T 04 LAA r'r MAR-ý -"'. id 7..:q, 4w =~ ~ ~ ~ . 14-- * -. AFRPL-TR-76-76 USAF PROPELLANT HANDBOOKS NITRIC ACID/NITfROGEN TETROXIDE OXIDIZERS VOL II * MARTIN MARIETTA CORPORATION DENVER DIVISION P.O. BOX 179 DENVERt COLORADO 80201 AUTHOR: AFRED C. WRIGHT C FEBRUARY 1977 APPROVED FOR PUBLIC RELEASE DISTRIBUTION UNLIMITED Prepared for; AIR FORCE ROCKET PROPULSION LABORATORY DIRECTOR or SCIENCE AND TECHNOLOGY C AIR FORCE SYSTEMS COMMAND EDWARDS AFB, CALIFORNIA 93523 , (cid:127) . . ,. .... . ... .,.:,.:,.. . .(cid:127) ,.. ..,: ;(cid:127) vL,. .z: ,. .: .:; .- ;:,; -. (cid:127),.' a":., -.:(cid:127):(cid:127), " :" (cid:127) (cid:127) (cid:127) :i.'.. "I NOTICES When U.S. Government drawings, specifications, or other data are used for any purpose other than a definitely related government procurement operation, the Government thereby incurs no responsibility nor any obligation whatsoever, and the fact that the Government may have formulated, furnished, cr in any way sup- plied the said drawings, specifications or other data, is not to be regarded by implication or otherwise, or in any manner licensing the holder or any other person or corporation, or conveying any rights or permission to manufacture,use, or sell any patented invention that may in any way be related thereto. FOREWORD This propellant handbook Is the product of a program sponsored by the Propellants Branch of the Air Force Rocket Propulsion Laboratory. The objection of this pro- gram was to provide a comprehensive and systemized text of the properties, hand- ling procedures, compatibility and safety of nitric acid and nitrogen tetroxide and selected blends of these oxidizers. The program was initiated in February 1976 and was conducted by Martin Marietta Corporation, Aerothermal and Propulsion Engineering Department for the AFRPL, under contract F04611-76-C-0026. Lt. R. Butts served as the Air Force Project Engineer. Mr. A. C. Wright was the Martin Marietta Program Manager. This report has been reviewed by the Information Office/DOZ and is releaseable to the National Technical Information Service (NTIS). At NTIS it will be avail- able to the general public, including foreign nations., This technical report has been reviewed and is approved for publication; it is unclassified and suitable for general public release. iR ODNEY CV/ BUTTS, -2nd Lt., USAF Project Engineer pellants Section FOR THE COMMANDER I . ]U-EWARD E. STEIN, Deputy-CC.ie .. Liquid Rocket Division . ) '4,. N_ __ __ __ _ _ __ __ __ __ _ UNCLASSIFIED " , Y' p* - SECURITY CLASSIFICATION OF THIS PAGE. ("On Daet Enitred) REPORT DOCUAEN1TATIONPOAGE READ INSTRUCTIONS "REPORT D P UBEFORE COMPLETING FORM A T NUMu'Ie I2/I O VT ACCESSION NO. 3. RECIPIENT'S CATALOG NUMBER ik t R-76 6 TITLE .)nd Subtille) 5. TYPE OF REPORT & PERIOD COVERED (cid:127)UAJ'-PROPELLANT 11A;'DBOOKS- . . FINAL March-December 1976 NITRIC ACID/NITROGENI TETROXIDE OXIDIZERS oi PERFORMING ORG. REPORT NUM1EA 7. AUTv' (e)s a. CONTRACT OR GRANT NUMBER(e) Alfred C/Wright! F0461 -C76-C-0026 9. 1ERFORMING ORGANIZATION NAM AND ADDRESS 10. PROGRAM ELEI.ENT. PROJECT, 1.kK f A. & WORK UNIT NUMBERS Martin Marietta Corporation Denver Division JON: 30(cid:127)bi0 PR P. 0. Box 179, Denver, CO 80201 II. CONTROLLING OFFICE NAME AND ADDRESS 7(cid:127)71 Air Force Rocket Propulsion Laboratory/LKDP I Feb..... . Edwards AFB, California 93523 13 .NUMaIgRC.F2Ae(cid:127)aES "(cid:127)I. MONITORING AGENCY NAME 6 ADLRESS(i/ ditferent trom Controlling 0ffico) IS ITY CLASS. (011bI. epori) Undo l)siried 16a. DECLASSIFICAIT 7ONDWNGRADING SCHEDULE - 1l.6 DISTRIBUTION STAA. , "rnlW a4R1 eport) Approved for Public Release - Distribution Unlimitid 17. DISTRIBUTION STATEMENT 'of the abatracl entered in Block 20, it ditetor(cid:127)e from Report) IS. SUPPLEMENTARY NOTES It. KEY WORDS (Continue on reveree slde iI neceoary and Identity by block number) -Liquid Rocket Oxidizers -IRFNA -Handbooks -WFNA -Nitric Acid -Inhibited Red Fuming -HDA -Nitrogen 'ý-ides Nitric Acid -Liquid Rucket Propellant-s -Nitrogen 2:troxides -Pigh Density Acids -Chemical Properties -Nitrogen Dioxide -Safety -Physical Properties . ABSTRACT (Continue on reverse side it neceeeary end identify by block number) The Nitric Acid/Nitrogen Tetroxide Oxidizer Handbook is a compilation of engineering information on the physical and chamical properties, storage and handling, production, transportation, safety, and material compatibility of the nitric acid/nitrogen tetroxide family of oxidizers and their blends. It ,- contains information on the following propellants: DD 1473 JA FDITION OF I NOV 65 IY OBSOLETE Unclassified SECURITY CLASSIFICATION OF THIS PAGE (When Date Entored) UNCLASSIFIED SECURITY CLASSIFICATION OF THIS PAGE(Whl, .:414 ffnfe.ed) 20. ýAstract (Cont'd) Nitric Acid (IRFNA), High Density Acid) Nitrogen Tetroxide, MON-i) MON- 3, NON-i U MON-25, Minutemun Grade N 0 . 2 4 The propellant handbook is intended to be used for R&D personnel and test engineers who are directly involved in the utilization of liquid rocket propellants and the design of liquid rocket propulsion systems and facilities. UNCLASSIFIED SIKCURITV CLASSIFICATION OF THIS PAGE(When Dst, Entered) ACKNOWLEDGEMENTS During the course of the compilation of data the following individuels and organizations contributed to this handbook. Their cooperation is hereby gratefully acknowledged with thanks. Name Organizrtion Lt. R. Butts AFRPL/LKDP, Edwards AFB, California Mr. F. Forbes AFRPL/LKDP, Edwards AFB, California Ms. J. Trent Air Products, Allentown, Pennsylvania Mr. A. Followi,. Allied Chemical, Solvoy, New York Mr. H. Ph. Heubusch Bell Aerospace, B iffalo, New York Mr. L. Thompson Bell Aerospace, Buffalo, New York Mr. K. Pullen Boeing Co., Seattle, Washington Mr. D. Evans JPL, Pasadena, California Mr. W. Watge Kelly AFB, San Antonio, Texas Mr. R. F. Hausman Lockheed Missiles & Space Co., Inc. Sunnyvale, California Mr. D. F. Stone McDonnell-Douglas, St. Louis, Missouri Dr. M. Faget NASA, Houston, Texas Mr. H. Brasseaux NASA, Houston, Texas Dr. S. Wood Naval Weapons Center, China Lake, California Mr. G. W. Burdette Mr. M. Constantine Rocketdyne Division of Rockwell Mr. J. Weber International, Canoga Park, California M0r. G. Caton Thiokol Corporation, Newton, Pennsylvania Mr. E. Sutton Thiokol Corporation, Elkton, Maryland Mr. R. Vaughn TRW Systems, Inc., Redondo Beach, California Mr. R. Schmitt United Technologies, Sunnyvale, California Dr. H. Sislcr University of Florida, Gainesville, Florida Special thanks are also extended by the author to the following personnel at Martin Marietta Corporation, Denver, Division, who contri- buted to this work. Dr. R. Anselmi Mr. G. Roum Mr. J. Kling Mr. R. VandeKoppel Mr. R. Herzog Mr. L. Williams Mr. D. Ong TABLE OF CONTENTS Section Page List of Illustrations............................................................ ii List of Tables............................................................... iv 1.0 Introduction 1.1 General ............................................................... 1-1 1.2 Scope and Content.................................... I........ I.......... 1-7 1.3 Instructions to User.......................................................1.9 2.0 Properties and Logistics 2.1 Nitric Acid (Types lIlIIA, I I I8, and I II LS 2.1.1 Property Summary Sheet........................................... 2.1-1 2.1.2 General........................................................ 2.1-3 2.1.3 Phy~icaI Properties................................................ 2.1-4 2.1.4 Chemical Properties ...... **.................................2.1-23 2.1.5 Thermodynamic Properties ........ ................................. 2.1 -25 2.1.6 Logistics ....................................................... 2.1-31 2.1.7 References .............................. 2.1-33 2.2 Nitric Acid, Type IV (HDA) and Modified HDA (PF,) 5 2.2.1 Property Summary Sheet........................................... 2.2-1 2.2.2 General........................................................ 2.2-3 2.2.3 Physical Properties................................................ 2.2-5 2.2.4 Chemical Properties .................. ............................ 2.2-27 2.2.5 Thermodynamic Properties.......................................... 2.2-3 1 2.2.6 Logistics ....................................................... 2.2-38 2.2.7 References....................... ............................... 2.2-39 2.3 Nitrogen Tetroxide (NTO, MON-i1, MON-3, MON-'I0, MON-25) 2.3.1 Property Summary Sheet ........................................... 21.3-11 2.3.2 General........................................................ 2.3-3 2.3.3 Physical Properties ............................................... 2.3-7 2.3.4 Chemical Properties............................................... 2.3-39 2.3.5 Thermodynamic Properties.......................................... 2.3-43 2.3.6 Logistics ........................................................ 2.3-51 2.3.7 References ..................................................... 2.3-63 3.0 Handling, Storage and Compatibility 3.1 Introduction...........................................................3-1 3.1.1 General.......................................................... 3-1 3.1.2 Organization...................................................... 3-1 3.1.3 Scope.................................... ....................... 3-14 3.1.4 Usage Limitation................................................... 3-1 3.2 Handling and Transfer .................................................... 3-3 3.2.1 General .................................... 3-3 3.2,2 Handling and Transfer of Nitric*Ac~id a'n'd 'H*DA***.................3.-5 3.2.3 Handling and Transfer of Nitrogen Tstroxide .............................. 3-9 3.2.4 Disposal and Pollution Control......................................... 3-12 3.3 Storability ....................................................... 3-13 3.3.1 Generai ......................................................... 3-13 3.3.2 Storage Procedures ................................................. 3-13 TABLE OF CONTENTS (cont.) Section Page 3.4 Compatibility of Materials ................................................ 3-17 3.4.1 General ............... .......................................... 3-17 3.4.2 Materials Compatibility ot Nvitric Acids................................... 3-18 3.4.3 Materials Compatibility of HDA........................................ 3-21 3.4.4 Materials Compatibility of Nitrogen Tetroxide ............................. 3-25 3.4.5 Flow Decay Phenomena ............................................. 3-40 3.5 References ............................................................ 1-43 4.0 Safety 4.'1 lntrodoction........................................................... 4-1 4.2 Toxicity ............................................................. 4-3 4.2.1 General Introduction ............................................... 4-3 4.2.2 Hazards and Exposur-e Limits.......................................... 4-3 4.2.3 Preventive Measures................................................. 4-4 4.2.4 First Aid ......................................................... 4-6 4.2.5 Detection of Fumes ................................................ 4-7 4.2.6 Leak Detection.................................................... 4-7 4.2". 7 Area Monitoriig ................................................... 