Professional Documents
Culture Documents
AD NUMBER
AD819081
FROM
Distribution authorized to U.S. Gov't.
agencies and their contractors; Critical
Technology; JUL 1967. Other requests shall
be referred to Air Force Rocket Propulsion
Laboratory, ATTN: RPPR/STINFO, Edwards
AFB, CA 93523.
AUTHORITY
00 By
Chemical and Material Sciences Department
Research Division
Rocketdyne, a Division of North American Aviation, Inc.
Canoga Park, California
July 1967
By
Chemical and Material Sciences Department
Research Division
Rocketdyne, a Division of North American Aviation, Inc.
Canoga Park, California
July 1967
Ii
ADJSTHACT
i i i/iv
AGNOWQ(ILNT
V
In addition, a special acknowledgemcnt is due the folloving organizatioa'
(and the noted personnel) for providing technical consultation du'iug the
industry survey:
bell Aerosystews
F.M.C. Cor'oi-ation
U. H. Robinson, A. B. Featherstona
Picatinny Arcise I
W. Buckley
D. Coucl
vi
CONTLNT8
1.3 leferences . . . . . . . . . . 6
Section 2: Physico-Chemical Properties . .3
2.1 General Description ..... .......... . . 13
2.2 Physical Properties . ............ .. . 14
2.3 Chemical Properties ..... ............ 34
2.4 Solubility and Miscibility .... .. ........... 35
2.5 Gelation ......... ............ .. 37
2.6 Heat Transfer Properties . . . ........... 37
2.7 Ignition Characteristics ... .......... . 39
2.8 References ....... ............... 44
Section I, Production ...... ............ . 135
3.1 M4anulacturing Techniques ... ... ........... 135
3.2 Current Production . . . ........... .. 140
3.3 Propellant Specification ............ . .142
3.4 Chemical Analysis ....... ............... 144
3.5 References ....... ................ 150
Section 4: Storage and ltandling . ........ 154
4.1 Storability ..... ................ 154
4.2 Materials of Construction 4 ............. 169
4.3 Materials Treatment and Passivaticn . . ...... 208
4.4 Facilities and Equipment . . . .. 227
4.5 Decontamination aad Disposal . . . 262
4.6 References . . . ............ 0 264
Section 5: Transportation . . . . . .... ... 371
5.1 Chipping Containers and Vehicles . . ....... 371
5.2 Shipping Regulations ........ 374
5.3 Operation and Maintenance of Equipment . . . . . . . 375
vii
5.4 actcznces . .. . .. . . . . 380
Section 6: Safety . . . . . . .. .. . . . . 381
6.1 Hazard, . . .. . . . . . . . . . . 381
6.2 Hazard Prevention . . . . . . . . . . 9..
359
6.3 Hazard Control . . . . . . . . . . . . .. . 398
6.4 N-ruoo el Protection &.. .. .. . 400
6.5 Referencos . . . . . . . . . . . . . . . 405
Section 7: Decomposltlon . . . . . . . . . . . . . 417
7.1 Decomposition Mechanism . . . . . . . . . . . 417
7.2 Controlled Decomsposltion ..... .......... 422
7.3 References ....... . ............ . . 434
Section 8: Bibliography ...... . . . ............ 437
8.1 General References ....... . ......... .. 438
8.2 Physical P'roperties .................. 439
8.3 Structue.. .. . . ..... . . .......... ... 446
8.4 Solubility ..... .. . ... ........
.... 447
8.5 Hindig and Storage ...... . .......... .44
8.6 Materials Compatibility ....... . ........ .452
8.7 Transportation ....... . . . ....... .... 454
8.8 Safety ........................... 4511
8.9 Dccoposition . . . . . . . . . ............. 459
vI L
ULUJSTIATlONS
ix
2.12s. Beat& of Formation of Props Il.at-Grade WI~drone-
Peroxide-Water Solutions . . . . . .. 0.
2.13 B" s of Formtiou of Fropellat-Grad. Hydrogeu
Peroxide-41ater Solutions at 25 C a . . . . . 109
2.13 . Boats of Forution of Propellaut-Grade Hydrogen
Perox4de-NJater Solutions at 77 r . . . . . . . 310
2.14. Baots of Ysporization of Hydrogeu Peroxide-
Vats 8olutions . . * . . .. . . . .. . 111
2.14s. Beats of Vcporiuation of Hydrogeu Peroxide-
Water Solution 1. . . . . . ..... 112
2.15. Beats of Mixing of Hydrogen Peroxide-Water Solutions . 113
2.15s. Boats of Mixing of Aydrogen Peroxide-Water bolutions . 114
2.16. Ematm of Deomposition of Propell"t-Grade Hydrogen
Feroxide-Watea Solutions at 25 C .. .. ........ 115
2.16a. Boats of Decomposition of Propellant-Grade Lkdrogeu
Peruxide-Woater Solutions at 77 F . .... . . 116
2.17. beat Campactios of Propellant-Grade Elydrogeu
Peroxide-Water Solutions ..... ......... . 117
2.17a. Beat Capacitiea of Propellazt-Grade Hydrogeu
Peroxidi-Water Solutions ..... .......... 118
2.18. Viscosiy of Liquid Itydrogen Peroxide-Water Solutions . 119
2.18a. Viscosity of Liquid fldrogen Peroxide--ater Solutions . * 120
2.19. Viscumities of 98 w/o Hydroaeu Peroxide, 70 w/o
rkvdrozen Peroxide,- and W-.,- .
........ ... .
2.19a. Viocomitito of 98 w/o Hydrogeu Peroxide, 70 W/o
*ydrogen Peroxide, and Water ... ......... . 122
2.20. Viscosity of Hydrogen Peroxide and Water Vapor . . . . 12.3
2.21. Thermal Conductivity of 98.2 w/o Hydrogen Peroxide . * 42(.
2,22. Velocity of Bound in Propellant-Grade kdrogeu
,roxide-Uater Solutions .... .......... 12
2.22s. Velocity of Sound in Propellant-Grade B3-drogeu
Peroxide-Water Solutions . . . . . . . . . . 26
2.23. Dielectric Constant of Propellant-Grade fydrogon
Peroxide-Water Solutions .............. .327
2Xi
6.. Ignition Delay of hydrogen Peroxide With Filt .. . . 413
6.2. Ignition Limits of Hydrogen Peroxide Vapor . . . . . 41
6.3. Liquid Comnpouitions Which Result in Ignitable Vapor
Concentrations . . . * . . . . . . 115
4
Xii
TABLES
Solutions . . . . . .. . . . . . . .... 73
2.12. Vapor-Phase Thermodynamic Properties of 90 w/o H202
Solutions . . . . . . . . . . . . . . . . 74
2.13. Vapor-Phase Thermodynamic Properties of70 w/o H202
Solutions .... . . . . . . . . . . . . 75
2.14. Vapor-Phase Thermodynamic Properties of 70 w/o %2
. . .S olu tion s . ....... . • 76
Xiii
2.17. Miscellaneous Molecular and Electromagnetic Properties
of Hydrogen Peroxide . . . 80
xiv
4.16. Compatibility of Hydrogen Peroxide With Ceramics,
Iefractories, and Miscellaneous Materials . # . . * 318
4.17. Results of Evaluation of Protective Coatings for 90 w/o
Hydrogen Peroxide Service . . . . . . . . . .. 320
4.18. Evaluation of Clothing Materials for Contact With
90 w/o Hydrogen Peroxide . . . .. .......... 324
4.10a. Clothing Materials not Suitable for Use When Handlirig
90 w/o Hydrogen Peroxide .. ....... . .. 325
4.19. Compatibility of Various Metals With 98 w/o Hydrogen
Peroxide at High Temperatures . ....... . . 326
4.20. Compatibility of 90-Percent Hydrogen Peroxide With 1060
and 1100 Aluminum Alloys ...... ..... 328
4.21. Compatibility of 90 w/o Hydrogen Peroxide With
6061-T6 Aluminum Sheet ............ 329
4.22. Compatibility of 90 w/o Hydrogen Peroxide With
304 Stainless Steel .... ........... . 334
4.23. Compatibility of 90 w/o Hydrogen Peroxide With
316L Stainless Steel .... ........... 335
4.24. Compatibility of 90 w/o Hydrogen Peroxide With
321 Stainless Steel . ....... . .... 337
4.25. Compatibility of 90 w/o Hydrogen Peroxide With
Selected StainlessSho Alloys . .. . . 342
4.26. Compatibility of 90 w/o Hydrogen Peroxide With
Vicone 185 Elastomer . . . . . . . . . . .. 3"
4.27. Compatibility of 90 w/o Hydrogen Peroxide With
Silastic 9711 Elastomer Sheet ........ 345
4.28. Compatibility of 90 wio Hydrogen Peroxide With
Selected Viton Elastomeric Materials . . . . . .. 348
4.29. Compatibility of 90 v/o Hydrogen Peroxide With
Selected Plastics . . . . ... . 349
4.30., Compatibility of 90 v/o Hydrogen Peroxide With
Selected Composite Materials . . . . . . . . 351
4.31. Heterogeneous Decomposition Rate of Hydrogen Peroxide
as a Function of Surface Preparation ... .. . 353
4.31a. Procedures Used for Surface Preparation in Table 4.31 357
4.32. Comparison of the Various Methods of Tank Temperature
Mauremnt in Order of Increasing Cost . . . .. . 359
6.1. 90- to 100-Percent Hydrogen Peroxide Thermal
ewnsitivity Data .. . . . . . . .** 4105
xv
8WTIk
l 1: rINTRODUCTIIN
1.1 GOIGAL
A" uin work, Thenard ciie. reaction! with soe 1%1 elements,
oxides, salts, acids, and bases with frequent notations of
2
are readily attainable). Reaction control systems using hydro-
gen peroxide have already demonstrated space storability in excess
of 2 years (with an estimated storability of 5 years).
Section 1: Introduction
Section 3: Production
Section 5: Transportation
Section 6: Safety
Section e: Bibliography
C'
Thus, for those users who desire additional details on specific
Items, 'Pousultatiou of the many referenced publications is
: recomk~uude' ,
erenced are from final repor ts, whenever applicable. This was
done to eliminate confusion in efforts whcre progress reports
included incoq)lete experimentation and/or analysis of the data.
In those efforts where a final report has not been issued or
does not contain sufficient detail of the itesm, the e.a* were
taken from the latest progress report giotainiug the pertinent
results.
The tables figures, and references noted in each section are con-
tained in that section for convenience. Each table, figure, and
reference Pumber is preceded by the section number (i.e., Table 1.3
to the third table in Section 1, etc.).
A.
TABLE I.I
IiXICAt CQdSW4TS
7
CONVERSION F'ACTORS
Temperature
C + 273.16-K
F + 459.69 -R
(C x 1.8) + 32 - F
(F - 32)/1.8 - C
K(1.8) - R
Pressure
megabaryes x 1 -bars
Was5
Length
Area
*square ceaitimetors x 0.1551)0 -square inches
square centimeters x 0.0010764 - square feet
- qquare feet x 14 - square inches
TAJBIZ 1.2
(Concluded)
Viscosity
Thermal Conductivi&
Velocity of Sound
Compressibility
k9
TA.BZ-1.2
(Coutinued)
Volume
cubic centimeters x 0.061023 cubic inches
cubic centimeters x 3.531445 •10- 5 -mcubic
feet
cubic Inches (U.S.) x 5.78704 x 10 - cubic feet
Time
seconds/60 -'linutes
seconds/3600 - hours
seconds/86,O0 - days
Force
Surface Tension
10
TABLE 1 .3
TIf AUk1
tE CONVIMION
C V C t C 9 -VC- T C V V
-A"
,-
- -17.3 oj 32.0 10.0 322.0 100*12 260 50 9356 0 043316IOUQ 1900 2712
-466 -4) .47.2 1 353.5 10.6 it 123.5 43 110 2)0 S"6 330 930 -A) 3010 1250 4) ,1,0 27W0
411W *4449 -16.7 2] 35 6 11.3 12 13.6 %9 12" 2458 271 320 960 'A9 10231 351. W7 1120 276
4157 -4)0 -31.13 371.4 11.7 9) 127.1. %4 130 26k 17,7 530 ~f
9% 56 1 03(2 9 6539 1140 2751.
-51 -420 -15.6 4 391 12.1 329.2 10 1%0 251 252 %4 3001 "o4) 19" 11) 1.0 goo.
.4. .410 -33.0 5 41..0 12.4551 131.0 ".' 130 102 98 5 023 456 t(0150 192 1.)0 3 10 2W2
4140 -400 -14.. 1. 42.8 13. 93o IN.@ 71 3.O4320 29) 51.0 040 13 106W 191.0 5491%06 2540
-23. -19W -0-9 7 4%.b 1).9 37 134.b 77 370 330 299 570 10)58 377 33rG17
39) 014 5370 2"")
-229 -140 -13.3 5 Io.k 14,1
4 1. 9 16.1 O5 35b
) 1% 0404 1076 W02 IooUj ,7 5N64)3)500 2576
-23 -170 -12.4 4.6.2 13.0 "9 3,2 50 13 7A 110 30 109 30 !Io 99 1390 2094
-30 -yo -12.2 30 51.0 15. 60 140.0 93 204)592 336 600 1112 4,) 3300 0012 :471
33o 2912
412 -350 -33/ 33 51.5 361 11.8 9 210 10 21 10 33,0 W9 3330 2010 57 10 2910
-801 -o40 -11.1 30 3.6 1.7 b2 31%3.6 120 2k2 1.k 317 624 331% 604 112o 20)40 31l0 u 29
2.ta~opelst t .. -401 -330 .10.6 13 53.4 17.2 1.) 1 0 220 %2 132 630 311 630 3310 2064, OFF l30 29t,(
-19 "320 -10.0 14 37.2 17.5 64 Ik..2 130 230 116 3)0 61.0 1154 61%0 MW 11w
-190 -,10 -9.% 15 59.0 18.3 65 34.50 116 210 161 11. 6)0 1202 1 30 21 59 30 3002
3.13 2 31. -154 -300 - 3.59 1.6 .5 13.9 16 10.5 32501.52 11.9 660 1220 627 3360 920O 941 360 1020
3.67i3i 5.41 -179 294) -5.3) 37 b2,. 39.1 67 32.6 Sri
27 60 500 154 670 123846)w 3370 21)8 9310 1.70 303N
2.22 1. 7.:,, -17, 4-7.75 IF 6%,1. 20.0 61.5 34.1. 3) 210 51635 60 60 125b 635 3350 231.-, 931. 31,0 3056
5.7 3 9.
1.)3 6 10., -1 -173 -439 - 7.2 19 1..2 20.b b9 3b.I 115 220 536 690 .274 1.3 3390 2371 921 3690 07
3.14 7 3 269
4..41 ,4:1 -31. -270 -454 -6.67 20 W0 23.3 70 35.0 M 90 54 1 70 1292 69 3200 2192 9 09
5.001 9I 3. -.31 41 -41 - 6.11 1 .. 23.7 71 159.8 1.9 )01 572 377 730 1)10 b54 3230 2230 9)2 1710 3110
3Z
0 1 .0 1 -17 -450 -418 - 5.-3b 2 71. 22.2 71 361.6 154 330 94 3342 720 132 660 3290 2U8 91s 1720 3120
151 An43 -400 - 5.00 2) 73.1. 92.5 7) 16,.36013201 600 303 730 1316 6(4. 13)0 2246 91.)3710 31.%b
-1.6 -430 -34U - 4,44 24 71.2 23.3 71363.2 36 330 62b 19) 7%0 1)6. 673 3210 26 9 1740 311A
-140 -220 -164 - -0 15 77.0 23.9 75 367.0 171 340 64. 39 750 IM 67 1250 122 94 3710 312
-134 -210 -46 - 3.33 26 7".5 24.4 76 360. I 3 50 662 404 7M 3400 6W 1260 5300 9-0 1760 3200
-129 -400 -25 - 2.75 27 5u.6 25.0 77 17ft 3. 36f) 600 1.10 770 3435 650 1270 2318 966 1770 3218
-123 -10 -310 - 2.21 24 5,.4 33.. 78 172-4 18 370 60 13 750 131. 493 32310 336 971 37380 3234.
-18 -100 -92 - 1.67 29 5.2 6,1. 79 374.2 13) W 736b1.23 7) 1.54 69 3294 23)% 9,7 3790 1254
-112 -170 -274 - 1.11 0 5.0
06 b 0 17"39907341.2P 5 1.72 70 3 0172 923 0) 1272
-107 -360 -M 0.56 131 7. 7.2 1 377.8 O0 400 752 1.5 110 39 730 310 2190 95 0 3290
-101 -1"o -" a0 32 59.1. 27.0 2 179.6 RIOf430 770 453 520 3505 7(6 3 21O 991"320 33)0
- 95.6 -1.5 A0 0.51 33 91.4 U.3 33 35.1.4l 816 4" 75S 41. 030 136 721 330 042 99 1030 33A1
- 90.0 -130 -200 1.11 34 93.3 53.9 84 13.8 523 40 0 19 54 1341 727 310 541 4 40 314
- "4. -330 -154 3.67 " 9 19.4 5" 355.0 327 41.0 524 1. 35
M L1M 7W2 13,0 *1.62 3430I350 1)62
- 79?-310 -366 2.32 36 96.5 0.0 36 3346.5 212 4" S4240 660 OW 350 7V15 360 OW1.5 016 3540 )300
- 73. -51 -146 8.7 37 95.6 W.6 a7 3.6 217 4 560 466 570 15" 71370 249 3023 17) 3395
- 67.0 - "0 -130 3.33 2 160.4- 3.3 1 . 54 1.70 07" 471 NO 1616 749 30 2516 1Or IOU 40 16
-62.v - -112 1.5 19 3nl.5 31.79 1".2. 949 We006 1.77 "a 314 7.0 390 8534 303s 3o034
- 6.7 - 70 - 94 4.44 1.0 304.6 U.2 90 19.0 254" 91, 42 900 1.32 764 3400 2)52 1035 39oo 3452
- 51.1 - 60 - 76 5.00 41 13.5 32.3 91 1".0 W 90 3470 76 3.10 "70 104) 1910 3470
- 45.6 - - 5.36 It
1 17.6 33.3 " 1397.6 49) 90 163 771 3420 2553 1%9 1920 545
- 40.0 - 40 - 40 6.11 43 109.4 31.9 93 399.1. 1.930 370 7 13)0 2606 01 19") !306
- 3%A - 0 - 32 6.6744 111.C 34.4 94 203.2 50 "03173475234403 M 1001%0 3524
- .9- 0 - 4 7.11 45 111.6 3.4 95 0
803.0 310 9503762 730 964 3066 10 5542
-2.5-10 14 7.75 46 114.$ 3.6 96 3o.3 56 960 7934 1760
610 073 3960 5560
17.6 0 32 0.33 47 316.6 76.1 97 *.6 522 970 1778 " 1.70 3673 307 1970 35
I.3 48 110.4 56.7 " W.4. 2 "0 796 5N 340 6 1062 11 3396
9.1.449 320.3 57.5 99 30.2 933 99 1034 53O 14"95 731. 105 10 361.
