US3384675A - Stabilization of nitroform salts - Google Patents

Stabilization of nitroform salts Download PDF

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Publication number
US3384675A
US3384675A US92091A US9209161A US3384675A US 3384675 A US3384675 A US 3384675A US 92091 A US92091 A US 92091A US 9209161 A US9209161 A US 9209161A US 3384675 A US3384675 A US 3384675A
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nitroform
salts
oxalate
salt
stabilization
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US92091A
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John A Brown
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ExxonMobil Technology and Engineering Co
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Exxon Research and Engineering Co
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/16—Hydrazine; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B23/00—Compositions characterised by non-explosive or non-thermic constituents
    • C06B23/006—Stabilisers (e.g. thermal stabilisers)
    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B47/00—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase
    • C06B47/02—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase the components comprising a binary propellant
    • C06B47/08—Compositions in which the components are separately stored until the moment of burning or explosion, e.g. "Sprengel"-type explosives; Suspensions of solid component in a normally non-explosive liquid phase, including a thickened aqueous phase the components comprising a binary propellant a component containing hydrazine or a hydrazine derivative

Definitions

  • This invention is concerned with stabilization of a nitroform salt of an amine by addition of a small amount of a suitable salt additive. More particularly, it is concerned with the use of certain salt of a metal and of a suitable acid, either an inorganic or organic acid, to increase the thermostability of an amine nitroform salt, such as hydrazinium nitroformate.
  • the amine nitroform salts are potent oxidizers in rocl cet propellant compositions. These salts are represented foremost by hydrazine nitroform N H -HC(NO which is also termed amino ammonium nitroformate' or hydrazinium nitroformate. Hydrazine nitroform is relatively more stable than other amine nitroform salts. Other amine nitroform salts are amino guanidine nitroform, polyamine nitroform and polyalkyleneamine nitroform salts.
  • the data indicate that the decomposition rate of an untreated nitroform salt, such as hydrazine nitroform, rises rapidly, as in a parabolic curve at elevated temperatures.
  • the decomposition rate is measured by the cubic centimeters of gas evolved per gram of sample tested during a period of time at a test temperature.
  • the salts are mixed in finely divided powdered form with the nitroform salt which is to be stabilized and the additive stabilizing salt may be used in amounts of about 1% to 5% by weight of the nitroform salt.
  • the amount of additive is in the range of 1 to 3 wt. percent of the nitroform salt stabilized.
  • the salt additives for stabilizing the nitroform salts are useful in storing the nitroform salts and in handling of the nitroform salts and compositing of the nitroform salts with other materials.
  • Stabilizing salts which are relatively free of undesirable side eifects of free acids can be used in combination with other materials that are sensitive to free acids.
  • the stabilized hydrazine nitroform may be composited with various other high-energy propellant oxidizers, fuel ingredients and binders. It may be encapsulated in suitable materials, e.g. compatible resins or metals, such as aluminum.
  • Hydrazine nitroform stabilized by about 1 to 5 wt. percent of mercurous oxalate admixed therewith.
  • Hydrazine nitroform stabilized by about 1 to 5 wt. percent mercuric oxalate admixed therewith.
  • Hydrazine nitroform stabilized by about 1 to 5 wt. percent of zinc chloride admixed therewith.
  • Hydrazine nitroform stabilized by about 1 to 5 wt. percent of admixed lead oxalate.
  • Hydrazine nitroform stabilized by about 1 to 5 wt. percent of admixed zinc oxalate.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)