4-7 4.2.8 Dosimeters ....................................................... 4-8 4.3 Fire and Explosion Hazards.......................... ..................... 4-9 4.3.1 General. ............. .......................................... 4-9 7 4.3.21 Fire Hazards ..................................... ................ 4-9 4.3.3 Explosion Hazard................................................... 4-9 4.4 References.......................................... .................. 4-13 5.0 Appendices 5.1 :4ndex of Propellants, Acronyms and Compositions ............................... 5-1 5.2 Units and Conversion Factors 5.2.1 General........................................................... 5.3 5.2.2 Defined Constants ................................................. J3 5.2.3 Basic Constants.................................................... 5-4 5.2.4 Derived Constants............................. I.... I................ 5-4 5.2.5 Conversion Factors ................................................. 5-5 A3: LIST OF ILLUSTRATIONS Figure Page 1.1-1 N itric A cid H istory .......... ................................................. 1-2 1.1-2 H DA Hi story ............. ................................................... 1-3 1.1-3 N2 0 Hi story ................................................................ 1-5 4 2.1-1 Vapor Pressure of RFNA versus Temperature (°K) ................................. 2.1-6 2.2-2 Density of R FNA ......... *. ...................... ......................... 2.1-9 2.1-3 Rough Estimate of Sonic Velocity as Function of % N 0; .. 2.1-12 2 . . . . . . . . . . . . . . . . . . . . . . . . 2.1-4 Viscosity of RFNA versus Temperature .................. ..................... 2.1-14 2.1-5 Estimated Values of Surface Tension of RFNA versus Temperature .................... 2.1-17 2.1-6 Thermal Conductivity of RFNA versus Temperature .............. ................ 2.1-20 2.1-7 Heat Capacity of RFNA versus Temperature ............................ ...... 2.1-28 2.2-1 Phase Diagram for HNO -N 04 System .......................................... 2.2-4 3 2 2.2-2 Vapor Pressure of HDA versus Temperature ............. .... ................... 2.2-6 2.2-3 Density of Liquid HDA versus Temperature ............ ......................... 2.2-9 2.2-4 Sonic Velocity in HDA versus Temperature .... ............................... 2.2-12 2.2-5 Adiabatic Compressibitility of Liquid HDA versus Temperature ....................... 2.2-15 2.2-6 Liquid Viscosity of HDA versus Temperature ..................................... 2.2-18 2.2-7 Experimental Values of Surface Tension of HDA versus Temperature .................. 2.2-21 2.2-8 Thermal Conductivity of Liquid HDA versus Temperature ........................... 2.2-24 2.2-9 Helium and Nitrogen Gas Solubilities in HDA ..................................... 2.2-28 2.2-10 Haat Capacity of Liquid HDA versus Temperature ................................. 2.2-36 2.3-1 Freezing Point of the Nitrogen Tetroxide-Nitric Oxide System ........................ 2.3-4 2.3-2 Vapor Pressure versus Temperature, Liquid Nitrogen Tetro:ide ....................... 2.3-8 2.3-3 Vapor Pressure of the Mixed Oxides of Nitrogen .................................. 2.3-11 2.3-4 Vapor Pressure of the Mixed Oxides of Nitrogen at 536.67°R (298.15°K) wersus Weight Percent of Nitric Oxide ....................................... 2.3-13 2.3-5 Density versus Temperature, Liquid Nitrogen Tetroxide ............................. 2.3-15 2.3-6 Density of the Mixed Oxides of Nitrogen versus Temperature ........................ 2.3-17 2.3-7 Density of the Mixed Oxides of Nitrogen ........................................ 2.3-19 2.3-8 Sonic Velocity versus Ternperaturc Saturated N 0 -NO .. 2.3-21 2 4 2 .. . . . . . . . .. . . .. . . . . .. . . .. 