10.00 0 It.o 37.5 3o0 132.0 5v IG503" 093 3m5"
11/12
SECTION 2: MN[SICO-JIkICAL POPLU1TI
13
drastically increased. Rapid decomposition ctu occur in situations
where extreme temperature levels and/or mass contamination are
present. As the decomposition rate increases, the attendant heat
release causes additional decomposition; this bootstrap effect
can lead to a runaway reaction.
It should also be noted that the data reported for "pure" (or
100 W'/o) 11202 is questionable since there is some doubt as to the
existence of 11.0. concentrations above 99.7 to 99.8 v/o. Some of
the data reported for 100 w/o 1t0 were obtained by extrapolation
of property data of IL20 222solutions of low er concentration, wbile
161
the methods of determining these concentrations are not reported
or are based on an assumption e: purity related to the purifica-
tion technique.
--.
Although it is suspected (because of discontinuities in the data)
,that many of the measurements on the "100 w/o" 112 represent, in
.-
reality, measurements on 20 2 of lower concentrations, p operties
are reported for 100 w/o ll.00 wherever an extrapolation (from
lower concentrations) seems reasonable. This characterizaLion is
of academic interest only because - 98 w/o H202 is the highest
concentration presently available commercially. Future aerospace
industry utilization of higher concentrations appears unlikely
because of practical and economical considerations.
15
resulting from computer curve-fits of some of the data are
presented in attendant discussions.
16
The freezing poirt of "100 percent" 1t202 hau been reported as
-0..61 c (31.17 F), -0.43 C (31.23 ),and -0.41 C (31.26 F)
in Ref. 2.2, 2.4, and 2.5, respectively. Based on a reported
sample purity of 99.97 w/o Y202, the freezing point deter-
tination of Ref. 2.4 was selected as representative of 100
percent I22 . Meusurements of the freezing points of aqueous
solutions of,1120 (Ref. 2.2) indicate eutectics at 45.2 w/o
11,02 and -52.4 C (-62.3 F), and at 6.2 w/o 11202 and -56.5 C
(-69.7 F). The results of these measurements, which are
graphically illustrated in Fig. 2.2 and 2.2a, represent the
temperatures at which 20 to 30 percent of th liquid had
solidified. Experimental melting point otudies (Ref. 2.6),
based on observation of the temperature at which melting was
complete, resulted in slightly higher melting temperatures for
concentrations above 60 w/o ' 2 0 2 .
2.2.1.3 Triple Point. The triple point of 99.97 m/o H 2 02 was estimated
am 272.74 K (-0.42 C or 31.24 F) from experimental heat of
fusion studies (Ref. 2.5). Although no vapor pressure
measurements have been made on solid H202, the vapor pres-
sure at the triple point has been calculated (Ref. 2.10) as
0.26 ma 1g (0.005 psia).
17
for prolellant-grade I 202-1LO solutions represent extrapola-
tions of the vopor presoure data of Section 2.2.2.4 to 1
atmosphere of pressure. Other references (i.e., Ref. 2.11
and 2.12) give very similar boiling polats even though these
toeperatures were calculated from extrapolations of different
individual sets of vapor pressure data. The correlation of
these individual sets of data, which rebults in the newly
calculatLd normal boiling points, is discussed in Section
2..2..4.
18
2.2.2 Ihase Properties
19
10(~' c -100479 +. 2.455 x 10-31 + 1.7831 x lO-W-6.76 ~
20
Curve fits of theme calculation~s are presented in Fig. 2.5
and 2.5a.
2.2.2.!i Vapor Pressure. The vapor pressure data resulting from four
different experimental measurements (Ref. 2.11, 2.12, 2.20,
and 2.21) on various aqueousfo o~utions of "202 over temperature
ranges of 0 to 90 C (32 to 194 V) have been correlated. Using
a least squares curve-f it computer program, these data were
curve-fitted with the following equations (in the metric
Sys tem):
21
,95 wto .~""
W J... ("g),a) -7.68235-
log P(m 16 47.17
(K) T(K)
12S665
2 og '(n
...."" fi) 7 729 -1606.47 =
w/o 0 0 (H 7.67297 - ~ 176
T(K)
T(K)
T(K) T(K) 2
T()(R)
(R) T(R)
log P(psia)
" 5.67747 (R) 60()
T(a1)
2
75 w/o 110 -
23
2.2.3 T~hermodynamic Properties
The AHF data for the liquid and solid phases of propellant-
gade H202 solutions are given in Tablcs 2.3 through 2.8 and
Fig. 2.12 and 2.12%. Figures 2.13 and 2.13a illustrate the
AHF of the liquid at 25 C (77 F as a function of composition.
The heats of formation of the vapor of propellant-grade H2 02-H2 0
solutions are given in Tables 2.9 through 2.14.
24
and 2.14a. Heats of vaporization of propellant-grade 11202
solution. at other temperatures can be obtained by computing
the difference in the heat. of formtion of the liquid (Tables
2.3 through 2.8) and vapor (Tables 2.9 through 2.14) phases of
the VH22-H20 solutions at the corresponding temperatures and
11200 concepitrations.
p p. 23 ..
heat capacities of solid 11202 were taken from the data of
Ref. 2.5. Since solid solutions of 11202 and 110 are not formed
mental data from the curve fit of the data with increasing
temperature. The differences in these data from extrapolations
of the data presented in Fig. 2.17 and 2.17a, which are '0.0l
Btu/lb-F (cal/gm-C), ere assumed to be theresult of H2 0 de-
composition in the experimental study.
,0 2.2.3.8 Enthropy and Enthalpy. The entropy and enthalpy of the solid
and, liquid phases of propellant-grade H 0 solutions were cal-
22
".culated from the other thermodynamic functions given in Tables 2.3
0 5.
5~2j'
through 2.8. The basis for the vapor-phate entropy and entbalpy
data on propellant-grade H202 solutions, given in Tables 2.9
through 2,14 is discussed in 8ection 2.2.3.9.
U1 -3610 cm- 1
r O-H - 0.965A
u 4 - 520 cm-l
V = 95 degrees
2 U 5 m3610 ia-1
IA n 2.785 x 10-40gm-cm
2.2.. Transport.]Properties
27
2.2.4.1 Viscosity. Experimental determinations of the viscosity of
liquid H2 0 2 -I0 solutions ranging in composition from 0 to
100 w/o !102, have been reported in Ref. 2.6 (0 and 18 C),
Ref. 2.24 (0 and 20 C), and Ref. 2.22 (0, 25, and 50 C). Curve-
fits of these data at 0, 20, 25, and 50 C (32, 68, 77, and 122 F)
are graphically illustrated as a function of w/o 1YO2 (from 50
to 100 w/o) in Fig. 2.18 and 2.18a. In addition, viscosity
measurements have been conducted on 98 w/o lO 2 (Ref. 2.19) from
20 to 85 C (68 to 185 F) and on 90 w/o 11202 (Ref. 2.18) from
77 to 325 F (25 to 162.8 C). The data for 98 and 70 w/o 12
from the various sources has been plotted as a function of tem-
perature and compared to the viscosity of water in Fig. 2.19
and 2.19a.
where
'2
Using the two experimcntal data points, the thermal conductivity
of 98.2 w/o H202 was extrapolated to the critical point (Ref.
2.31). This extrapolation, shown in Fig. 2.21, used I,20 a
reference substance and assumed no deromposition and a thermal
conductivity of 0.100 Btu/hr-ft-F at the critical point.
29
These properties generally are related to the electronic
structure of the atoms ia contrast to the transport properties
which involve only molecular movement.
2.2,5.3 Dielectric Constant. Figures 2.23 and 2.23a show the dielectric
constants of propellant-grade It202-1120 solutions as a function
of temperature. These data were interpolated from the experi-
mental studies reported in Ref. 2.39, in which the dielectric
constskzts were determined as a iunction of composition at con-
stant temperatures from -40 to 30 C (-40 to 86 F). because
of the supercooling of the !1202-4120 solutions, measurements
were obtained on the liquid below the freezing point. The data
from the measurements on 100 w/o It202 were curve-fitted from
-60 to 30 C (-76 to 86 F) to the following equation (Ref. 2.40):
2
C - 84.2 - o.b2 T(C) + o.0o32T (C)
30
2.2,.5. Electrical Conductivity. The conductivity of "pure" 12% has
been reported by several investigators with values ranging from
2 to 0.39 micromhos (microolus-I ). Experimental studies (Ref.
2.41) of the (.nductivity of unstabilized i1,02 were coiducted as
a possible means of determining its purity. The results of this
study are summarized as follows:
31
-L.polarized light. This is expressed as:
"k t'H
whlere
Ot - dege. of rotation
- path length
ii - field strength
k - Verdet constant
V
Xg 10 6 -0.720 * 0,218w
wiscre
w- weight fraction H2 0 2
33
Hydrogen peroxide is the simplest molecule having an internal
rotation motion, and, therefore, has hod fairly extens.ve study
'with respect to absorption spectra. Hindered internal rotb-
tion effects are observed in all regiuns of the spectrum.
Extensive studies have been conducted on the vapor, the crystal-
line solid, and dilute solutions. Less work has been spent
on the concentrated liquid 6olutions, because of decompooition
effects and t2 diffic"lty in fiuding suitable window materials.
Since the 6pectrum as a whole is very complicated, it is con-
sidered beyond the scope of this handbook; thus, references to
H 2 02 spectrum characterization are provided as a guide for
interested ind-viduals.
2 3 C_ fMICAL PROPERTIES
35
chemical nature of the proposed solution as well as the solu-
bility of the solute before solutions of H2 0 2 with other mater-
ials are attempted.
36
2.5 GELATION
37
7 forced convective heat transfer. It was found that heat fluxes
its high as 11.75 Btu/sq in.-sec (at liquid velocities of - 80
ft/sec) could be obtained with 90 w/o 1202 without complication
by decomposition of the hydrogen peroxide. A least-squares fit
of the heat transfer data obtained on 90 w/o 11202 resulted in
the following expression:
1/ 3
(N )f - 0.0287 (N~ 0e'f0(Nr)
38
to the fluid velocity by the relationship: heat flux -
0.21 x velocity. These results indicated good correlation Gf
heat ilux and fluid velocity with the studies of Ref. 2.102 and
2.103. During these tests, no appreciable difference in heat
transfer could be associated with feed temperature, and no
detectable decomposition was evident. Four similar tests with
90 w/o hydrogen peroxide indicated no discernible differences
from the results of the 98 w/'o hydrogen peroxide tests. As in
the studies of Ref. 2.103, the Dittus-Boelter correlation wab
found to represent the data more closely than either the Colburn
or Sieder-Tate relationships.
39
handbook. Howevcr, because a detailed characterizatior of
these parameters would involve a discussion of system design
variables (such as configuration, intended use environment,
operating sequence, etc.) that are beyond the intended scope
of this handbook, this review of hydrogen peroxide ignition
characteristics is limited to a general and brief summary and
reference guide to various ignition studies previously con-
ducted. In addition, this summary is limited further by the
security classification of many of these studies as opposed
to the unclassified nature of this handbook. For the purpose
of clarity, the characterization of hydrogen peroxide ignition
is 'presented in terms of its two primary application areas:
monopropellant systems and bipropellant systems.
4o
catalysts used in the decomposition of hydrogen peroxide
concentrations ranging from 76 w/o (Ref. 2.109) to 98 w/o
(Ref. 2.18, 2.110 and 2.111).
4i1
500 m to several minutes depending on the technique employed.
Ibpergolic slugs of Iydrazine containing mixed cyanide salts
(Ref. 2.18) have produced initial start transients (i.e., the
period measured from injection of the hypergol) of 10 to 20 me,
but this technique required 300 ms hydrogen peroxide leads and
500 ma hypergol injection periods.
42
peroxide in a catalyst chamber upstream of the main combustion
chamber) as the ignition source. Through the use of this con-
cept, successful system ignition haa been demonstrated with
various liquid (including those noted above, as well as with
JP-5 in the AR-2 system), solid (Ref. 2,114) and heterogeneous
(Rtef. 2.104) fuels. Ignition delays between the hot decomposi-
tion gases mid the fuels are minimal (5 to 10 ms), althiugh the
system design controls the overall start transient period (ie.,
from injection of the hydrogen peroxide into the catalyst chamber
to the achievement of main chamber combu tion). Many system
designs employ only a small "pilot light" catalyst chamber with
subsequent main stream liquid injection (which bypasses the
catalyst chamber), while other systems utilize prior decomposi-
tion of all of the hydrogen peroxide throughout the operation
of the bipropellant system.
43
2.8 iUa'U"CJI
2.4 Socco, E. A., Ph.D. Thesis, Laval University, Quebec, Canada, 1953.
2.7 QFR-LU-15 and 19, Freezir Point, Depressants for I &,1"1C Corpora-
tion, Buffalo, New York, Ccitrat 110a(s) 53-10341-c, 1963.
779-c, 1954.
2.9 111-78, Part I, Final Report, Low Freezing llydrogen Peroxide-Based
Propellants and Oxidants, FMC Corporation, Buffalo, New York,
Contract NOa(s)-53-103'i-e.
212 Scatc hard , i., G. M. liavantigh, and L. 11. 'Tichi)or, " Vajlm -Li qtd d
lKlu Ilbri mu. VI. llydroreix Peruxid-Water Nix , Chem.
J. Antes.
Soc., 71, 3715-20 (195'-').
2.13 Kay, W. 13. , "D)nsity of Hydrocarbon Gases and Vapors at High Tempera-
ture and Pressure," Industrial and Elginering Chemistry, 28, 101h
(1936).
45
2.'22 bulletin No. 07, lb"iyrozzc9 Peroxide J)hysical Pioi~ertius Dataibook,
'MC Corporation, Buffalo, Nov York, 193.
2.1' iguere, 1'. A. nd I. 1). Liu, "Iteconurended Values for the Therwody-
numic Plopertiem of iydrxogen and lDeutcritun Peroxides ," J. Am. Chem.
Soc. , 77, 0,77-9) (1955).
Ites. , 18 - 91 (19w0)
'-))Is=.=
,Call, J.
of Vapor Mixtures of' Hydrogcn JPtroxi do and hsater, " J. Arm. Chem. Soc.
2.33 McM-utrie, It.L. and I'. G. Keyes, J. Am. Chow. Soc., 70, 3755 (191.8),
us given by Ref. 2.22.
46
2.39 J.tkar, 8. K. K., "lipole HoJwutm of V'olyatowic Muleculue," N4ture,
._.2., 316-17 (19 1').
2.36 Amako, Y. and 1'. A. Giguicx, "Cialculation of the 11,0 Holeculu by
the IAAO-HO-SCI" Method," Cun. J. Chem., 1hO, 765-7/1 (1962).
2.37 Maissey, J. T. and I). It.Bianco, "lhe Micowlave Spectrum of Hydrogen
2.tI A}P'L-TI-66-13, Final ltelort Itedearch on the Stabi lity of Ifigh Strength
10,00 E. I. dul'out de Nemourts and Company, Lic. , Wi hini ngton, N laware,
Conti-act AIF04(611)-I0216, Hatch 1966.
47
2. 485 Giguere , 1'. A. utid V. V. Sclifiownke, "Aii EU ct.rosi-IDi fractti ol ltudy
of 11,A), witd Hydi'uzzi," J. Am. Chumi. Soc.., U, 2025-9 (19113).I
!2. t4 ) Itodingtoii, It. L. , . Bi. Olison, and 11. C. CrossM, "Hlydroge~n P'eroxi de,
Itil zred Spect rwu iond the lziteul, Itotati ol Przob lem," J. Chem. J'IiyI.
1(-, 1311-26 (19w2).
2.50 Illujt , Rt. If. , It. A. 14vauch~k, C. W,' Peters'M, wald K. T liecit, "nteoruuul-
Itotutiozu in Hlydrogen Peroxide: the Jur-lzuivured Spectri-i-i aid tile
IX, tzi nti on of the Ili Aide ii jig J'ol'euti it I, J. Chema. I' ,s42 (W)
2.51 Masseuy, J. 1'. iad It. IV, Hurt, "J1,3fuut of ui high ciliUrrieri onj the
Mi c'oiuvu SPectruw of Htydrogen Peroxide," J. Cheri. JIy.,~ 4
2. Ta Calculated,
~.4)"u I1~J
w *
l'uroxide-.Piyicuad
thius study.
5A"% l 1111d1 1" F. Gr tfn
2
I
2. 56 Klunutuck, M., Beichte, 2L, 108 (1918); J. Chem. bop.., 111, (11),
107 (1918).