Description

United States Patent 3,384,675 STABILIZATION 0F NITROFORM SALTS John A. Brown, Berkeley Heights, N.J., assignor to Esso Research and Engineering Company, a corporation of Delaware No Drawing. Filed Feb. 27, 1961, Ser. No. 92,091
6 Claims. (Cl. 260644) This invention is concerned with stabilization of a nitroform salt of an amine by addition of a small amount of a suitable salt additive. More particularly, it is concerned with the use of certain salt of a metal and of a suitable acid, either an inorganic or organic acid, to increase the thermostability of an amine nitroform salt, such as hydrazinium nitroformate.
The amine nitroform salts are potent oxidizers in rocl cet propellant compositions. These salts are represented foremost by hydrazine nitroform N H -HC(NO which is also termed amino ammonium nitroformate' or hydrazinium nitroformate. Hydrazine nitroform is relatively more stable than other amine nitroform salts. Other amine nitroform salts are amino guanidine nitroform, polyamine nitroform and polyalkyleneamine nitroform salts.
The mechanism by which the amine nitroform salts are stabilized by a small amount of a stabilizing additive is not completely understood. Studies show that the decomposition of the nitroform salts appears to be autocatalytic at elevated temperatures, e.g. 90 C. and higher. Alkaline substances and certain metals (e.g. Cu, Fe, Co, Ni) and their metal ions promote the instability. Ferric oxalate induces decomposition, and cupric oxalate induces an explosion after a brief induction period. It has been found in accordance with the present invention that salts which improve the stability of the amine nitroform salts especially well are mercuric and mercurous oxalate, zinc oxalate and zinc chloride.
The data indicate that the decomposition rate of an untreated nitroform salt, such as hydrazine nitroform, rises rapidly, as in a parabolic curve at elevated temperatures. The decomposition rate is measured by the cubic centimeters of gas evolved per gram of sample tested during a period of time at a test temperature.
Test data on the stabilization of hydrazine nitroform (HNF) are given in the following table:
TABLE.STABILIZATION OF HNF BY SALTS AT 90 C.
Decomposition, era/gram at SIP in- HNF Specimen Percent Additive 1 No data.
3,384,675 Patented May 21, 1968 'ice In the foregoing table the signs indicate that the decomposition rate has increased to well above 50 cc. per gram, the gas volume being determined as under standard conditions of temperature and pressure (ST-P).
The salts are mixed in finely divided powdered form with the nitroform salt which is to be stabilized and the additive stabilizing salt may be used in amounts of about 1% to 5% by weight of the nitroform salt. Preferably, the amount of additive is in the range of 1 to 3 wt. percent of the nitroform salt stabilized. By using the proper stabilizing additive in small amounts, the nitroform salt is inhibited from decomposing prematurely and the additive salt does not detract appreciably from the energy value of the nitroform salt when it is used in a rocket propellant composition.
The salt additives for stabilizing the nitroform salts are useful in storing the nitroform salts and in handling of the nitroform salts and compositing of the nitroform salts with other materials. Stabilizing salts which are relatively free of undesirable side eifects of free acids can be used in combination with other materials that are sensitive to free acids. The stabilized hydrazine nitroform may be composited with various other high-energy propellant oxidizers, fuel ingredients and binders. It may be encapsulated in suitable materials, e.g. compatible resins or metals, such as aluminum.
What is claimed is:
1. Hydrazine nitroform stabilized by an admixture of about 1 to 5 wt. percent of a salt selected from the group consisting of mercurous oxalate, mercuric oxalate, zinc chloride, zinc oxalate, and lead oxalate.
2. Hydrazine nitroform stabilized by about 1 to 5 wt. percent of mercurous oxalate admixed therewith.
3. Hydrazine nitroform stabilized by about 1 to 5 wt. percent mercuric oxalate admixed therewith.
4. Hydrazine nitroform stabilized by about 1 to 5 wt. percent of zinc chloride admixed therewith.
5. Hydrazine nitroform stabilized by about 1 to 5 wt. percent of admixed lead oxalate.
6. Hydrazine nitroform stabilized by about 1 to 5 wt. percent of admixed zinc oxalate.
References Cited UNITED STATES PATENTS 3,140,317 7/1964 Groves 260644 CARL D. QUARFORTH, Primary Examiner.
LEON D. ROSDOL, L. DEWAYNE RUTLEDGE,
Examiners.
J. W. WHISLER, L. A. SEBASTIAN,
Assistant Examiners.

Claims (1)

1. HYDRAZINE NITROFORM STABILIZED BY AN ADMIXTURE OF ABOUT 1 TO 5 WT. PERCENT OF A SALT SELECTED FROM THE GROUP CONSISTING OF MERCUROUS OXALATE, MERCURIC OXALATE, ZINC CHLORIDE, ZINC OXALATE, AND LEAD OXALATE.
US92091A 1961-02-27 1961-02-27 Stabilization of nitroform salts Expired - Lifetime US3384675A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5557015A (en) * 1992-11-03 1996-09-17 Aerospace Propulsion Products B.V. Method of preparing hydrazine nitroform

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3140317A (en) * 1961-03-03 1964-07-07 Dow Chemical Co Nitroform-hydrazine coordination compounds

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3140317A (en) * 1961-03-03 1964-07-07 Dow Chemical Co Nitroform-hydrazine coordination compounds

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5557015A (en) * 1992-11-03 1996-09-17 Aerospace Propulsion Products B.V. Method of preparing hydrazine nitroform

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