2.3-9 Adiabatic Compressibility versus Temperature .................................... 2.3-24 2.3-1 C Isothermal Compressibility of Nitrogen Dioxide ................................... 2.3-27 2.3-11 Viscosity of Nitrogen Dioxide at the Bubble Point ................................. 2.3-30 2.3-12 Surface Tension of Saturated Nitrogen Tetrnxide .................................. 2.3-33 2.3-13 Thermal Conductivity of Nitrogen Tetroxide ............. ....................... 2.3-36 2.3-14 Helium Gas Solubility in Liquid Nitrogen Tetroxide ................................ 2.3-41 2.3.15 Heat Capacity of Liquid Nitrogen Tetroxiie ...................................... 2.3-45 2.3-16 Heat Capacity of Solid Nitrogen Tetroxide ....................................... 2.3-47 iiI LIST OF TABLES Table Page 1.1-1 Index of Subject Matter 2.1-1 Fuming Nitric Acids-Chemical Composition Limits ............................... 2.1-3 2.1-2 Reported Surface Tension Values for Nitric Acids ................................. 2.1-16 2.1-3 Heat of Formation, Various Nitric Acids ........................................ 2.1-25 2.1-4 Melting Point of Various Forms of Nitric Acid .................................... 2.1-26 2.1-5 Pseudocritical Constant of Nominal RFNA ....................................... 2.1-26 2.2-1 Ethalpy Contributions of HDA Components and the Heat of Formation of HDA ......... 2.2-31 2.2-2 Heat of Formation of Pure Compounds at Standard Conditions ....................... 2.2-32 2.2-3 Paeudocriticil Constants of HDA .............................................. 2.2-34 2.2-4 Estimated CP Values of !_iquid HDA ........................................... 2.2-35 2.3-1 Chemical Composition and Physical Properties ..................... ............... 2.3-5 2.3-2 Calculated Isothermal Compressibilities of NO2 .... 2.3-26 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.3-3 Test Data, Helium Solubility in N 0 ... 2.3-40 2 4 .. . . . . . . . . . . . . . . . . .. . . . .. . .. . .. . . . . . . . 3.4-1 Compatibility of Materials with Red Fuming Nitric Acid and Inhibited Red Fuming Nitric Acid ........................................ 3-18 3,4-2 Metal Strip/90% Nitric Acid Storage 1 est Data at 20 ± 5°C ............................ 3-20 3.4-3 Compatibility Classification of Materials with Rocket Propellants ....................... 3-21 3.4-4 Compatibility of Various Non-Metals with HDA ..................................... 3-22 3.4-5 Compatibility of Various Metals with HDA ........................................ 3-23 3.4-6 HDA Corrosion Inhibitor Comparisons ........................... ...... ......... 3-25 3.4-7 N204 Summary Compatibility Chart ............................................. 3.26 " , 3.4-8 Materials Compatibility (Exposed to N 0 at 275'F for 600 Hours) ..................... 3-,1 2 4 3.4-9 Compatibility Rating Summary for Selected Non-Metals with N 04 .. 1-32 2 .. . .. . . . . . . . . . . . . . . 3.4-10 Physical Appearance of One and Four Month Aluminum Specimens Prior to and After Removal of Propel~ant (N 04) ...................................... 3-37 2 3.4-11 Physical Appearance of One and Four Month Stainless Steel Specimens Prior to and After Removal of Propellant (N 04) ...................................... 3-38 2 3.4-12 Physical Appearance of One and Four Montth Titanium Specimens Prior to and After Removal of Propellants (N 04) .................................... 3-39 2 4.3-1 List of Safety Tests Used to Determine Fire and Explosion Hazards ...................... 4-9 4.3-2 Fire Hazard Tests of Various Materials Exposed to N 0 .... 4-10 2 4 . . . . . . .. . .. . .. . . .. .. . . . . . . 4.3-3 Results of Impact Tests in Liquid N 0 . 4-12 2 4 . . . . . . . . . . . . . . . . . . .. . .. . .. . . .. .. . . . . . . IV