2.57 Jamiesona, G. b., AM. J. Sd.-, 1*4, 150 (1917); 1-d. WuJehind, !aM
12.61 llanebrack, K., licriclite, 20L, 213 (OW~); J. Rusnw. anid 0. Kalluzwzer,
.2 Hssonuz, 0., Proc. Chum. Soc., j ,i7; J. Chum. Soc:.vp ''t 10)
° 2.3 tSchum ter, '., Z. anorg, al lgem. (Qbwm, 1W, 253 (1930).
2.70 KintiLAkowksy, W., Z. phyiCik. Chew., 22, 43' (1900); E. IAeck, ,AMoth,
"tg, 4 87 (1919); 14. 1(bui, Holut'iA., 66, 393 (1935); 0. )laudibuh,4
Science, 108, 443 (1948); 11. B. L il, Proc Indian Acad, Sci., 36A,
244 (1932); D. D. Deord and A. W. Davidson, J. Am. Chem. boc.. 73.
- 1'69 (1951).
1 "49
56 (15 E- J. Doel an A. W. bi rky, Tri .aruday Soc., I'L,
580 (1951): W- C. E. Ifiigi1L)SQJ, 1). Sutton, und 11. Wh'jjIt, J. A.
Sboc., 138U 6a953).
50
L. Abel, Huw . jM, 1239 (19U7); E. Abtl, Houut.h., 2., 821
(1913); E. Abel, Z. ;Jyktrocbeg., 18, 705 (1912); L. Abel, Mountusi.,
U,, 798 (1950); Y. Usumia mud T. Oku, J. Chem. buc. JAtn, Ptue
Chem. buct., nj, 4e (195U).
'_.8 1.+,i.!tv, j,
lwcbig, F., tr 2743 (1885).
2.89 Thonmen, kxu. I'hys., (2), 11, 19, T); S. lluebelkog, Svend.
(18"'
YU rm. Tidi., ;, 149 (1921); 11. Lido and G. Ythuyunw , Sclciece,
Itepts. Reseurch 1n&ts. , Toboku University, ber. A, , 49 (1950).
2.90 Schluck, G., Muutli., a7, 489 (191b).
2.91 fliggimoun, W. C. L., D. Sutton, and 1'. Wright, J. Chum. Suoc., 12.2,
1380 (1953).
2.92-' Jul-, K. J.v, l' l.. Ger. Sci. , Purt 111, P. 170 (1948).
.95
2.93 Oddo , K.. and
Klyachko, IA andRAng,
Y. A. lDlevLchtiovu, Dkludy Akud.33(92)
L. 1. Gu.chn.il,51I Nauk. S.S.S... ,
b, 8~23 (1947); Chew. Zeatr. (RuMwiau Zone U.), 121t, 11, 555.
II 2.94
.95 Nee, B.i., and
Oddu, B. binughi,
P. It. Guzz. (framn
IRePort 74717 chiii. 199-2U5).
itul- , 31
11I 192i 4
(1923).
2.96 Greeuspa, F. P. imd. b)&. Chew., R, 847-b (1947), us givel by
IRef. 2.55.
-51
2. 100 LILIL5-20, -No#iai Gertui Vy c4iei&J)al~ne~ of Ligiiid
t'oz elLWufjl, T'eclujidyt, Incorpuzruted, West Chevster, Villinsylvuliiu,
April 1965, CoutI4ct 1)A-30-034.-ANC-OI53Z, CON1kZFl'1FA.L.
2. 103 btudlev done by J'rutt and Whitneuy, as reported by James McCuruii ch,
Alydrogea Peroxide IRucket Narrwul, I"MC Corpurutioni, b~uffalo, New Yorh,
4
2. l0'i AG42 10785-03, kulrterb- Report. Advanced J'ryupelinit 6tiLd(-
ComubustLion leasi biIi ty I'ro>win, Acrojc t-4iencriAl Corporati on,
5.2
L b"
CONFIDENTIAl .
53
TADLL 2!.1
. ait
'.
n
Bgi properties's.1.3L
. b'u t17 o" t4 C1.7 t &ita 9. .~. t.
1
sod S.e puke U1-7 a t)v LU.a atU~a1 ~ 1b 0a1'a1' I
Iatem lo
Adabti
s*- .4 o ~ vA1 .4o,165.1.1 1.w .- ~ ,9,1- t
4
3.40
.lowI
poln9.6",
o-
tso
TABLE 2.1
(Continued)
Thermodynamic Properties
Soats of
cal/g Stu/ib -1320 -2376 -1369 -2464 -1'4-4 -601
Formation
Gas
Btu/lb-F 0.303 0.30 0.306 0.300 0.310 0.310
C cal/g-C
Entop cal/g- Iitu/lb-F
Enropy Cal/Ig- C Btu/b- see Section 2."
cal/s Btu/lb Be* Section 2.2
Enthalpy
Transport Properties
Viscosity
- - 075a1
lb/ft-sec 1.153 0.770 x 1u 1.158 0.772 x 10 1.160 0.775 a 10
Liquid Contipoises
-
lb/ft-eec 1.91 10- 1.283 x 10 5
Gas Centipoises
Th rml Conductivity 3
Liquid cal/cm-eec-C Btu/ft-bhr4 1.40 10 0.4
Gas cal/ca-eec-C Btu/ft-hr-
Coefficient of cm /eec in.2/8ec
Diffusion
Sonic Velocity
Liquid %/soc ft/eec 1781.0 5843 1774.6 5821 1767.0 5791
-1445 ..a601 -1571 -2628 -19%6 -3503 -3070 -372to T2.3.. 2.14, 2.35, 2."4
12. 12 -2. l3e
85 153 18 148 77 138 72 129 T2.3- 2.0 2.2
376 677 369 700 427 768 438 789 T2.3 -2.1It 2.26
F2.14, 12.14*
.1
2.4 14.2 14.3 7.6 8.15 14.65 9.0 16. 011 F2.15, 12.15. 2.2b
see Fit. 2.1o and 2.16&
12.16, 12.16. 2.25
10 163 0.75a 1.150 0.777 x 10-3 1.136 .79a 0' 1.123 0.738 a 10 1.2.18, t2.18& 2.6, 2.22, 2.24
12.20 2.30
12.21 2.314
1767.0 579%s 1758.5 5745 1706.9 5598 1690.3 551.3 F2.22, F2.22& 2.16
TABLE 2.1
(Cor.c luded)
sl.t,.mdmtie rpit
Ledesa iS 3.raties (Goile 3-Li..)
1
Electrical Cmd"itivity me-lu SeSet.
J 91i"l~ip~lt _______________________ se T
madmtis 0"
Pooribilty
30a
to C 14
rBLE 2.1
'oucluded)
I."1
lpoo'l~ ~ ~~ !rd Va ) .03 k
KI:Ann9I a -~4..
C, &-VQ. ~ N *Vs3.g-
~eI.0 0 0 0 0 0 a 0 Q e00
C 000
00 00000C C
Wo 0 . re r0 0
gl IA I' R I " . EC
N 1
C-4,
LL4 alL
z .Z
6-4 t3 4. .44 44
ow)~ Ow~' - N-
57
cisE~ A I I-
G~. a
J- L
o . . .
a 0 0 c o e 4 0 a0 v 0 * c o 0 0 0 0
_ _ _
VI. _ __ __ __ _ __
* E..
Pic. 1 %0
. . . . ..
PO 3P4* * * 4 ** * .4
c 1-
wV\0 Pi ~ U .~
5C4
C!i
0 C) 04 0; C c~
95
41
4 .) - 04 P. - - - 4 - - - -
(m a lU- -)
C4 tI, -: A o
go r.N 0- r- i WN
C'l OU~
*4j
-- - U'a
c~J 'a
:3 1
00000009999909
.r
0o
j.J~~o 0 9 0 0 0
4.)i N
60
G) vt~
C) V, C4J -I %o o 0- tCJ
~- - -- - W - - - -
U- ~~~~
~ ~ ~ I D t e\ -W
t \ 0* ' _l
j iN t- - -U-o C
-- -
.4 -)0C)0 o-;C ;C ;C
Wt P4 e2
Im Ar.O hll
00
4-4 'I
C
.- ' . d I- C'J ou ) f1- a.p 0 in
C- d, W" wr W A&r e~ S' IV~ w
~ V' CNI 01 C2I N CI C
C C-4
04 C J NI N' N C4 CIA
S In ff I r crI I Ir 04 I) Iu S .1 l I-
f- I- - - -r - - - -
.. I I I I II I c !"I In In I I I
) 6
vC to T oO NO).C O n0 SC 0
.r . .. .
-:
I s I u W - o c o -
C;u
C.P-4
CN t- ,-l M. u C
VIAu ~ u u
i i, i~ I- i I
cyi v, tiI I
t V
o,% -e'
C7 - -r - - - -n -
-rW rNV-t.11 an in~ b-, &n in- &r- in- if-* Srn In
P-
"-. v &.-W V~ r-
0.
s4 -0
+00.41.
1 14
ON - 4 - - a l, ', I -. e"\ O.
In4) .4.440PI
-44
#01V\ V d
-0 l Ol404 v'441C
N444C1
00 or - -
_T e -,
tN -T -- 0
00
.w
M~ O4 04 te,"I,- UN 0-4 C4 C;
L0 I' I -4 -U
+~) -4
a w 06 '0 o. '0 8. '0 '0 '0 '0 '0 '0 '0 '0 Q. '0
( 4 ODP-
EA 4. 0 0v 0PIN00
1.- 5-0 0 0
a r-4
.0
%4 0
o -4 WOO%
to% -i O t % '0 LM 1 %D O 0
r4 p4P4 "0 P-4 P- P-4 r- -4 - -4 r-4 -4 r-
C.
$4
+) C; C;C C ;C;C ; )
0'0n %0 040 01
---0 4 04'% ICN n -W e
F-4 340
.0 .p
P* U INC I . l W '
0 1 f0n N N - - r4C% O
0 -U At el~ %1 4 CCJ -s LI OD
I cii 11 11 r:- In:;; I
-c
1:O14tA
0o
.I t l UD ~m irN irN Ir,
P-4 -4 P-4 P- .. 4 ,4 ... 4 - -4 -4 r-4 -4 0- -4 'A
A0 Uir %o
CN trl olU-
r- %
0 0
0 tf
Ch
OD-W
00 OD
0''.10
NNFr- tNCIA
>,.C'
000 -. - - a,~
1I7 0 C4~ %,6'. 06
rli
C - f'% W%~ r- cys -4
V% T D r'-0OD '.o c'N
-4 N CI.0
N~\ OD 4 -ir 00 C 1.0 -4 O C4
-4 0 -t' 0D N 00 -1' - M 0 %D tfl 0% No0
.. Cd
t~ LL~0 14 rN - N - 4 W Q
-4 N4 r-4 r-4 04 Nd 141%41, W "I% %.o
0 0%Q0- tU* 0 OD
NNCI o'%OO %0
U 4-
td' -M 4 %V0 0
CW OD 'Z0 -r CIR O D ; N
teO 1 OD 0 0 C
-. %0 tC - n r
66
r4 I
* FU-
.0-
-4 . 9.f
%w
Q~~C C% v -
OD- u C; C;
1-44
0 04 r,: j0 4* 4'-
4 u s4r l n N P4
C)
a ~ ~ 5-- P4 - .4 P
C4 C5-
of _ _ _
N_ _ _ _$_P4_ N "_ N_ _LI
*4 "10 Ccli 67 %
o in o I'wt
LIN - - - - at - f p4 - P-
VI Nca r4P 0 -0 0
. . o. 1 . .4 .4 r
-- P t' C4 -4 oN oo aD- C% 0-
O %D r%
Q'- - 1- r- r- OD OD OP OD N C N% N N 4N ND N
'~ 00 00 0 00 90 0
41
-41-
I-'4
N C*4
N
.4P.4
0o w w ; w & '
r-4 4 -d r4 P- d w .-
I I I " I I I I I I I I
- i ef f- 0N r
4
to -
tf- -" r r4
c..d - . CI -4-
o~ C 0! Co
VI N
eFa
ODa
C;0
.d
r % C7.
60 NA 4J
C; C;
C; C;C; C
OD C0
69
_ _ - P
V~~ -A W ___M
OW Sr - % t -
0 C4 C4d Nd NO Nd ca co C4, I C4 N NI C4
Or0 0 V -LI e
41. -, L ION 0T ~
Cj 00 Ar r ' r- Lf
cl v
c ~ 4 0l 0 C 1 0 0g) 0O 0 . 0 00M
I~~ - --
0 C ww D -W N ' 0 10' Ci D 0
etp- Ag-..N' r% IN n-
If% or% 1% to, m .
70
TABIJ 2.9
71
TABL: 2.10
Enthalpy
Teuperature Heatca C-
I/g-Icty ca A/ -.,k
Entrupy ("1 11298) Yeat of Formation
K a (Btu/I-4) Btu/Ib-4R2 cal/gm Btu/Ib cal,/gm Btut/Ib
72
11515 2. 11
Dthu Ipy
eat cpaity Eitro,,y (ca _ IL) mtiu
of Furm
(" - 298eat
a (Btu/lb-41)
city c&lropy
(Btu/lb-Ii) cal/gm Dtu/Ib cal/gm Btu/1b
B sCa
Teapersture
0 0 0 0 -79.0 -142.2 -1024.9 -1644.8
FJUa
L'v (
in a8;DL I I . I I-
ll f
..6 l
).9 180.
d,9YA7 .v I
-I. -n
.- I ta..
-L7044.v I
Te
-- Ileat Capacity,
cal/gm-&
Lutropy,
Val/gm4
1 ,(Ii 8
'1"298'
Blout of
Fox mati.;;
IL II (tu/b-L) (Btu/1b41R) Ca]/gni Btw'lb vu/gm - Btu/lb
0 0 0 0.0 -81.76 -147.17 -1137.8 -2048.0
100 180 0.256 1.38 -56.34 -40U.41 -1157.0 -2082.6
200 360 0.277 1.56 -'27.55 - 49-59 -1167.9 -2102.2
298 536.4 0.317 1.72 0.0 0 -1181.5 -2126.7
300 540 0.318 1.72 0.58 1.04 -1182.0 -2127.6
'dO0 720 0.351 1.81 34.l k1.i U -1191.2 -2144 .2
500 900 0.379 1.90 70.69 127.24 -1198.3 -2156.9
600 1080 0.400 1.96 jo9.73 197.51 -1203.8 -2166.8
700 1260 0.416 2.03 151.53 272.7 5 -1208.1 -2174.6
800 1440 0.429 2.09 192.91 347.24 -1211.7 -2181.1
900 1620 0.4A42 2.15 236.50 425.70 -12141.7 -2186.5
1000 1800 0.452 2.19 277.59 499.66 -1217. 2 -2191.0
110 1980 0.42 2.23 326.92 588.46 -1219.2 -21911.6
1200 2160 0.471 2.27 373-57 1672.43 -1'0.9 -2197.6
• 1,
,I.. 0.479 2.31 2.0.97' 757.75, -122.
1400 2520 0.488 2.39 469.42 84.96 -1223.3 1-2201.9
7'
MIE 2.13
75
TABLE 2.14
Enthalp tkat of
Temperatture Heat Capacity, Entropy, (I -4I298r
("-28Formation
cal/gm-K cal/gm-K
K R (Blu/lb-R) (Btu/Ib-R) cal/gm Btu/lb cal/gm Btu/lb
76
TABLE 2.15
77
TABLE 2.15
(Concluded)
78
TABLE 2. 16
79
TABLE 2,17
-24 m/. e
Polarisability 2.30 x 10 c.4oe1 25 C 2A3
so
VA 2.18
-tructure
Structural Parameters
~~R(O-H). A (
0(ooH),
deres.degrees (oooo),
A degrees
Electron Diffraction 1.4*7
Microwave 111.5
4o
TANA 2.19
Reference
INOiQA.NIC CWMUNIH
AS 4- 1202 acid S dissolves (Ag ) 2.56
PI-A (OH)2.10
PlAs0 - 2.17
As03-3 H
+ 2 02 1O,
alkaline_
Oxid' A gold + N02 a - reduction 2.58
82
4
TABLE 2.19
(Continued)
-1 + N02 alkaline or
CO neutral no reaction 2.63
Fe + %102 F + e+ 2.10
83
TANX 2.19
(Continued)
Refereace
12 + 1202 .- 1 Jl 10 1 2.71
-2 2.10
MOS2 + 11202 ,--S04_
Ni 4H HCl or 0d l 2.10
22 H2 SO 4 -
H+
NiSO 4 - H0 no reaction 2.72
NAI
4 + H202 - various products depending upon conditions 2.73
84
TABLE 2.19
(Continued)
Reference
Po 5+
5, 1202 + 1120 H3p' 5 2.78
,n . a
Pt + 1202 no reaction & &I
85
TABLE 2.19
(Continued
Reference
O -2 - 0b- 2
2 2.85
11202 2.86
Sbb2S3
s antimoniate
Sc
+ 5e2 2.87
2.10
Se 22 2 eO
Sl
2.10
I2 Se + N202 . rapidly attacked
-2 2.88
SeO 3-2 " _22 S SeO
Sn + 2.89
Sn +2
2.90
Te + "2 0 2 ski 6Te0 6
TIOH 2.10
TI + B202 .
23TI203 2.10
TI0 2 + 1202
W + H202- _____ 0
2.10
96
UWA1 2.19
(Contirnued)
RWference
f3RLWIC CcHP0IMWS
Alkanes:
Alkiiues:
= !W4+
. - - -4 h--4
fl '+ %%RISH'OB
j0 j~' --. 2.10,
4S N' 2.55
glycol
87
TA131E 2.19
(Continued)
Reference
ROR
+ co ld wito reaction 25
H202 noe catalyst~
Carbuxylic Acids:
1% H2 SO 10001+1
RCOOH +HO202ROO 2.55
peroxy acid2
Aldehydes,:
R-COH2 2 80 C -9-RCOOH 25
H+
Aromnatics:
Refecrence
OW~ANIC COM~POUNDS (cont.)
