USH306H - Method for preparation of amine salt bonding agents - Google Patents
Method for preparation of amine salt bonding agents Download PDFInfo
- Publication number
- USH306H USH306H US06/874,312 US87431286A USH306H US H306 H USH306 H US H306H US 87431286 A US87431286 A US 87431286A US H306 H USH306 H US H306H
- Authority
- US
- United States
- Prior art keywords
- amine salt
- bonding agent
- tetraethylene pentamine
- salt bonding
- stoichiometric amount
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
- 238000000034 method Methods 0.000 title claims abstract description 32
- 239000007767 bonding agent Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title description 7
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims abstract description 30
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical class NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 125000001731 2-cyanoethyl group Chemical group [H]C([H])(*)C([H])([H])C#N 0.000 claims abstract description 11
- 229920000768 polyamine Polymers 0.000 claims abstract description 11
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 239000003085 diluting agent Substances 0.000 claims abstract description 7
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 239000008240 homogeneous mixture Substances 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 18
- 239000003380 propellant Substances 0.000 abstract description 18
- 229910021529 ammonia Inorganic materials 0.000 abstract description 9
- 238000010926 purge Methods 0.000 abstract description 3
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 11
- 150000003863 ammonium salts Chemical class 0.000 description 7
- 239000000376 reactant Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- -1 amine compounds Chemical class 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 3
- 235000011130 ammonium sulphate Nutrition 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 2
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- ZHXAZZQXWJJBHA-UHFFFAOYSA-N triphenylbismuthane Chemical compound C1=CC=CC=C1[Bi](C=1C=CC=CC=1)C1=CC=CC=C1 ZHXAZZQXWJJBHA-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
Definitions
- Certain amine compounds such as TEPAN, a partially cyanoethylated tetraethylene pentamine, have long been used in the propellant industry as bonding agents in composite propellants containing ammonium perchlorate (AP). They greatly improve the mechanical properties of such propellants by chemically bonding AP particles to the binder matrix. TEPAN is also known to facilitate processing relative to other bonding agents since the mix viscosity of the propellant is not increased as much by TEPAN as it is by most other bonding agents.
- the disadvantage of using amine bonding agents is that ammonia is liberated during the mix and cure cycles due to displacement of ammonia from AP by amine groups in the bonding agent.
- the amine-ammonium perchlorate reaction requires subsequent ammonia removal from the mix because any residual ammonia will consume part of the isocyanate curing agent and thus interfere with propellant cure.
- an object of this invention is to provide a method for changing the polyamine to the corresponding ammonium salt that reduces the amount of water to be removed from the finished product by a substantial amount.
- a further object of this invention is to provide a method which employs the appropriate mineral acid for reacting directly with TEPAN or TEPANOL to yield the corresponding ammonium salt adduct without generation of noxious ammonia fumes.
- FIG. 1 of the drawing is an IR spectrograph depicting % transmittance versus wave number cm -1 of the adduct of cyanoethyl substituted tetraethylene pentamine and ammonium perchlorate prepared by a prior art method;
- a polyamine compound selected from the group consisting of cyanoethyl substituted tetraethylene pentamine (TEPAN), and the glycidol reaction product of cyanoethyl substituted tetraethylene pentamine (TEPANOL) is reacted with a stoichiometric ratio of perchloric acid to yield an adduct reaction product having only diluent water from perchloric acid solution that is subsequently stripped from the adduct reaction product.
- TEPAN 25.2 grams, is weighed and placed in a glass beaker. Perchloric acid (60%) in an amount of about 21.3 grams is slowly added with stirring to the TEPAN. After mixing for approximately 10 minutes to achieve homogeneity the reactant mixture is transferred to a vessel appropriate for stripping the less than 18% residual or diluent water from the product. In the prior art process, product at this point would be diluted by at least half with water.
- IR spectroscopic examination of the above reaction product prepared by this method is the same as that prepared by the old procedure. Compare IR curves, FIGS. 1 and 2.
- the prior method required ammonia and the copious amount of water present to be stripped off by heat, purge, and vacuum.
- the prior art method involves several additional steps and requires much greater preparation time than the method of this invention.
- the disclosed method is applicable to preparation of all amine salt bonding agents described in U.S. Pat. No. 4,493,741 by substituting the corresponding stoichiometric ratio of reactants. Since the finished bonding agent shown by IR spectroscopic examination, as depicted by FIGS. 1 and 2, to be equivalent identites for its intended use, the advantages set forth hereinabove for improved method are readily recognized. Also, the use of this amine bonding agent in a baseline propellant is shown under Example II below. This combination further illustrates the proven performance of an identical amine bonding agent made by the new method of this invention.
