203

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16 Test 2 was determined to be more absorbent than Test 1; however, the pH values of both solutions were approxi=ately the same. The lov pH in both tests indicated that vet, uncoated team would be corrosive. CONCLUSIONS Since substituted and specified materials behaved in a similar manner during the foaming, fire, and water tests, it is evident that the quality of the final product is not entirely dependent on grade, mesh si::e, or product vendor. An unexpected discovery was that the hydrated form of oxalic acid (H C 0g + 2H O), accidently substituted for the anhydrous 22 2 form (H C 0g), did not affect the quality of the foam, indicating that 22 water content in materials can be varied. It is reco= mended that the required properties of the final foam product be detailed in the material specification along with suggested component materials that are known to yield an acceptable team. Specification of component =aterials to be used should be avoided because material avail-ability, material variations between vendors or between lots from the same vendor, and other differences vould necessitate obtaining formal deviations from the specification or issuing frequent specification revisions. 1594 206 6 k

17 DISTRIBUTION 1. Administrative Offices Winkel, R. A. 2-3 Engineering Division Gregory, J. W. Stout, F. W., Jr. h. Gaseous Diffusion Dev. Div. Wheatley, S. J. . _ _ _ _ _ ~ 5-12. K-25 Technical Services Div. Carpenter, L. J. Daugherty, C. E. Harris, G. E. Levin, R. W. Napolitan, D. S. (2) Newlon, C. E. Wri6ht, R. R. 13 Library 1h-17 Oeerations Division Barlow, C. R. Cates, P. S. Golliher, W. R. Legeny, A. J.

18. So=:erfeld, K. W.

19. ORGDP Records Derartment (FC) 20 kl. U.S. Derartment of Enerry Fletcher, H. D. Lamb, J. A. (20) Pryor, W. A. h2 h3 Goedyear Atemic Correration DeVito, V. J. Wolt:, F. E. hh. Faducah Stitt, D. H. h5 Y-12 Plant 1594 207 Dyer, H. R. 14791}}