Aromatics:
Aniline +- u2C2 22 -
2 3 C baniline black products 2.55
Primary Amines:
Secondary Amines:
* Tertiary Amines:
89
00
j t14f I1m
11
A'111i 1 1
70 tO0
WEIGHT PREtill0
~~
9011
0
T-0
1 4 Ci
lit-.4
11MIN11"I13
14 M
ttC
OD/
IM
11 it
Sn
VIM :1 t 1M
WINMI 0
4,++4.. *i
44- 4)
_4414
ME0
~ ~ ~
. ........... ~ ~.
... ~ ~ K
a -4)
04
911
I-AM11111111 Mj113 HM
'd iHIPth
411111TS"IT it 11,0
1 lit 11ql [111t ItIM"' lifii'lali
fl~10ifilfiff1 il li11
1 tI I
11 1-14 In,1444444,11111
11 "fllil'til
H I ilt 119
ItIUJ~it'l Jil 11-1
1 tj iI
W i 01
liltif 14
111i IH I I I ilt
1 IM 11t
111 fi mvm 111HIII Z-
411 AM 11-1!i,14:1 11R0
4,'10
"410 * 1 "IIT
MR- H.
1911"A1111
lff *,~:
1911f
14 B l 1114 A 'I-1 t W IA0e
4 lilt tI
H I~ I?* :J 0
f92-
430
Ix w
4
Iw f
110 w
42
f II 140R-
0 Rfl 1M1 1
TOO 00
70 mm 4w0 '410 10 70 g I0 111010il
0M
WEGH 'ERE
M N1 T0T
Fiur 2..Ciiaaeprtue:rtclPesre n oln on
of Pr4lat11d1yrgn eoieMte ouin
36 2693
0
02
QN
I ASH
0i~"4,
NH;, it H if H11
OM
TAll K HN !H1111
. .i .. . .. jr .
ft (u
It,-
-fit
......... N ,f +
1 fit
ftC.
1 1 iTH
If -
00I o-
IN
4p
CL
Cl)
z 1
0
w S.0
-IH
ill1 5, w iy
:1 ,1, 11~:~
!Wi < '
7.4
zW
w 70 809
w 7.6
z
0 4.8
411
0T ill, i.;
Ow I fl T 1
14 If ii, Jliiwo P-vt" flti j
~
itz r24
I VII r' _
Ii
4i ; ITT ~
Fiur oefcets(uial
1.a fTera xaninfr
N yrgz Peoit-ae rplan-rd
Sidution
IL I97
III4
1 i
IIT
ITCUV Ir "'I O E 2. !I
lit
2.~.j4 *ilk ~
if~p .9 No
W4GH PEREN I ,O.
2.6.
Figure Aiat Copesiilt ofiriel't:rd
titoenPrxdeWtrSouin
I98tlk 1
if~ ~ tl It- 4
II
04I
t i i
~
4: ~TJ*',,o I ' 1
T
41 II hk-f il 411
14.4t 1
70" ii100111 t !
~~~~~ qE(~1
tECNTH
Figure~~~~~~~~~~~~!t roeLzVGad
866.Aiba4FCqesiiiyo
Ldoe
PeuztD~a~ 4oltiikl
* ~ ~~ * ~ L41,I'% . .
1000- -
------
Soo
600 It
........-
Z= Z L
:Z 7Z __7
200.___
EXTRAPOLATED DATA
100 (ASSUMING NO DECOMPO ITIONN
t _t a I I 4 I 1 4 :-t t -- A
so
E 60
E
if-2-f- 100 W/O 2O
UF 40 98 W/o
5
-_ -.--==F:- = - -
w =--e m.090 W/o
ac ------ _T
10L.20 70
Ix 70 W/O __t___
0
> io
0
4 t 4 4
100
20.0
------ 4+- M_4*
-- -- - -- - - -- e.
10.0
.00
8.0
4.0
EXTRAPOLATEj DATA
ZE -t(ASSUMING NO DECOMPOS1100h)
:7-T
2.0
tv t
?v
1.0
K 0 V/o NX 09
0.8
Lj W/o
0.6
4 +
OQL
go *,a 1.
A H
IL
- - -
73 W/o
_-:7
0.2 T
>
1_r4
H
T_
0.1 T
CLOB 4- El 14 ' 11*4 1 1 111
T_'-T
a0e
CURVE FIT OF DATA FROM RE
2.11, 2.12,2.20, AND 2.21
OL04 -
-4-4- -4-- -
_T_
CLO I
40 60 So 100 120 140 160 180 200 220 240 260 280 300 320
TEMPERATURE, F
101
11 Hi : tl ! I M 111
1il 000
so
I
I70 IlIil i 1 I1
1 1 V!l
60i Ii.
c 0 4j
S1
v
T4~ ~ ~ 1<
0 O a 0 4 060 0 60 v tO
510
lid I
I.0l
tt 1
30z8F
foT0......
60C( 4 ) -;
-
-- I
0
0.6 0.M10
0 103
I t
0.2
4
DAT
OFRF.2
DON~~
z 0 0 ow04l.-08,.
MOLE~C 7RCTO:j0
Figure
Ativity.10. oefficents fo Hydroen Perxid-teSluin
I(ReL 2.22)
~1____________T-10
63 T~ oil~4
I: 4 i-T IT,
1 4
Iii+
.... ...
1 1~I
,~~7,,
tit
t,i .Iw1 ~lI
;t i til I4!,Ii;+4 iti
......
I I
4,4 4 -
114
T: l!: -'
-i
5.8F2~
_
'7
4i 4
OF.R 2.24 1
0
Fi ur 7
2. l .
Si f c
e si n
o? h d
o e e ox d
- a e
o u i
4 4
0106 2E 5.44
-J30
DAABSDO NEAT DISSOCIATIONJDAT
ffiiiIitHI-ILIUDH~
a 2 'oI IIII 1 11
U1 II-li
-I(=
ItI
i-1107
..
.t ...
-4100 TtIITt l
i HI
70 /oHe00
II
TE TURE, R
10
2000
T1
00
1500N
BASEDlO! HETOF'SSCATO
70 80 l90 l 100
WEIGT
PECENTHZO
16109
- 3800 _
-3600 1!1--
0 13 1b1 .11'''
Lj~
1.4P4~
1,_j~i
~
..1
fLill1
i
T
-30 -
TwI
1111L" lit
110
Go6001Z
300.. .....
if1
40
00
0MT
I1I
0 4400 I
H- li
1100 *
1000 1 ' 4j
I t
~t
t
S0 0
IIT
F-7
204 08 O
00
WEIGHT PERCENT H 02
Figure 2.14&a. Heats of Vaporization of Hydrogen Peroxide-
Water Solutions
112
[0l
1002 I
o [0.0 7
z
0
I fMI-
S6.0 251
HIT 14i
5 . 0C I T
i~
.-
HillIIiHi f f I
0 20.
0II
113
Ito0
17.0
16.0 ml
13.0
~fHill
0
1460 441y Br
13 F
120 1 4 Tt'T , ,4
U110 It
00 J0 ''0 60 010
117
00
-404
MINN II lii' ~ i
WEIGHTT
PEREN 20
115 i; t 1
- 1200
-1100-
-400~~H i,Of ,
-j401
"10 logV
) 4/2O f
-1000
706 5 9 5 O
Peroxde-Wter olutin 77
ida
c11 __00
i _ _ _
;fi; 44 ) Ill i
I! 'Y ii'
ad~~c mhUiiii
ifi
H 0
oj; -wbIs ;1 d 1)( !Z1!3
I J!Iji1t7
0
-C1111
tv o
Mill
I Iol;
I.
I, t
TH
o4
1, f, I
o 00 00 0 0 0
4 I
A!!! 1 /f l ilt ' I EIl 3
11
LO r: rT.~"7 7~2~I~
I '1
It0
1119
1. T i
12Z% 11'
ir
IIT
f-7, i- --I -
0.60
I
2. T K4T -4 -
C'V FIIOf,,A U
.1. .1
TT 1
'VTIt
IILI
TEMPERATURE, C
Figurec 2.19. Visusitiee of 98 W/o Bydr-ogenL Peroxide,
70 w/o flydrogon Peroxide, und Wuter
121
- a,
,I
'.3 - -- -- I -1-'
-,
- ' 1 401'
f
- -- - -, -I11 - l l
-Ji
1.0 -
~ - -
7 -~
0W I
.9 _1
0.5
0.4 202-
0.3
TEMPERTURE, 2
112
1.4 1 If7
1.3 t 1
1.0 t :ili
0.9~
.. .. w 4 .
-7
,
!: __ __ ., l
0
0.7
*L 4. -.. 4 4! 4 - +1
Id ,, <7.it
74 74441
0L. 1 IL J~ .!L
0.44.4
HI
__ 72W62o 222
0.2 -r
4I
+i HI 'it
122
M.
T.
Ifl Will -till I Ilif H
If T. cr
AI
WjI t J.
W
W: a- r .1 e ON l- - 1114011
M, 'T-
IN 'thimfilof I ::t 11...
- I
Mtititl
lHiff MAI
I:
It at M M
-it -_x bo
Li
TT ---
------
MW OR ---f- t
5 TT"T
E0 1:1
cr
w T:
XIM
Z .,4
TT T 1-If OD
TRMM I ......
......
Mm 4 flumil: F ITTP
X1
TM,
.':!14A77 8
. M .
vf+4 ++
f C
-- w Itlif - . .1 N
M a Tl.:7 T
IFW+Mo
MlOdOUDIN "AIISOOSIA
123
U4
t ------
iiflj ..................
4
X
ti
Q36 fpjlul tt-t
El. I St m Q. t lm
rat Al.
14
t! t" t-t i i f-t4 +
034 I+ , Hi t 4- --fffj+
P7. _J& :Tffff
EXPER-IFALAYAL D'"A AtHt
TTr-M W 4
0 aw ',T4W44jT:RM J+H4
41
4
-V
X 0.327
TT
R44MA V
w
OL31
0 100 200 300 400 GDO
TEMPERATURE, F
124
1820
- Hi 'I ILI*
4!4'ui'TrJ1
1680 it tL
1205
6000 if~T
it' 1 i
5900,
70 60 F 0 10
U. 126
ill
0
0T
V) gin
41,4
u- t
ITi1 TT
ivy1.4
ii !H 2
H C
- 0 0'
±NV±SNZ~ Z~Iiliai
IN I il 1rl l127
0
2
0 . 0
in
if 54
*~ I~i~*~tii.,,,Hill-
-- 1
1124
10 __
1/2/U
LAJ 0,
0- 0 (G /P) 120.04
REPRINTED FROM
REF. 2.101
1 1 1
129
N-I-I--- n i - -
-- a - -n, -_ - - - -
4. - -r-
I0 .-.......---
44 _ _ _ ___
_..._ _ ..
- - - -.-
fOf
- -- I , -p a
4 - , OU 0RNOUT CONDITIONS
Ps 700 .aSIA
- {Q/A(014 , 15.4 BriSEC IN2 ' -
_ _ _ _ _I .. 3000
Inside Wall Temperature, F
130
DITTUS-'BOLL~TR EQUATION /0
NU,023 R4 4, .-PR 10 01 .
2
-
*0v
C-4
>40 -
NUb% NUSSELT NUMBER
Rb= REYNOLDS NUMBER
PRb PRANDTL NUMBER
10 LL1
kmow
1 1 111I --.
Figure 2.26.Correlation of Beat Transfer Coefficient. of 93 W/o
Iiydrelcu Peroxide With Dittus-iloeltcr l4uation
(Convectir* Region)
600
0
200 - - -- - &
.100 -----
60 n Nur. NUSSELTNUM
6, 0
" Ref : REYNOLDS NUMBER
Prf : PRANDTL NUMB"R"
40
SUBSCRIPT f DENOTES
20 PROPERTIES BASED ON----
ARITHMETIC MEAN FILM
TEMPERATURE Reprinted from Ref. 2.1013
p2. 4 6 8 105 20 40 60
Ref
132
60-000- - - --- , ,
- - -
9 - - - .
zI
rbi. .- m u -. - -
tt
/LzFLUID VISCOSITY
3.1.1 Preparation
131
The first record of comoercial production of hydrogen peroxide
appeared in the 1865 to 1875 period. The first comercia, pro-
duction in the United States was by the Oakland Chemical Company,
Brooklyn, New York, in 1881. Laporte Chemicals Ltd. established
a factory in Yorkshire, England in 1888. With the exception of
substitution of fluorosilicic acid for the hydrochloric acid,
Thenard's process was used essentially unchanged for the manu-
factureof hydrogen peroxide until nearly 1900. The formation of
hydrogen peroxide in the electrolysis of sulfuric acid was first
reported in 1853; later developments made the manufacture of
hydrogen peroxide by an electrolytic process possible in 1908.
By 1939, only 10 percent of the world's production was by the
barium peroxide process.
136
stoneware distillatiou column. The resulting solution is approx-
imately 30 w/o O2 . Both the cathode liquor (after purification)
and the bisulfate from the evaporator (and separator) are recycled
bak to the cells.
0 H 0
137
The second organic process used in the present comercial manu-
facture of hydrogen peroxide is based on the oxidation of pro-
pane or a propane derivative (such as isopropyl alcohol).
Although the actual details of hydrogen peroxide manufacture by
these processes are not defined, the basic reactions of the pro-
pane oxidation are postulated as follows (Ref. 3-.3):
C3% 02 -C3H7*
C9 7 . + 02 - 3 H6 + HO2 .
C3..L. + + CII
H__4PCR
(c 3 )2CoH + 02 - (C 3 )2 co + Y2
3.1.2 Concentration
138
peroxide is normally concentrated commercially by fractional dis-
tillation to concentrations 1 90 w/o 1202, other concentration
procedures, such as fractional crystallization combined with vacuum
distillation, have been frequently used for small-scale purifica-
tion. The concentration of the 9G w/o H202 solutions to - 98 w/o
202 is presently being accomplished commercially (Ref. 3.4) by
fractional crystallization. This crystallization process also
removes most of the impurities.
3.1.3 Purification
3.2.1 Availability
3.2.2 Cost
141
For the purpose of estimation, the citrrent price list (Ref. 3.6)
98 w/o 12 02 -40.60/lb
90 w/o H. 20-40.50/lb
70 v/o 110 2 -40.34/lb
142
In edditioL. during the development snd utilization of the
Redstone Missile System, there we a "purchase description"
document, A£RA-)-4-763, dated 14 August 1958, which was issued
by the Army Ballistic Missile Agency for the purpose of procure-
ment of 102 used in this systam. Altuough no longer applicable,
upon request.
144
Necaua . the space limitations of this handbook and the ready
availability of the analytical procedures, they sw'. not repro-
duued ii this Landbook. Movever, in summ'Lion of th6 analytiLal
techniques recommended by NIL-P-b0U5D, R2 02 ausay is determined
1by standard titration with ceric sulfate to a ferroin end point.
The Alt Cl, NM&, N0 3 , P0 and 80,1 ions are all determined spec-
trophotometrically, and tin is determined polarographicull.,.
Carboa content is determined by combusting the sample in a fur-
nace to change the carbon materials to C02 ; this is subsequently
determined by titration (Ref. 3.9). There are some differences
in the analytical techaiques recommended by NILJ-F-16005D arA
those recommended by the various manufacturers and vsed in the
irdustry. The differences in these procedured, which are for
the most part minor, are summarized in the following paragraphs.
The Air Force Rocket Propulsion Laboratory has recognized these
differences and has indicated probable changes in the presently
recommended analy io.1 " chuiques during tke next revision of
the procurment specification.
3,4.1 I 0 Assay
3.4.2 Aluminum
143
color forimtion. The FMC (Ref. 3.6a) procedure suggests that
the pcmple size be increased from 10 to 25 milliliters and that
the buffer solution, prepared by the specification method, may
be slightly less stable than the buffer solution preparation
detailed in the FMC procedure.
3.4a.3 Chloride
3.4.4 Ammonium
3.4.5 Nitrate
FMC (Ref. 3.6) reconnends that the heating step with the phenol-
dislfonic acid reagent, employed in the determination of the
nitrate ion, be increased to 15 minutes (from 5 minutes) to
ensure complete contact and nitration of the sample residue.
The Shell procedure (Ref. 3.14) utilizes t,larger sample size
and increases the heating time to 10 minutee.
146.
.6 Phosphate
3.4.7 Sulfate
147
3.4.8 Tin
'Both duPont (Ref. 3.10) and FMC (Ref. 3.6.) suggest the use of
a polarographic method for determining tin in contrast to the
spectrophotometric technique recommended in HIL-P-16005D. Shell
(Ref. 3.17) uses a spectrophotometric technique which is differ-
ent from that in the MIL-P-16005D; the stannic ti.n in extracted
into an 8-bydrozyquivoline-chloroform solution at a p1 of 0.85,
and the tin in determined spectrophotometrically in the chloro-
form extract.
3.Ia.9 Carbon
3.4.10 Residue
5.4.12 Stability
150
3.8 Naval Research laboratory, Washiniton, D.C., The Role of
Inorganic Contaminants in the Catalytic Decomposition of
Hydrogen Peroxide, Report No. 5117, 15 April 1958.
k~4r PIN.
IH 0 0 0 U
N 16
U so- 40 w~ 40 go-
qA40
-. U 1U 2
TABLE 3. 2
Military
Specification DuPont Sbell FWC
PO - , mg/liter
g 0.2 maximum 0.1 0.04 0.07
153/154
SECTION 4: STORAGE AND HANDLING
1.1 STOHABILITY
41 .1 General
Until tho early 1960's, the generally accepted decomposi ion rate
A0L* of comercial, unstabilized, propellant-grade hydrogen peroxide
under normal storage conditions (e.g., in a 30-gallon storage drum
at an S/V of 0.38 in.- )was -I percent/year at ambient temperatures
of 77 to 86 F (Ref. 4.1). This rate is theoretically equivalent to
a propellant-grade hydrogen peroxide concentration loss of
-0.5 w/o %0 2 /year. Some examples of decomposition rates actually
experienced during drum storage (under field handling conditions) of
various types of hydrogen peroxide between 1945 and 1963 are shown
in Table 4.1 in terms of concentration changes and actual oxygen loss.
These results, which are essentially representative of propellant
manufactured before 1960 and of storage at the S/V (0.38 in. - )
typically found in 30-gallon storage drums, were reported in Ref. 4.2.
157
improved surface pretreatment and passivation techniques and use
of stabilizers. Extrapolations of the data indicated the oxygen
losses of 98 w/o %02 were less than 0.4 percent/year at 70 F in
the bladders. Compatibility screening studies indicated that
other bladder mterials such as NAA Vicone 185, duPont Viton B
(805)l and 3K Fluorel 2141 were superior to the TFE Teflon material.
158
rates of untreated 90 w/o H202 after storage in aluminum for periods
of 1 year. It was also determined that the minimum decomposition
rate of hydrogen peroxide in contact with aluminum surfaces was
achieved vhen the aluminum was subjected to a caustic-nitric acid-
hot (212 F) 90 w/o H202 pretreatment sequence prior to testing;
however, only minor changes in stability resulted from various
types of chemical pretreatment of stainless-steel surfaces (Tables
4.31 and 4.31a and Section '.2.2.12 The decomposition rate of
90 w/o H202 in contact with tin-plated (electroplated) aluminum
was greater than that observed with either the best tin surface
or the best passivated aluminum surface.
159
generally attributed to the decrease in impurities and ionization
with the loss in water content, and to the decrease in container
contact area with decrease in surface tension. This effect is
illustrated as a function of concentration from 90 to 98 w/o in
Fig. 4.1; comparisons of other decomposition rates between 90 and
98 w/o 202 are shown at two other conditions in Fig. 4.2 and 4.3.
16o
4.1.3.4.1 Container Material. The effect of various materials in
contact with the hydrogen peroxide is described and compared
in the Materials Compatibility Section (Section 4.2.2). How-
ever, for comparison purposes, decomposition rates resulting
from the effect, of selected materials in combination with
other effects are shown in Fig. 4.4 (Ref. 4.1) and 4.5 (Ref.
4.1 and 4.10) for 90 w/o H202.
162
peroxide could be protected against contact with soluble and
insoluble contaminants, stabilization irould not be required. In
addition to the contamination of the hydrogen peroxide by the
system fabrication materials, 202 contamination may result
from improper storage and/or handling systemcleaning and
passivation techniques. The incomplete removal of organic
solvents, acid, detergents, chromic acid cleaning solutions,
etc., by inadequate rinsing or the use of rinse waters which
contain various impurities can readily cause contamination of
hydrogen peroxide by the storage or handling system. For
the preceding reasons, and because the normally manufactured
hydrogen peroxide does contain traces of impurities that will
cause R 202 decomposition, some degree of stabilization has
been effected in most of the conmercially manufactured hydro-
gen peroxide. The degree and type of stabilization has de-
pended on the planned ue of the 1202.
163
these substances, the most notable success was obtained,
especially in the case of the highly concentrated hydrogen
peroxide solutions (Ief. 4.5),with sodium stannate or 8-
hydroxyquinoliae ("oxine") in the presence of a soluble pyro-
phosphate, or e phosphate-pyrophosphate mixture. A detailed
discussion of hydrogen peroxide stabilizers is presented in
Ref. 4.19 and 4.20.
164
and electrolytic tin having low-6/V demonstrated decomposition
rates as low as 0.1 percent/year. The ra'aj predicted for
these materials as a function of S/V are shown in Fig. 4.Sa.
165
(Ref. 4.2) heavily stabilized to provide enough ions to com-
plex all of the potential catalytic sites. Therefore, the
quantity and type of hydrogen peroxide stabilization is dictated
by the end use of the material.
167
The hNdrogeu perexide bulk temperature will lag changes in air
temperature depending on the container size. A large tank 'which
has been warmed during the day will require some time to cool
because of" the volume of solution. For a tank to be warumcr than
air temperature at night is normal and no cause for alarm. For
the tank temperature to be gradually increasing toward an in-
creased air temperature is normal. For the temperature of a
tank not exposed to direct rays of the sun to be increasing
in temperature when the air temperature is decreasing is ab-
normal. For the tank temperature to be consistently higher
than ambient air temperature is not normal.
168
tin will also reveal varying concentrations depending upon
the age of the solution when tested. Comparison of analytical
reports from separate laboratories on the same solution must
allow for this variation.
170
standard compatibility classification definitions, and standard
rating criteria. Although the illustrated procedursa and
classifications do not necessarily reflect the most desirable
methods for all purposes, they do represent the most typical
(as noted in Ref. 4.25) of the general tests, classifications,
and rating criteria presently employed.
171
wetted condition, a sample strip, 1-1/2 by 1/2 by 1/16 inches,
is usually immersed in 75 milliliters of the hydrogen peroxide
solution. This test condition simulates an apparent sample sur-
face area of 1 sq in. per 42.8 milliliters of hydrogen peroxide
(which approximates the 0.33 in. 2/in . 3 S/V of the wetted surface
of a standard drum containing 250 pounds of 11202). If it is
necessary to test a differently sized sample, retention of this
apparent S/V will aid in comparison of the results with those
of previous studies. In evaluating materials for specific
applications, the S/V of the application should be duplicated
if possible. In testing the compatibility of liquids with 110 2 ,a
5-milliliter sample size is normally used; evaluations of greases
are usually conducted with samples of 5-milliliter size which
have been smeared on the inside of the test flask. It is im-
portant to record and report surface area of the test sample
and the liquid volume of the H202 used. Vapor space or ullage
should be minimized or held constant in comparison of different
materials.
172
Stainless-steel samples should be degreased by scrubbing with
trichloroethylene, rinsed with water, allowed to drip dry,
and immersed in 70-percent nitric acid for 4 to 5 hours at
room temperature. Then, the samples should be washed with
clean water, washed with distilled water, and finally pre-
treated with 35 w/o H202. In instances where the stainless-
steel specimens do not respond well to the preceding passiva-
tion technique (as noted by decomposition activity in the
35 w/o H202), stainless-steel specimens may be passivated
by the following alternate procedure which has been utilized
successfully in the past:
173
3. Passivate by imzersion in 70-percent nitric acid
for 4 to 5 hours at room temperature, rinse with
clean potable rater, and finally rinse with dis-
tilled water. Expose the specimen to 35 w/o 11202
at 68 to 72 F for 8 to 24 hours.
174
The percent of active oxygen lost is calculated as follows:
WI - W2
Percent Active Oxygen Loss -1 O. 76 x 100
wtere
where
175
color, transparency, tensile strength, and tear resistance;
and (3) for fabrics-changes in color, tensile strength,
burning, and tear resistance.
176
In HIL-P-16005D the stability is expressed in percent AOL,
although most procedures essentially express stability as
(100-AOL) percent.
177
Protective coating materials are usually evaluated in accordance
with standard compatibility procedures. The coating i3 applied
according to the manufacturers' specifications to standard
test strips and is tested as generally described in Section
4.2.1.1. (It is important to differentiate between compat-
itiblity of the coating material and the effectiveness or
covering ability of the coating on the base metal) The percent
AOL is determined, and visual observations of any physical
changes in the coating are noted. Other varlations of this
coating test involve filling a coated steel cup with 11202,
inverting a second coated cup on top of the cup containing
the liquid, and maintaining two such sets at 86 and 150 F
for 1 year and 1 week, respectively. A final laboratory test
involves the half-filling of a coated 5-gallon container with
1202 and allowing the test container to stand at room tempera-
ture in the laboratory or in a controlled temperature room.
Containers with a 12-inch ID and 12 inches high with a 2-inch
vented opening in the top are recommended for a 12-month test
duration. Ifydrogen peroxide concentration is determined
initially and bimonthly thereafter for both the cup tests and
the container test. Prior inspection of the coating for
blisters or pinholes should be made before the tests are
initiated.
178
4.2.1.2 lHydrogen Peroxide Materials Compatibility Classifications.
The results of the various laboratory matcriuls compatibility
evaluations and of application experience have shown that
materials can be classified into various categories based
on their contemplated types of use in hydrogen peroxide service.
All materials need not, be suitable for indefinite storage
because in applications requiring only short-time contact with
11202, materials of a lesser degree of compatibility can be em-
ployed. To facilitate selection on this basis, materials have
been generally classified according to the types of applications
for which they are suited.
179
160 F or 1 hour at 70 F. An example of a Class 3
application is materials for use in a flow system.
The hydrogen peroxide should be consumed iii the
application or disposed of after the test because
contamination of hydrogen peroxide solutions with
Class 3 material is usually sufficient to render it
unsuitable for storage. Many Class 3 materials in-
dicate satisfactory room temperature service; how-
ever, the material should be checked prior to use.
180
compatibility tests are usually subjected to the following
modifying considerations (Ref. 4.25):
181
The weight loss is measured over a specific period of time
at a controlled (and known) temperature. The generally
accepted criteria for AOL vsacompatibility rating are pre-
sented in Table 4.3.
182
considered a Class 4 material. The criteria of impact sensi-
tivity of a material in contact with the 1102 is the incidence
of any positive detonation on the basis of a minimu of 10
trials. A mixture which gives negative results during the
initial 10 valid tests is tentatively considered to be non-
impact sensitive unless later tests produce a positive result.
183
1
condition; the material fibers are not appreciably weak-
ened after immersion for 1 month in 11[02.
set of standards.
185
The materials compatibility data presented in Tables 4.4
throulh i .a31 are sumnarized with respect to various types
of materials in Sections 4.2.2.1 through 4.2.2.10, and various
controlling effects in Sections 4.2.2.11 through 4.2.2.111.
186
D-356 has indicated Class 1 compatibility during laboratory
tests with 1100, mid satisfactory service experievee has re-
sulted with various i1202 concentrationm.
Lxp rience with use of the wrought 300 series atvinjlc.u steo l
for 6c=Iesa tubing, soreleas pipe, fabricated equimjuent for
piping systems, ajad welded tankslhia been r_.-..isfactoir. The
use of 300 selics stainless steel ia recomended for high-
pressure flow systems and applications wV: re te presece of
aluminum oxide, which is difficult to avoid in 120 handled
in tluminuz, cannot be tolerated.
188
service in flight vehicles; however, the material hardness
wust be less than 412 Ic (llockwelJ Hardness Scale C), or there
is an increase in !1 02 decompositioin said development of metal
rusting. The 7 P11 material has proved very successful
'With 7t w/o 11202 and moderately atccessful with 90 w/o 11202;
however, a peCLial pa&&esivatioai treatment (itf. 1,.31) is re-
quired to achieve a Class 2 rating for this material. Surface
finishing of the sample with 120-grit abLasuije compound was
found to be effective in improving the compatibility of this
a llo)y.
189
and should be smoother if possible. This is especially im-
portmt In stainless-steel storage and hindling systems; i
rough spot in a tank, for example, will cause H)0 2 dec mpoa-
4.2.2.3 Pure Metals aid Other Metal Alloys. The compatibility of pure
metals and various other metal alloys with 90 w/ hydrogen
peroxide is presented in Tables 4.6 and 4 .7,respectively.
Many metals other than tic al 'wiiajuw and stainless-steel alloys
have been evaluated, but few have been fotnd suitable for 11002
service. Silicon, tantalum, tin, and zirconiun are exceptions.
Of these, tin has been utilized to the greatest extent, i.e.,
for gaskets and an a solder for stainless steel.
190
4 .-. 2.. Illntics _and Itubber Compounds. An exeAlent sumary of tile
results of compatibility tsts with vaiouts pitnitic and
rubber compoundn, presented in Tnbl is 4a.8 tI!rough It.12 1ad
4. 2 through 4.30, was p~resented in lie '. 4.-.25, ilecatse plastics
and rubber compounds are ogan i ini na ture, t he compatibility
with hydrogi'n peroxide varies coansiderably. INe those tuatetiala
•ihich have shown excollea't compatibility with 90 wj/o 110r,
both in the laboratory wad in use, may be suslmect when new
coniditions arc met which have not ben encountered or simulated
prevIously . Conditions which may lead to reactioii between a
plastic materia and II202 are extremely varied and di fficult
to predict or to evaluate in the laboratory. lowever, the
following erie generalization must always be considered:
the c ombination of high-tren.tth hydroglci perovide, organic
materials, and heat itrout either an external source or from
112)0 deoomposition may lead to an explosive reilction.
191
differences caused by various prucossing and handling tech-
niques. Compatibility of plastic and other polymeric or
composite materials are therefore usually associated with it
mavtufactu-i-ei's3 name.
where the ll0(02 will remain below its nurmal atmospheric boil-
ist point. However, mixtures of these materials with other
materials must always be evaluated becauue reactions arc
varied and the compatibility of any added ingredient must
alwa)' be considered. Glass-filled Teflon is acceptable,
carbon-filled Teflon may be acceptable, and asbestos-fillest-
Teflon is not acceptable. Kel-F, Aclar, and "virgin" Teflon
are the mast compatible plastic material, at high operating
temperatures and should be utilized wherever the physical
properties are suitable. It is especially recomended that
these materials, which have exceptionally low coefficients
of friction, be applied in i 02 service as dynamic bearings
192
and seals without lubricants wherever possible because of the
limJ.tationb of the available lubricants. Special high-pressure,
2-hur compatibility tests at 132 C (270 F) and 1000 psig with
90 W 1o 1 02 demonstrated that Teflon and Kel-F are not ad-
versely affected. The AOL for these 2-hour periods is com-
parable to the percent AOL experienced at 66 C (151 F) in
7 days. Filled plastics such as Kel-F elastomers, 9711
Silicone, and Vitons show swelling at the high test temperatures.
There are many plastic materials that break down upon extended
exposure (> 7 days) to 90 and 98 w/o H202 at elevated temper-
atures (151 to 165 F) but exhibit no effect uron 24-hour
exposure. The majority of Viton A, Viton B, Fluorel 2141,
and Fluorel 4121 compounds show this effect. However, most
service applications are at ambient temperature conditions
10 to 50 C (50 to 120 F) and these same plastics and rubbers
demonstrate excellent service at these temperatures.
193
Viton A and Fluorel materials demonstrate Class 1 ratings in
10 to 49 C (50 to 120 F) service. Viton A 271-7, produced
by Parker llannefin Corporation, has demonstrated exceil)edt
service as O-rings in 90 and 98 w/o V102 solenoid vaives and
for component seals. Seuls Ersteru Corporation's Fluorel 2141
and Fluorel 4121 O-rings, seals, and bladders have proved
satisfactory in the moderate temperature range. David Clark
Company's Omnii (Viton A) has proved useful as O-rings and
when used to impregnate glass or Teflon cloth, produces a
material which is satisfactory for use as an 1102 splash
cloth or curtain (Table 4.8).
194
absorbed 11V2 may be shock sensitive although no adverse
experience of this nature has ever been encountered, Polyvinyl-
chloride plastics will also leach chloride ion into the 1V2
which will cause corrosion of aluminum even when present in
minute quantities.
19W
American Aviation's Vicone 185 (Table 4.26). Other satis-
factory bladders are the 1).F. Goodrich Company's 9711 high
purity silicone material, and duPont'. thin film I'4T Teflon
(heat sealed). There are oter materials that show promise
as bladder materials, such as Viton A aid B.
196
Several tests have been made of built-up diaphragms, usually
a plastic and cloth sandwich type construction using Dacron
or glass fabric. The compatibility of these diaphiagms with
90 w/o 1102 has been satisfactory when using Omni (Viton A)
impregnated glass, Teflon, or Dacron cloth. Polyethylene
and Kel-F sheet diaphragms have been utilized successfully
in pressure transducers with water on the pressure gage side.
Stainless-steel diaphragms have also been utilized satisfac-
torily. In designing equipment for 1102 service, it is best
to avoid diaphragms if possible. If a diaphragm must be
used, there should be adequate testing of diaphragm materials
with 1 02 before the materials for its construction are
chosen.
197
Stainless-steel filters fabricated of wire, either wrapped
or woven, yield Class 2 or 3 results. When using these mate-
rials for filter elements, welding should be kept to a
minimum. Filters made of 316 stainless steel have been used
successfully in various "202 operations, such as fueling
operations involving flight vehicles. Porous stainless-steel
elements formed by sintering powdered metal have not proved
satisfactory for 1102 service.
198
The pr-sont fluorinated hydrocarbons do not possess good
lubricating qualities and their viscosities vary widely with
temperature. Some lubricity additives were evaluated sev-
eral years ago, but none was completely satisfactory because
of the difficulty of attaining stable emulsions. In addition,
use of fluorinated hydrocarbons as lubricants for aluminum
threads or in conjunctior with aluminum with a high surface
area in applications where L~at may be created (which is a
natural condition in all applications requiring lubricants)
may lead to detonating reactions without any 1102 present.
Two instances of such an occurrence, one during a thread cut-
ting on aluminum pipe using Fluorolube as a cutting lubricant
and the other when fluorinated hydrocarbon was used as a
thread compound on the aluminum head bolts of a decomposition
chamber, have been reported. This reaction was reproduced
in the laboratory by dropping a fluorinated hydrocarbon on
heated aluminum in powder form.
199
is subject to vuriations in results with different operators,
and the condition of the anvil plunger or weight is another
variable. Despite the practice of regular calibration of the
tenter with a "known" mixture of ethyl alcohol and 90 w/o
"202 in equal-volume propcrtions, poor reproducibility has
been experienced. Because of this situation, it is thought
that any positive detonation should be sufficient to place
a lubricant in Class 4 for H202 service. Thus, even though
a lubricant or grease may pass all tests with negative re-
suits and then give a positive result during a later check
test, it will be classed as unsuitable for H-0 2 service.
200
Selas porous porcelain microbiological filters have shown
satisfactory service with 90 w/o and 98 w/o 112 02 at,d may be
used to filter high-strength 11 202
201
or paints is recomnended for surtfaces of materials subject
to corrosion. Prcvention of rust in 11V2 handling and stor-
age areas is a safety measure because the possibility of
contaminating the 11202 is reduced.
202
on a worker ic the possibility that the worker's clothing
will ignite. The materials were also evaluated for resimtince
to deter iration by the action of concentrated hydrogen
peroxide.
to the 8202.
203
4t.2.2.10 Joint Se] llg Compounds. The results of physical and chemi-
cal tewts of joint sealing compounds with 90 W/o hydrogen
peroxide are summarized in Ref. 4.25 and Table 4.15. Host
commerical pipe joint sealing compounds 'ere found to be
unsuitable for high-strength hydrogen pero.ide service. In
systems for concentrations of less than 52 w/o 11202, Aviation
Grade 1'ermatex No. 3 and equivalent have been used satisfac-
torily. There are two thread compounds that have shown good
service in 52 thrvugi 98 w/o 11202 systems. These a'e T Film,
a Teflon wawer-disp-rsion paste for small pipe threads aid
Teflon tape for 1/4- through 4-inch-size pipe thread. Fluori-
nated hydrocarbon-based materials react vio.enily with hot
powdered aluminum. Therefore, these compounds must not be
used on hot aluminum threads and must never be used as a
thread cuttiij lubricant.
204
4.2.2.12 Evaluation of iassivation or Surface Preparation Techni ques.
Laboratory tests (Ref. 4.13) have been conducted to: (1)
determine the effectiveness of selected passivation methods
upon 321 stainless steel, 6061-T6 aluminum (bare and anodized),
and Silastic 9711, (2) determine the influence of cyclic ex-
posure of passivated surfaces to hydrogen peroxide; and (3)
investigate the effects of various storage conditions upon
passivity of materials used in hydrogen peroxide service.
The passivation methods employed in these studies are given
in the following references:
~205
The loss of oxygen in 90 w/o H2 02 solutions in contact with
316L and 321 annealed stainless-steel tubing for 3, 5, 7, and
10 days at a constant temperature of 110 F was determined as
a function of two different passivation techniques. One-half
of the tubing specimens was passivated by OVA Specification
10- 6 2a with a posttreatment of 35 w/o hydrogen peroxide in-
hibited with a 0.03-percent H3P04 solution; the other half
was passivated by Walter Kidde Co. Specification Nor.-520007.
The stability of the H202 solution was also determined after
each test. In general, 321 stainless steel produced less
hydrogen peroxide decomposition than the 316L material. The
best passivation method, as indicated by the AOL results for
both the 316L and the 321 stainless, was found to be CVA
Specification 10- 6 2a plus posttreatment (Ref. 4.18). These
data are summarized in Tables 4.23 and 4.24.
2o6
the active oxygen loss resulting from the anodized aluminum
in contact with the hydrogen peroxide indicated an increase
in AOL values with surface roughness. (Surface roughness
may simply be considered as a surface area factor; the
rougher the surface the higher the actual surface area com-
pared to the apparent surface obtained through naasurements
of the linear dimensions of the sarple.)
207
•., MATERIALS TREATMENT AND PASSIVATION
General
208
B3sically, items such as valves, pumps, actuators, system
piping, etc., cannot be cleaned properly in the assembled
state, because the solvent, cleaning solution, residual con-
tamination, etc., may be trappe in inaccessible areas. The
cleaning should be conducted imnediately before component or
system assembly, unless provisions are made for packaging the
passivated part to protect against re-contamination until
ready for assembly. After assembly, components, such as
valves, should be packaged until they are utilized in the
final system assembly. It is also standard procedure to
check all passivated items with propulsion-grade hydrogen
peroxide prior to assembly in the system.
209
material. Equipment to be used in the passivation procedures
should be large enough to accommodate all items to be placed
in the iintended system and provide a method of complete wet-
ting (with all solutions) of tLe surfaces requiring passiva-
tion.
4.3.2.2 Area Cleanliness. The area must be protected from dust and
dirt te prevent contamination of the cleaned parts. Although
a clean room atmosphere is not essential, it is recommended,
partiurilrly, for nsanivatinn nf flight, hardwsarp
210
4.3.2.5 Eye Wash Fountains. An adequate namber of eye wash fountains
should be provided in easily accessible locations.
211
4.3.3.1 Detergent Solutions. A 1 W/o solution of a powdered com--
merical detergent such as Dreft, Naconal, Tide, All, Swerl,
etc., in potable water is normally used for cleaning mater-
ials and glassware. Liquid detergent (of the same approxi-
mate concentration) or a mild solution (5 to 7 ounces/gal)
of a commercial alkaline cleaner such as Turco No. 4090
(or its equivalent) may also be used; however, it should be
noted that a strongly alkaline cleaning solution must be
avoided. The container for the detergent solution should be
rust-resistant and covered to minimize dirt pickup. Since
most procedures recommend the use of hot detergent solution,
provisions should be made for heating the detergent container
to 140 to 160 F.
212
container which has been previously washed with a detergent
solution and inued with clean potable water.
213
4.3.3.9 LVdrofluoric Acid (II)-Nitric Acid (1INO ) Mixture, 3 w/o-
10 w/o. A 3 w/o IF-1O w/o lNO 3 solution in used for pick-
ling and cleaning stainless steel when rust or other surface
contamination exists which cannot be removed by the nitric
acid solution. A polyethylene- lined container, with a lid
to keel) out dirt and confine the acid fumes, should be used
for storage.
214
.3-.13 jjydrogen Per oxide B~olution, 35 w/o. Although a stabilized
35 w/o hydrogen peroxide solution is available (from various
comercial manufacturers) for the initial propellant-conditiouing
step, many users utilize 35 w/o 1,202 solutious obtained by dilu-
tion of higher concentrations. However, various hydrogen peroxide
manufacturers recomend that if the 35 w/o 1202 is obtained by
dilution of propellaut-grade K202 (with no or minimum stabiliza-
tion), a stabilizer should be added to the dilute ,202 and the pH
of the solution adjusted so that residual active metal sites can
be deactivated by complexing with the stabilizer (recommendations
of the hydrogren peroxide manufacturers are encouraged in this
area). ihegardles. of the user's preference in the use of stabi-
lizers, any dilution of it202 must be conducted with distilled
or deionized wuter of duitable quality. The 35 w/o solution
should be stored in an aluminum 1060, 5652, or 52511 container.
The storage container must be vented at all times, and the
vent line should be provided with a suitable filter to keep
out dust or dirt. A hydrogen peroxide shipping drum is a
convenient container; however, once removed, the hydrugen
peroxidt uast not be returned to the original drum or con-
tainer. Uydro-en peroxide f rom a satisfactory act iv i t -A~
215
*orth American Aviation, Specilication NM LA (01J0-O03
Inc.
Reaction Motors Division Specification NI 7000
Walter Iidde Covaany Specification 5200)7
216
piping). The metal parts should then be rinsed thoroughly
in warm potable water to remove all traces of the cleaning
compound.
217
77
7 .7,T77", 77 77,T 7
4.3.4.2.1 Stainless Steel. Stainless-steel parts should be
etched for a minimum period, and not longer than 60 minutes,
at room temperature (60 to 80 F) with a mixture of 3 w/o
technical-grade hydrofluoric acid, 10 w/o technical-grade
nitric acid, and the remainder water.
218
4.3.-4.3 "4asic Passiaration." Immediately following the cleaning
(or descaling) operation, the metal parts should be sub-
jected to ,se "basin passivation" step. Although this step
is always accomplished with HNO3 solutions, the concentra-
tens used by different organizations vary. The following
procedures are those preferred by the w.jority. It should
b. noted that plastic and synthetic rubbers should not be
sabjected to this step in the passivation procedure.
219
'
220
-- '--77- - -.
.aterials. Parts, and Components. Before the initial
activity tests are conducted, components much as valves,
pumps, etc., should be assembled (care must be taken to
avoid contamination during assembly). The passivated our-
faces should be exposed to the selected 1202 solutions by
either immersion of the part or by filling the composite
assemblies (components) with the H20 2 . Low openings in the
composite assembly may be closed with passivated plugs of
the same material or polyethylene-covered rubber stoppers;
however, there must be a vent to allow escape of gases from
the assemblies. During the tests of the composite assemblies,
all sliding surfaces must be completely wetted (through
valve actuation, etc.) by the 1202.
221
222
<~-
utilize. Following this pansivation, the system is con-
sidered ready for hydrogen perioxide service. All such
passivated systems should be protected against further con-
tamination with dust caps. In addition, the system should
be continuously surveyed during use for evidence of exces-
sive H202 decomposition.
223
4.3.6 Passivation Aid.
43.6.2 Sirfup Fin i__,. All surfaces which contact hydrogen peroxide
should be as smooth as possible, with manufacturing marks,
identification symbols, and irregularities reduced to a min.-
imum. All surfaces contacting hydrogen peroxide should be
free of cracks, pits, inclusions, and foreign material.
Whenever practical, sharp corners should be broken and a
surface finish of 40 rms (root mean square) or finer achieved.
224a
4.3.6.4 Anodized Aluminum. Aluminum surfaces which contact hydrogen
peroxide should be anodized. Exceptions are surfaces whose
shape makes anodizing impracticable (i.e., tha interior of
long tubes). Sulfuric acid anodizing is preferred and should
be used where that process is avail3ble. Sealing of sulfuric
acid-anodized surfaces should be done in hot water (195 ±
10 F for 30 minutes). Deionized water is preferr,.d for seal-
ing although tap water may be used.
4.3.6.5 Rework. All fabrication and fitting of detail parts and com-
ponents should be completed prior to pasivation trecment.
Any rework on passivated areas makes rrepas~ivation mandatory.
-.
3.7 RandlinM of Passivated Materials
225
should be purged with clean, dry gaseous nitrogen and vrapped
and see.led in clean plastic or metal foil bags. These com-
pouens should be kept sealed until installation.
(Date) (Inspector)
NOTI: If a part is contaminated before
packaging or if a packale containing a passi-
voted p~art is torn, the part should be re-
turned to proper area for passivation or
activity tetst as needed.
226
'T7 -
4.4 FACILITIIS AND EQUIPMNT
227
personnel under any given condition. Since the layout of
test areas is depetident upon particular requirements and con-
sideratious, in which many attendant hazards must be accepted,
the i.ayout considered here is related primarily to storage or
handling areas which can be i~ituated as desired. All such
facilities should have adequate drainage and be situated so
that they are exposed to the minimal climate changes for the
particular arca. Some air flow slould normally be available.
transportation.
228
Propellant Distance in Feet to
Quantity, Inhabited Buildings, Intragroup and
pounds Railroads, Highways, and Compatible Group II
Over Not Over Incompatible Group II Storage Storage
100* 60 30
100 500* 100 50
500 1,000 120 60
1,000 10,000 180 90
10,000 50,000 240 120
50,000 100,000 270 135
1ooOG 300,ooo 330 165
3GoO000 500,000 360 180
500,000 1,000,000 410 205
229
- mo
located aboveground to facilitate the detection of leaks.
All main tank connections should be made through the top
portion of the tanks to reducs the possibilities of propel-
lant spill.
230
.
-'-,
good housekeeping are the best safety precautions in hydro-
gen peroxide storage and handling areas. These areas must
be kept neat, clean, and absolutely free of any type of
combustible material. All leaks and spills should be flushed
immediately with large amounts of water. Frequent inspec-
tion of the areas to ensure compliance with these regula-
tions should be maintained.
- - - - -5.
. . Electrical Concepts. All electrical installations through-
out the hydrogen peroxide storage and handling areas should
conform to thenational, state, and local codes for the type
of area and service involved. The areas should be flood-
lighted in accordance with good industrial and safety prac-
tices for the type of operation involved. Electrical power
distribution within the areas should be through rigid alum-
inum or steel conduits, which are preferably located under-
ground. Spark-proof or explosion-proof fixtures are not
required, but vapor-proof fixtures are recommended. Adequate
electrical receptacies should be strategically located for
miintenance purposes.
232
"
..
.
.... " . . ... . - --
.. .... ...... 1 ,.. ~ .- - -- - -- - -- - -- -- - -- ... ~ - ~- -.
~~VI
I" - -
woo "Mi. "I W"
233
_j-
and do not apply tc- flight hardware although many of the'"
considerations may be applicable.
alloys 5254 and 5652 are normally used for bulk storage.
In considerati~n of requirements for high-pressure light-
weight tankage, AM 350 stainless steel has been used success-
* 2Y
are usually fabricated from 347 stainless steel. Other
mterials successfully utilized in tankage kor these types
of applications are the low-carbon 304, 316, and 321 stain-
less steels.
235
- W "
7•W P ... . . . . ..." , '-r . ,,,•,,
capacity to limit the liquid level from rising above the
head attachment weld.
236
4.a.2.l. Pressure or Volume Changes. Throughout the design,
fabrication, and application of hydrogen peroxide storage
vessels, the pressure and volume changes resulting from hy-
drogen peroxide decomposition must always be considered. A
liberation of oxygen from decomposition results in a subse-
quent change in gas volume and/or pressure of a sealed con-
tainer. To illustrate this point, Fig. 4.10 shows the volume
of oxygen liberated per uait volume of hydrogen peroxide as
a function of hydrogen peroxide concentration and temperature,
assuming a decomposition rate of 0.1 percent AOL per year
and a constant pressure of 14.7 psia. Figure 4.11 demon-
atrates the pressure increase resulting from this decomposi-
tion in an unveuted system with an initial ullage volume of
10 percent. Pressure increases observed under actual stor-
age conditions are illustrated in Fig. 4.3 and 4.6.
of the container."
238
- , , - ,- . . -..
self-heaLing is desirable, adequate instrumentation should
be provided for all bulk storage tans; this instr-tmeaation
is discussed more thoroughly in Section 4..2.11.t
239
. .2.2 PipingSystems. Information of a general and specific nature
relating to pipe, pipe material, and piping itistallation is
extensively covered in Ref. 4.3"1 through 4.60.
240
_ -0 -- - - . . . -- - - - .*
4.4.2.2 Piping Systems. Information of a general and specific nature
relating to pipe, pipe material, and piping installation is
extensively covered in Ref. 4.57 through 4.60.
240
is to be used, the cavities must be vented to relieve any
gas formation. It is recommended also that the number of
valves in a system, be kept to a tainimum to prevent trap-
ping of the hydrogen peroxi e between valves.
241
_-~___
J i _~
llJ
l U J -
K
Welded and flanged construction is recommended in hydrogen
peroxide piping with a minimum of fittings and joints. Bends
are preferred to elbows, and joints should be stud-ends with
lap joint flanges or flanges welded to the piping. The use
of stainless steel and galvanized or aluminum-clad bolting
with galvanized steel back flanges is recommended, because
rusting of carbon steel would afford a source of possible
contamination of the piping when the flanges are opened.
If popsible, threaded fittings and connections should be
avoided; however, where they must be used, it is recommended
that the tapered pipe thrLads be sealed with Teflon thread
tape. Normal pipe thread compounds must never be used.
242
--AI -lw
A%
(or Kel-F) seal between the plug and valve seat is normally
A metal-to-Teflon I
21i
2
I
*- - . --* - - - _ _ -!-- -
preferred over metal-to-metal contact. Materials approved
for gaskets are normally used as valve packing.
2411
AE
,- v. r - i
the pump normally used in this service is a 2-inch, self-
priming centrifugr.l. Wfhiere higher pressure or low capac-
ities are desired, a special rotary pump is reconmended.
245
47H
246
I"
An noted previously,"dead ends," which are those places
that could be filled with hydrogen peroxide without per-
mitting adequate recirculation of the fluid, should be
avoided wherever possible. (A common example of this in
instrumentation design is the typical Bourdon tube pres-
sure gage.) The disadvantage of having a dead e:"7 in.,
piece of apparatus is that there is a possibility that
small impurities will accumulate in the dead end until
extensive hydrogen peroxide decomposition results. If
dead ends cannot be avoided, they should be placed above
the low point in the system so that liquid hydrogen per-
oxide solutions will not collect in them.
4
For example, a stainless-steel diaphragm held between
two bolted stainless-steel flanges should be used in con-
junction with a Bourdon tube pressure gage. with the
placed &it a Vertical Pubitionl.
-~ebY Gas legs and
diaphragm protectors have also been used with success in
preventing direct exposure of the gages to liquid hydro-
gen peroxide.
247
regardless of which technique iL used, its limitations,
operating characteristics, and relationship to potential
"red line" conditions must be fully understood by facility
personnel to ensure the usefulness of the system.
248
alami point of such a systeLi at 14t3 F to eliirinaLte false
alarms resulting from sun heating effects transferred into
the vapor space. One maitufacturvr of this type of inistru-
ielnt does not recommend it for this use.
249
alarms, it might providle a false sense of security). An
alarri system could be set up to operate oi a given tern-
perature differential between ambient and storage t mp -a-
tures; ho,'ever, this involves additiuial expense.
250
- ' m . .. . .--
251
2. All storage tanks, vessels and drums should be designed
so that sampling of their contents may be accomlplished
witlhout the use of a sample thief or i nscrt ion of aly
device into the storage container.
fabrication.
252
12. Flux and carbon formed in fabricatiol 1 be
should
cleaued from welded areas in stainiless steels by a
100 seies stainlCs-steel wire brush. Any inclusions
remaining should be ground out. For the grindint, of
cast surfaces, welds, and weld spatter on surfaces
that will contact propellant-grade hydrogen peroxide,
a clean white aloxide (alumilum oxide) abrasive is
recommended.
253
20. All plastic :aterials must' be checked for 1tial
particles, inclusions, etc., pri or to use. The ell-
254
5. Any lack of fusion will ot be accepted.
255
Staitiletis-teel welds exposed to hydropen peroxide should
a.so be Machilked smooth if possible; however, aluminum
uelds should not be wire brushed or machinied because this
mny ituroduce impurities and thus do wore haii than good.
256
Aluminum welds should not be wi r- biushed or machined if
at ill possible, because impurities may be inttroditced i|ito
t lie mieta li in ttt'iicrs where wire butshing i s a iiecessi y
a 50 scries staitileH-Oteel brush will be used, and care
must be takesi to confine the bvushiiig o the immodiate weld
area.
weld when the arc is initiated and when the arc is discon-
tinued; these exposed tungsten deposits will cause decompo-
sition of the hydrogen peroxide. The tungsten "spitting"
may be decreased and, iu amany cases, eliminated by using
a pure tungstei electrode, striking the arc on a separate
piece of material and currying the weld into the work,
and then discontinuing the arc on a separate piece. For
inert-gas welding, where the welding rod is not coated,
it is recommended that strips be cut off the work scrap
and used as the welding rod. Stainless-steel electrode
tip cups should be used,
The weld resulting from the metal-arc process has two dis-
advantages: (1) porosity, and (2) brittleness. These
characteristics are highly undesirable in hydrogen peroxide
systems, and for this reason, the inert-gas processes are
usually preferred aud recomiended. The metal-arc process
257
( '-ucii It m a tilt slit Iom ii. oj
() X rup.~, ) itiid i a qi it c si it i) I c
fn I this ph Iome.
ve Iii g mHn licen itt i Iiized for pii pei aind eniil I partus mande oif
III itIti 111118 WliiCII 1t igl i lt i I Ied Miid V' I' i Ciii'i' We' it'I- ire
.13 2. 2 Stai iti ss steel . I itert-gaN anid flictal are-we hii g pro-
cebmes are liati sf actory iit tile lield i fig of Stainless steel
fO Ilty 11FO1-g~itje'Oile HStrnIH . Tue iitert -gusH 111-0tess is
[)ie fV ared bVCInubt' tie i Ie utL-gutS b I ailte I. resu Its illit weld
wi th less fore igii matter~ il. lII gezzerau1, tiorinted tuuigsteu
ec c .rudes tir tsed(.
ut Stanidard we iiq; procedures should be
timed for both of these procemses, antd it is n ecessary that
uilli we Id be oif hight quality , smnoothi, lhowogetiious , iand free
of intcl usi ons muid bIoufitoles . Carb))i de precipi tati on du.rinug
we Iditig must be avoided by the use of stabljjIized alloys
muchi aa 3117 Jr 321 or thle extrit Iow-tctthoh il loym, 3011 or
316,.
259
7 ItI I
tiect ion
(hI lld liu Of the AN t-ie, aind (-ti be irovided b',
Ll 1.*.34
lll Ie(j ,1 I1. II tihe c'oIMtrIUt ioul, iiiit illLti(i11, 41l!d m0di fi -
cat ion of I1Yll(Irogetl pe roxide systews, inlspection it; 1Im otI llt
C.
11 c 11l i lie S
2. v I I u'
('ru i cit1tt (if t 11 o wal Ic)
4. i'essuiC-lproof test
260
iI
5.l'rpe fitb £ i ut ion workmuanhip
I I
. ~Cuizrosmazace tu deuigna spec ificaltion
codeta
0115 fti pp i cable
2. Adeqaute grounding
3.1iiiultitoi it uist*tice
to 1i ti Itit oil.
lta
261
After paosivation, all proof and leak testing should be
conducted only with deionized or distilled water, or with
clean, filtered, hydrocarboti-free nitrogen gas or air.
262
,!F
71-7'
Elk,-~
'* 5. Drainage
263
-2-TV .. -. -.
Cac bsn r 5-4 -.
Becase
eroxde
ydroen umpig ito pbli watr tble
Antol
beoetally
staeads fratohas not notnsufficiently
ig into trasdaeci
spublsich been otha otmnaeal
geoe
iwaeruirpertod
nsure hu s . Tfety.lin 4h rT
lal
ol totpef and 90de
pp auhrtiesolto.l f85
264
-. , -rv
AA
-I4.6 REFERENCUS
30 April 1965.
AFO4(611)-10216.
1
AV'fPL-TR-.66-.1
1 - - - ',
It; Manrrh 1066
-'. . . .
(Vnnfad
265
.. . .. . . . ' • ,
266
I .
-.-.
267
ii/-
1961.
268
Aj t
269
II II
4. 53 Naval Ordnance
..... boruory , Wh .c.'," " -4 ' iic'
.......
Iu
NOLTR 63-12.
4.55 ASME bioiler and Pressure Vessel Code, Section VIII, "Hiules
for Construction of Unfired Pressure Vessels," latest
edition.
270
7
-. ,' ;-. r-r -W .. r T - ; .
NWA~A
,.4-
j.64.
4.62 Crane Company, Catalog No. 53.
271
777.7-
. ..
..
...
TADLE .. 1
272
L.ifect ol lemitczaturw
ate of Dccompositioni (AOL)
Effect of Contamination
Decomposition Iate at 212 F
Additive to 90 w,"o 1)O, 1947(2) 1965(5)
test parameters
IO'
lDlta rpreangnrlzdcriteria
and techniques; from tests using assorted
d A* generally
[runder minimum S/V represent teats
conditions.
(3)
( Data reported for 99-1 w/o IL)O) in borosilicate glass containers tef. 4.5)
273
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KAII
TABL 4j.14&
NO VISlBLk, REACTION
Polytetrafluoroethylene (solid)
Tctrafluorocthylene-hexafluoropyropyrlene copolymer (solid)
* Polychiorotrifluoroethylene (molecular weight < 800)
Polychlorotrifluoroethylene (molecular weight > 800)
* Perfluorokerosene
Dispersion of Polytetrafluoroethylene in Trichiorotrifluoroethane (solid)
Perchioropentacyclodecane (solid)
Perfluorodiethylcyclobcxane (mixed isomers)
Dichlorodecafluoroeptane
Chiorofluoro llydroc~~rbon (approximate molecular weight 725)
Chiorofluoro iydrociwrbon (approximate molecular weight 1000)
Fluorinated Hydrocarbon (77.4 percent F; approximate molecular weight 640)
Polychlarotrifluoroethylene (approximate molecular weight, 775;
80 percent halogens)
Sil1icon Compounds
Silicon Fluorides
Tri(p-trifluorozethyl phenyl) Silicon Fluoride
Trilaurysilicon Fluoride
Trio (3,5,5--trimetvll'exyl) Silicon Fluoride
Dimethylpolysi loxanes
Dimethylpolysiloxane (2 -to 500 Cs)
Fluoropolysi loxanes
HCF (CF )CH OLSi(C1 3 Cl1
2 (CF )5 F2 1, Fluoropolysiloxane, n 1-26
311
-~ -- r-. -~- ~ 44
(Continued)
NO VISIBLE REACTION (Continued)
Cyclic Fluoz'osiloxanee
Cyclic Fluorosiloxane (3olid)
CH (R)SiOSi(CH, (R)OSi(CtI 3 )(R)O
RB 322 CH-
CF CF2CF
R =CF 322
CFCFCI
Dimethylpolysiloxane-Cyclic
n 3adhigher .4
Fluoropolysiloxane Blends
Fluorosiloxane Grease (No. 33 + inorganic gelling agent)
Fluorosiloxane Girease (No. 34& + inergan.-c gelinari ageiAt
.
Mixed Diwethylpolysiloxane and Cyclic Fluoropolysiloxane
Mixed Dimethylpolysiloxane (average molecular weight < previous
compound)
3-Heptyl-ni-terpheny 1
Isopropyl-ni-terpheayl
Dinonyliiaplithalerie (mixed isomers)
1,3-Big (trifluoromethyl) Benazene
312
77- f
TABLE 4..14a
(Continued)
NO VISIBLE BRUCTION (Continued)
fw,3,5,6-Tetrachlorofluorobel5Oie (solid)
l,3,5-Trimethyl-2,4,6-Trifluorobenzene (solid)
1,3,5-Trimethyl-2,A--Difluorobenzene
2,5-Dichiorobenzotrifluoride
2-Fluorobiphenyl (solid)
3,31-Difluorobiphenyl (solid)
4,4'-Difluorobiphenyl (solid)
3,6,4'-Trifluorobiphenyl (solid)
Estere
Nitrogen Compounds
Jexadecytriphenylurea
2,2'-Dinitrophenyl Ether (solid) -
313
TAbi 4. l4a
(Continued)
NO VlIBIX EACTION (Continued)
2,b -Difluoro-3,5-dinitrochlorobenzene (solid)
2,4-Dinitro-5-fluorobromobenzene (solid)
Per! luorotr ibutylaniine
Polytetrafluoroethylene (solid)
Tetrafluoroetliylene-hexafluoropropylene Copolymner (solid)
Perf luorokerosene
Perfluorodiethylcyclohiexane (mixed isomers)
Mixed Perfluorocyclic Ether, C F16 0 (five- or six-miembered ring with
aide chain, oxygen in the ringi
Per fl1uor ot ribu tylaw in
Per! luorodihexyl Sulfide
4-Chiloro-3,5-difluoroniitrobenzcne (solid)
3,3'-Difluoro-li,4'-dimethoxybiphenyl (solid)I
Bis(m-phenoxyphenyl) Ether
I ,4-bis(cresoxy) Benzene (mixed isomers)
CF CF o(CF ) SF5
2,2-Dinitrodiphenyl Ethei (solid)
Ia,4'-Dinitrodiphenyl Ether (solid)
4-Fliuori-6-wctiaoxya~cctanilide (solid)
3,3'-Difluoro-'4,4'-dimethioxydiphlenyI Sulfoxide (solid)
3,5-Difluoro-6-methoxyacet~anilide (solid)
Mixed Per! luorocyclic Ether, C FJ 6 (fv- or six-membered ring with
side chain, oxygen in the ringi
Fir - 77
7773 177
TABLE 4..14a
(Concluded)
p-bis(ui-trifluoroinethylphienoxy) BenzeneI
PARTLY MISCIBLE
GELL.ED ON MIXING
315
TABLE ,.15
RECOMMENDED JOINT SEALING COMPOUNDS FOR USE WITHMI)
90- AND 98-JPERCENT IYLDOGEN PEROXIDE
Teflon Tape
Eco Engineering
Various
Dispersion
Teflon-Water
Teflon
1
I
Suitable for
small-pipe service
Suitable for
I
most applications
Compound Supplier
316
zo",
TABIE Ji.15
Comp~ound (ocue)Supplier
317
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370
SECTION 5: TM NSPORTATION
371
and between the inner and outer metal containers. Cushioning
material shall be vermiculite or the equivalent in an amount
at least 10 times the volume of the solutibn -!hipped, and shall
be wet with at least 10-percent water 'by volum'e to which a sta-
bilizing agent has been added (Ref..5." ). TI9se containers should.-
then be crated in a wooden box.
5.1.2 Drum3
372
5.1.3 Tank Cars
373
5.2 SHIIPPING REGUlATIONS
374
5.3 OPEiRATION AND AINTENANCE OF EQUIIMENT
5. 3.1 Drums
375
After being ?aptied, the drum (and compartments) should be corn-
pletely flushed with clean water and drained. The bung cap
should be replaced immediately and tightened securely. All pipe-
lines and holses should be drained when tratnsfers are complete.
The standard tank car compressed gas fitting has been designed
for nitrogen. The gas pressurization line should be equipped
376
with a suitable pressure reduction valve, a safety relief valve
(act for approximately 13 psig), and a pressure gage. A pressure
of 5 to 10 psig is norumlly sufficienot to unload a 4000-gallon
tank car in '2.hours. This will consume about 6- to lO--cu ft/min
n.itrogen. Pressures in excess of 15 psig shouid not be used.
The compressed-gas feed line should be blown out before introduc-
tion into the hydrogen peroxide supply. Details of the unloading
procedures should be obtained from the particular hydrogen peroxide
manufacturer that supplies the tank car.
When either the tank car or truck have been emptied, the outside
of the tank and the ground sIould be washed thoroughly wherever
spillage of the hydrogen peroxide could have occurred during the
unloading. All lines, hoses, and the pump should be drained free
of hydrogen peroxide and flushed with clean water. All lines and
.hoses should then be covered with aluminum blind flanges or poly-
ethylene bags to prevent contamination, from dust (Ref, 5.4).
5.3.3 Handling
3V7
.. At least two trained opertdtoru should always be assigred
to ally operation involving the handling, transfer, or
storage of bydrogen peroxide.
'-
. location and proper'function 6- thisequip m ent ;hould
be checked before beginninty, OPrAo.
container.
378
8. If, for some reason, it is necessary to put some instru-
ment, device, sampler, etc.,into a hydrogen peroxide
solution, the device must undergo the appropriate clean-
ing and passivation procedure. With each addition of a
foreign body to hydrogen peroxide, the chance of con-
taminati~orn is increased.
379
15. In the opening of a pipe line or similar item that has
previously been used in transferring hydrogen peroxide,
it should always be assumed that there may be some hydro-
gen peroxide left in the line, and a supply of water
should be available.
5.4 REFEXENCFS
380
SECTION 6: SAFETY
6.1 HAZARDS
381
and 6.5). The TLV represents the average concentration over a
normal work day to which the average human can be safely exposed
on a daily basis without adverse effects.
The vapors can also irritate the eyes, producing burning, red-
ness, and watering. The effect is short-lived except in extreme
or continuous exposure. When hydrogen peroxide contacts the
eyes, the eyes should be flushed immediately with water.
382
In studies on human skin, 90 w/o hydrogen peroxide on the palms
and fingertipn,where the keratin is thick and nerve endings are
abundant, causes strong prickling and formation of opaque white
patches. This is extremely painful under the fingernails. "On
other skin areas where the keratin is thinner, irritation occurs,
but with less itching and the white appearance is confined to a
fev areas at the base of hairs. There in no evidence of pene-
tration deeper than the first layer of skin, or stratum corneum,
and all these effects disappear without trace" (Ref. 6.1, page 426).
384
material to give reproducible results.) The test simply consists
of placing two drops of concentrated hydrogen peroxide on the
piece of felt and measuring the time to visible flame. The ig-
nition time decreases with increasing concentration as shown in
Fig. 6.1.
General areas where the vapor phase in contact with the liquid
phase has reached the probable ignition level are shown in
Fig. 6.3 (Ref. 6.10).
(43 w/o at 200 mm Jig and 70 w/o at 40 mm 1ig) and decreased with
pressures above ambient. Ignition of these concentrations may
occur as a result of a spark, contact with a catalytic surface,
or contact with a heat source in excess of 300 F.
387
The results of various experimental efforts, which have involved
three primary areas of sensitivity testing (thermal sensitivity,
shock sensitivity, and detonation propagation), are summarized
in the following paragraphs to provide a guide to the potential
explosion hazards of the hydrogen peroxide liquid phase.
388
were heated at a controlled rate, and the temlperature-time profile
of each was recorded. The following results were eported on the
five tests run:
3F9
6.1.3.2.2 Shock Sensitivity. Hydrogen peroxide and hydrogen peroxide-
water solutions are considered non-impact sensitive in both the
solid state (low-temperature studies) and the liquid state up to
212 F (Rcf. 6.2, 6.4, 6.6, 6.12, and 6.13). No imimct sensitivity
was noted (Ref. 6.13) for 98 w/o Iydrogen percxide at. 212 F and
an impact height of 300 kg-cm.
Shock teets with No. 20 PETN boosters set off ill 30-gallon alutuinum
drums, and tests with 15 grams of lercowite dynamite exploded in
the same quantity at 70 to 72 F and 160 F showed no propcllant
detonation for 90 and greaier w/o hydrogen peroxide solutions
(Ref. 6.3).
396
6.1.3.2.2 Shod Sensitivity. Hydrogen peroxide and hydrogen peroxide-
water solutions are considered non-impact sensitive in both the
solid state (low-temperature studies) and the liquid state up to
212 F (Ref. 6.2, 6.4, 6.6, 6.12, and 6.13). No impact, sensitivity
was noted (Ref. 6.13) for 98 w/o hydrogen peroxide at 212 F and
an impact height of 300 kg-cm.
Shock test3 with No. 20 PETN boosters set off in 30-gallon aluminum
drums, apd tests with 15 grams of Hercomite dynamite exploded in
the same quantity at 70 to 72 F and 160 F showed no propellant
detonation for 90 and greater w/o hydrogen peroxide solutions
(Ref. 6.3).
'90
Although it is generally con.-luded that hydrogen peroxide iolu-
tions are not normally shock sensitive, it should be noted that
hydrogen peroxide with additives (or contaminants) capable of
being oxidized are highly impact sensitive. This sensitivity
theoretically depends upon the concentration and type of additive
and, in actual practice, upon the sample size and the method and
typc of impact. Various mrixtures involving hydrogen peroxide of
various concentrations with minimum (< 10 percent) quantities of
organic materials such as ethylene glycol, ethyl alcohol, benzene,
etc. have been found to be particularly hazardous (Ref. 6.11).
These mixtures will detonate violently when subjected to the
slightest mechanical shock with detonation velocities approaching
those of nitroglycerine, TNT, RDX, etc.
391
Siwilar results v;cre obtained (Ref. 6.3) by the Burvau of Mines
in tests on 99 w/o hydrogen peroxide contained ill 0.5--inch tubing.
392
excess of 450 cal/gw implies a possible explosive hazard for that
porticular mixture. A heat of reaction in excess of 900 cal/gm
predicts a possible detonation hazard. Thes't "critical energy"
values were selected after a very careful study of experimental
data accumulated from explosive aid detonation tests on mixtures
of organic conpounds with concentrated hydrogen peroxide. A heat
of reaction can be computed for a number of compositions and the
compositions for the "critical excess energy" values of 1650 and
900 cal/gm determined. These computed compositions may thcn be
plotted to map out hazard areas in the use of mixtures of these
materials. It should be noted, however, that these values are iot
infallible. Mixtures should always be tested experimentally before
actual handling operations begin.
393
1 iqid phuse interfaces. The solubility of a large inimber of
cowpoui.-i in hydrogen perox ide ig givena iii Table I4.1[4U, Siectioni
. This method of eva1 at ioni iti not real ly ajojii* iatc for
6,2 UZ JIJLELU7104N
:95
6.2.1 Ey stew lnItc'iy
396
0 .2.2 Tirai ned l'ersoxiul
397
6.3 UMZAJW CONMtOL
399
long-term storage as noted in Ref. 6.4). Hydrogen peroxide that
has become contaminated or shows an abnormal temperature rise
should be diluted and disposed of. Phosphoric acid (HO4) may
be added as an emergency stabilizer to reduce decomposition
(Ref. 6.4) before disposal.
The hands and feet are always subject to contamination during the
handling of liquid propellants or associated equipment. Gloves
ovd boots will keep hydrogen peroxide from touching the skin.
(Leather reacts quite readily with hydrogen peroxide, however.)
The gloves used should protect against hydrogen peroxide and also
should allow free movement of the fingers. Tbe vinyl-coated gloves,
Type R-1, Mil-G-4244 (Ref. 6.16) meet these requirements. Surgical
rubber gloves or lightweight Neoprene gloves are suitable for hand-
ling small parts. Since boots of the approved protective materials
4 N-3 W 1Mb
401
6 .4.2 First Aid
02
6.5 RLERENUCES
404
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*Data takeu from work of varioub investigatoru and summarized in Ref. 6.12.
These data, whichi are not referenced or otherw Ase detailed with regard to
additional test p arameters and techniques, are ineluded ae a general sxjiry
of twe efurt preceding ibe dat& reported in Ref. (.12.
410
TAI" 6.7
ftef. 6.19
tll
TABLE 6.7
(Concluded)
412
4-
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LAV II%
413
Ctow
O1I .1 0.
COCNRT PEOXD
. OF.... YDROGENi IN VAO PHSE
MOLiFACIO
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"
8ETION 7: DIECOMPOSITION
H+ 1/2 02
417
In a recent investigation ( af. 7.2) to define the contribut-
ions of these individual reactions to the ambient temperature
decomposition of 90 w/o hydrogen peroxide, reaction types (4)
and (5) were ignored. Reaction type (4) probably does not occur
when the temperature of the surfaces is below the hydrogen per-
oxide boilirg point aid the effects of reaction type (3) were
considered insignificant at the temperatures wider consideration.
In addition, it was indicated that reaction type (1) could
probably be separated into further types of reactions; however,
for the purpose of the particular study, the liquid phase homo-
geneous decomposition was considered as being essentially ionic
catalysis. The differen~ces between reaction types (2) and (3)
were considered to be in the effective concentration of hydrogen
peroxide on the surfaces, the concentration of contaminants
which may build up in this condensed liquid film, and in the
concentration of inhibitors which would be present in the con-
densed film (unless agitation of the vessel caused frequent
wetting and washing of all surfaces with the hydrogen peroxide
liquid phase).
"(HP)
k, 2 (Hr) (s/v)liq. + k(p) (s/V)vapo r
dt
where HP - concentration of hydrogen peroxide
kI - liquid phase homogeneous reaction rate
k2 - liquid phase heterogeneous reaction rate
k3 - vapor phase heterogeneous reaction rate
/V sumrace to volume ratio of the liquid phase
s/V - surface to volume ratio of the vapor phase
t - time
Through the use of various purification techniques, relatively
inert sarfaces, and the absence of a vapor phase, the experi-
menters of Ref. 7.2 were able to isolate, for all practical pur-
poses, the effective homogeneous reaction rates of the liquid
from 20 to 100 C (68 to 212 F). Using these data, the effects
of solubl' additives (such as stabilizers) on the liquid phase
were also determined. Although the data rosulting from this
work varied from test to test and as a function of stabilizer
concentration and type, temperature, and manufacturing process,
the homogeneous decomposition rate of the stabilized and
unstabilized liquid was generally found to be less than
~ 0.03 w/o active oxygen los (AOL) per year at 100 C (212 F).
In addition, it was indicated that for future comparisons of
results at different temperatures or the estimation of decom-
position rates at various temperatures, the activation energy
for the homogeneous decomposition of hydrogen peroxide caii be
assumed to be 18 kcal/mole.
419
(on the basis that the rate of decomposition was sufficiently
slow so that mass transfer of hydrogen peroxide to the vapor
space surface was not the controlling rate); thus the heter-
ogeueus decomposition rate for both phases was equivalent to
k, (A/V) where (!/V) represented the total exposed surface
area of the tank relative to the volue of the liquid hydrogez
peroxide. Results of these tests indicated that k2 for the
different materials at 25 C (77 F) appeared to be as follows:
1260 aluminumn - 0.0065 weight fraction AOL, cm/year
5052 aluminum 0.0160 weight fraction AOL, cm/year
tiu5 plate 0.286 weight fraction AOL, cm/year
420
2. Type of additives or contamuinants present
3. Concentration of additives or contaminants
4. pAt
5. Particuler combixations of foreign materials present
6. Temperaturn
For those users of this handbook who are inteheftted !.n more
details of various reaction rates and other aspects in the
decomposition of hydrogen peroxide, the use of the previcusly
referenced literature (Ref. 7.1, 7.2t 7.3, 7.4, and 7.5) as
well to the use of references to literature on decomposition
pi'ovided in the attendant bibliography (Sectioi, 8.9) will
provide the basis for further invastigation.
421
7.2 CONTOLL I
DI 'J1IT51ION
422
with the catalytic ^ant contained ii a mulveint with subse-
quent removal of the solvent (usually Ly dryriug. )Materials
that have been cmonly inked for thiu type of solid catalyst
are aqueoub solutions ol calcium or potassium permanganate.
or the metallic nitrates. Calcium permauganate is usually
pref6red to potassium pemanmganate, primarily due to its
higher solubility in water. The most effective results from
tbis type of catalyst are usually obtained with altaiina or
carborundum particles as the porous carrier medium.
Silver is probably the beut known and the =ost active cata-
lyst for the decomposition of hydrogen peroxide. This cata-
lytic material is usually applied i;,a rcreen type of con-
figuration. Sice pure silver has proven somewhat tmAesirable
frow a physical integrity standpoint (ispecially at the
teaperatures obtained in this type of application) and be-
cause of it, h4t. h t. the silver c'ttaiyst is also used is
a plating on brass, nicke,, "* t-,nless steel screens. To
further reduce the cost .impoved b. the silver, stainless or
nickel screens rre auaLvmingled with the silver or silver
coated screens, without reducing catalyst effectiveness; of
course a minimum number (which ias dependent on th particular
configuration) of catalyst screens, is required for satis-
factory oper tion. The use of the silver plated screens
usually ofters better initial starting characteristics than
4L23
Although the silver and the permanganate catalysts have
been the catalysts of choice for most of the controlled
decomposition concepts, there are a number of other types
of materials which have been investigated as hydrogen per-
oxide catalysts. Identification of these different materials
and a more detailed discussion of the catalytic decompobi-
tion process are contained in Ref. 7.1, 7.6, 7.7, and 7.8.
A complete bibliography of other data in this area has been
compiled in Ref. 7.9.
425
the packing is such that a stainless steel or nickel screen
(inactive screen) is placed between two catalyst screens.
The number of catalyst screens is dependent on system require-
ments (operational life, bed size, throughput, pressure drop
limitations, start transients, etc.) and may vary from 15 to
as many as 100 catalyst screens.
426
The initial development of a high temperature hydrogen
peroxide catalyst was undertaken by Rocketdyne, first
under company-sponsored funding and later under Contract
Nas 56-1052J. Although this catalyst, which ii described
in Ref. 7.11, has been used successfully at Rocketdyne for
several year& in thE decomposition of 98 w/o H202' the
catalyst's physical and chemical stability at temperatures of
2000 F is questionable. Thus under Air Force Contract
AF0(611)-11208, FHC initiated the development of new de-
composition catalysts for 98 w/o 11202. Their progress in
these efforts have been reported in Ref. 7.12.
U.7
Although the particular details of catalyst poisoning by
various potential contaminants are not completely under-
stood, most of the important hydrogen peroxide catalyst
poisoners have been identified. Attempts at characteriz-
ing limitations for each of the individual species and
the contributions and limitations of their interaction
have met with little success. However, the limitations
(which were determined under an extensive Navy "crash"
program and further refined through extensive use) placed
on inorganic contaminants in the hydrogen peroxide by the
procurement specification MIl-P-16005D (see Section 3.3)
for 90 w/o hydrogen peroxide have been effective in con-
trolling poisoning of catalysts used for decomposition
of propulsion grade hydrogen peroxide.
.30
A second factor leading tc the loss of catalyst pack
efficiency is the erosion of silver. This may occur
in two principal ways; (1) When the adhesion of the
silver plating to the base metal of the gauze is poor,
mechanical stripping of silver may occur at high flow
rates of H.T.P. through the interstices of the gauzes.
The type of silver catalyst known as 'activated silver'
which is a loose powdery deposit of silver made by
dipping copper gauze in amoniacal silver nitrate
solution, is particularly prone to mechanical stripping.
(2) Erosion occurs by solution of silver metal in the
liquid l.T.P. near the entry end of the pack: most of
the dissolved silver is redeposited downstream but a
small fraction is blown out, and this leads to a grad-
ual reduction in the total amount of silver available.
However, more important than the gradual overall loss
of silver is te fact that the gauzes at the entry end
of the pack eventually become completely stripped of
silver and then cease to contribute towards the decom-
position of the H.T.P. This leads to a gradual shorten-
ing of the effective length of the pack, the liquid
phase penetrating further towards the downstream end.
Eventually the penetration reaches the downstream end
and the efficiency of the pack falls rapidly.
431
in connection with the erosion of silver it in nec-
essrTy to consider the phenomenon kuown as 'chanueling,'
which is the term given to the preferential erosion
of silver over certain parts of the gauze area. As
a result of thanneling' the gauzes become completely
stripped of silver over certain areas whilst the rest
cf the gauze still retains silver. This process in
turn, leads to penetration by undecomposed HI.T.P.
along the channels. This condition brings about
very inefficient usage of the available silver on
the pack, since once a 'hannel' has been produced
the lI.T.P. begins to flow more freely along it than
through other parts of the gauze area.-
432
7.2.2 Thermal Decomposition
433
7.3 na~u"ECES
'35
.720 ,United States Naval Air Rocket Test Station, Lake Denmark, Dover,
.New Jersey, Mollier Charts for the Decompiosition of H~ydrogen
Peroxide-Water Mixtures, NARTSReport 43, November 1954.
4i36
SECTION 8: BIBLIOGRAPHY
4137
8.1 GE~NERAL REFE1kNCES
438
Shell Chemical Company, New York, New York, Concentrated Hydrogen
Peroxide, H202, 2nd ed. Properties, Uses, Storage, Handling,
Report No. SC: 62-23, 1962.
439
8. Density Solid
440
8.2.1.6 Parachor
804 (1955).
443
Egerton, A. C., W. Emte, and G. J. Minkoff, "Some Properties of
Organic Peroxides," Discustions Faraday $rtet-y, 1951 (10), 278-82
(1951).
-h 735-8 (1950).
445
Savithri, K. and B. Ramachandra, "Magnetic Susceptibility of
Some Peroxides," Proc. Indian Acad, Sci., I{A, 221-30 (194,2).
8.3 SU"L7TRE
446
Parsons, A. E. and A. W. Searcy, "Prediction of the Shapes of
Two Centered Covalent Molecules and Ions," J. Chem. Phys., 20,
1635-6 (1959).
Penney, W. G. and G. B. B. M. Sutherland, "A Note on the Structure
of Hydrogen Peroxide and HYdrazine With Particular Reference to
Electric Moment@ and Free Rotation," Trans. Faraday Soc., 0,
898-902 (1934).
Penney, W. G. and G. B. B. N. Sutherland, "The Theory of the
Structure of H,. rogen Peroxide and alydrazine," J. Chem. Phys.,.2,
Ik92-8 (1934).
8.4 SOUILITY
F.M.C. Corporatiob, New York, New York, Safety Code for BECCO
90 Percent Hydrogen Peroxide (H202), May 1947.
447
Kazanetzkii, P. V., "Behavior of Hydrogen Peroxide With Salts,"
J. Russ. Phys. Chew. Soc., 46, II0 (1914).
448
Davis, N. S., Jr., and R. Bloom, Jr., New Techniques for Transferring
H202 at High Pressures, 9th Annual Meeting, American Rocket Society,
December 1954.
449
Rocketdyne, a Division of North American Aviation, Inc., Canoga
Park, California, "Handling of iydrogen Peroxide," Engineering
Procedures Manual, April 1963.
450
Shell Development Company, Emcryville, California, Hydrogen
Peroxide by Oxidation of Isopropyl Alcohol. Part XVI. Vapor
Explosives and Miscellaneous Explosion Test Data, Tech. Report
No. 7-60, January 1960.
Shell Development Company, Emeryville, California, Thermal
Stability of 90% Hydrogen Peroxide, Final Report S-13801, Report
Period: July 1958-31 December 1979, CONFIDENTIAL.
451
Air Force Flight Test Center, Edwards Air Force Base, California,
Safety Procedures for Rocket Propellants, Report No. FJR-TM-58-1,
November 1958.
452
Connecticut Hard Rubber Company, New Haven, Connecticut, Development
of Rubberlike Materials for Applications InvoAving Contact With
Liquid Rocket Propellants, Report No. WADC-TR-651, Part II, 1960.
Davis, N. S. and J. H1. Keefe, Jr., "Equipment for Use With High-
Strength lydrogen Peroxide," J. Am. Rocket Soc., 22 (2), 63-9 (1952).
4153
Rocket Propulsion Department, Royal Aircraft Establishment, England,
The Compatibility and Engineering Application. of Various Materials
With Concentra.ted Hydrogen Peroxide, February 1955.
454
8.7 TRANSPORTATION
8.8 SAFETY
Meckert, Gi. W., Jr., Edwards Air Force Base, California, "Hydrogen
Peroxide; Problems and Operating Procedures at the Air Force Flight
Test Center," New lork, 1952.
Poesehl, 11. and 11. Seidel, "New Testing Procedures for Determination
of Friction, Impact and Heat Sensitivity," Chem. Tech. (Berlin),
18 (9), 565--7 (1966) (Ger.).
456
Shanley, E. S. and J. R. Perri., "Prediction of the Explosive
Behavior of Mixtures Containing Hydrogen Peroxide," Jet Propulsion,
28, 382-5 (1958).
457
United States bureau of Mines, Pittsburgh, Pennsylvania, Review of
Fire and Explosion Hlazards of Flight Vehicle Combustibles, Report
No. ASD-TR-6l-278, April 1961.
Air Force Flight Test Center, Edwards Air Force base, California,
Safety procedures for Rocket propellantsa, Report No. 1711-TM-58-1,
November 1958.
4a58
The Safety Equipmnent Manual, NAVXOS P-422, November 1900.
8.9 DECOMPOSIT10N
'59
Ahlert, R. C. and S. E. Stephanou, "Research Support of AR-1
Engine Development," Unpublished Data (Rlt 56-40), Rocketdyne, a
Division of North American Aviation, Inc., Canoga Park, California,
August 1956, CONFIDENTIAL.
460
Iroughton, D. D. , R. L. Wentworth, H. E. Laing, and D. M. Mauke,
"Mlecbanism of Catalytic Decomposition of 11202 Solutions With
Manganese Dioxide," J. Am. Chem. Soc., 69, 741 (1947).
461
Flood, P., T. J. Lewis, and D. H. Richard*, "Peroxy-Complexes of
Inioganic Ions in Hydrogen Peroxide-Water Hixtures. Part II.
Decomposition by Chromate Ions," J. Soc,, 12, 2446-55
(1963) (Explosives Research and Development Establishment Tech
Mcmo 5/R/62).
462
Giguere, 1'.A., Chemical Reactions in the Electrical Discharge,
U.S. Dept. of Commerce, Office of Technical Services, I'll
Report
14'. 2-, 6 vpI.(1959).
Gray, P. D. , "Effects of the Space Enviroiwient on Liquid Rocket
Systems," Ch m, Entgr, Progr. Sywp, Series, 60(52), 180-4 (196'.).
463
l*ewil, 1. J., I). 11. Hiclurtim, awd 1). A. Salter, "Peroxy-Colilexces
of lnorgaiicIoJns in Iydrogen P'eroxide-huter Mixtures. Purt I.
DvcoLmlpoUitiou by Ferric 101M," J. Chew. Soc., 1293, 2113'1-46 (1963).
Matt, It. J., "The Problems of Seal ir_ Hydrogen Peroxide ill a 3000"F
Environmeat," J. Equ. Power, 864, 341-4 (1962).
McCormick. J. C. , A. Lijewuki and G. Coraine, Storage of 90 anad
98% by Weight Hydrogen Pe oxide in Sealed Containers fcr Extended
Periods, U.S. Dept. Comnerce, Office of Technical Services, Rteport
No. AD 208 .7I, 1961
New York Uiverity, New York, New York, Liquid Protveilunt Review,
First Quarterly Report, June 1961, CONFIDENTIAL.
U.S, Naval Air Rocket Test Station, Lake Denmark, Dover, New
Jersey, Organically Produced 98% H 0
2 Evaluation Program, NARTS
Technical Note 0125, CON I ILAL.
U.S. Naval Research Laburatury, W%mbiugtuai, D.(. , 1,1t -e I ~v of1
l11a1rKlIlic Coitamiunuts il thff Caat ko~stjf ~'lyjjy
Younts, C. A., "Impr'oved Catalyst for the VAA 75-110 Gias Gvnerator,"
Unpub~lished Data (R 58-38), lRocketdyneI, a Divisiov of North Aweinuacaz
Aviation, Inc., Canoa Park, Califwiuia, 7 October 1958, CONIM1AL,
Swcuriy Classiicition
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