- the term TC-18 and TC-16 for identifying the amine salt bonding agent includes the amine TEPAN with about 1.8 and 1.6 equivalent ammonium ion donor per mole of polyamine. In each example there would be a nominal unreacted amine equivalents of about 3.2 and about 3.4 respectively for the TC-18 and TC-16 since prior to reacting there are about five amine equivalents present as secondary and a few tertiary amines (confirmed by IR).
- Example III For further information and comparison of propellant properties employing the amine salt bonding agents see Example III below and related comments.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A stoichiometric amount of a polyamine compound selected from the group cisting of cyanoethyl substituted tetraethylene pentamine (TEPAN), or the glycidol reaction product of cyanoethyl substituted tetraethylene pentamine (TEPANOL) is reacted with a stoichiometric amount of perchloric acid to yield an amine salt bonding agent useful in propellant compositions.
This improved method prevents the generation of ammonia (as in prior art method) which has to be removed prior to use of amine salt bonding agent in a propellant composition. Also, a lesser amount of diluent water is involved in this method which offers an advantage by not having to strip an excessive amount of water by heat, purge, or vacuum means.
The amine salt bonding agents prepared by this improved method are shown to be of like identity and quality as shown by IR spectroscopic examination and their testing in a propellant composition.
Description
The invention described herein may be manufactured, used, and licensed by or for the Government for governmental purposes without the payment to us of any royalties thereon.
Certain amine compounds such as TEPAN, a partially cyanoethylated tetraethylene pentamine, have long been used in the propellant industry as bonding agents in composite propellants containing ammonium perchlorate (AP). They greatly improve the mechanical properties of such propellants by chemically bonding AP particles to the binder matrix. TEPAN is also known to facilitate processing relative to other bonding agents since the mix viscosity of the propellant is not increased as much by TEPAN as it is by most other bonding agents. The disadvantage of using amine bonding agents is that ammonia is liberated during the mix and cure cycles due to displacement of ammonia from AP by amine groups in the bonding agent. The amine-ammonium perchlorate reaction requires subsequent ammonia removal from the mix because any residual ammonia will consume part of the isocyanate curing agent and thus interfere with propellant cure.
In a prior, commonly assigned U.S. Pat. No. 4,493,741 entitled "Amine Salts as Bonding Agents", ammonium salt adducts of TEPAN and TEPANOL and their processes for preparation are disclosed. The process for preparation of the adduct of TEPAN comprises reacting a water solution of the selected ammonium salt with TEPAN while stirring at room temperature. Similarly, a TEPAN-glycidol derivative product (TEPANOL) is also reacted with an ammonium salt to form the adduct of TEPANOL. The ammonium salt is selected from ammonium perchlorate (AP), ammonium nitrate (AN), ammonium sulfate (AS), and ammonium formate (AF).
Mechanical properties of a propellant composition, especially strain at maximum stress at -40° C. are substantially improved. The processing time, particularly the mix cycle time is shortened because of the amine salt bonding agent eliminating or minimizing in situ ammonia generation during the incorporation and mixing of ammonium perchlorate into the propellant mix.
As noted in the above described procedure from the prior U.S. Pat. No. 4,493,741 preparation of the amine salts involved solvation of the ammonium salt such as ammonium perchlorate, ammonium sulfate, etc. in distilled water, addition to the polyamine with stirring, and digestion for several hours at 170° C. or above. After these preparatory steps, ammonia and the copious amount of water present had to be stripped off by heat, purge, and vacuum.
An advantage of a more concise method of preparation of adducts of TEPAN and TEPANOL, provided the end products are comparable in quality, is readily recognized.
Therefore an object of this invention is to provide a method for changing the polyamine to the corresponding ammonium salt that reduces the amount of water to be removed from the finished product by a substantial amount.
A further object of this invention is to provide a method which employs the appropriate mineral acid for reacting directly with TEPAN or TEPANOL to yield the corresponding ammonium salt adduct without generation of noxious ammonia fumes.
The method of this invention comprises reacting a polyamine compound selected from the group consisting of cyanoethyl substituted tetraethylene pentamine, and the glycidol reaction product of cyanoethyl substituted tetraethylene pentamine with a stoichiometric ratio of perchloric acid by slowly adding with stirring the specified ratio of a 60% to 70% perchloric acid solution to the polyamine compound for approximately 10 minutes to obtain homogeneity, and thereafter, transferring the mixed reaction mixture to a vessel and stripping the diluent water from the reaction product.
FIG. 1 of the drawing is an IR spectrograph depicting % transmittance versus wave number cm-1 of the adduct of cyanoethyl substituted tetraethylene pentamine and ammonium perchlorate prepared by a prior art method; and,
FIG. 2 of the drawing is an IR spectrograph depicting % transmittance versus wave number cm-1 of the adduct reaction product of cyanoethyl substituted tetraethylene pentamine and perchloric acid prepared by the method of this invention.
A polyamine compound selected from the group consisting of cyanoethyl substituted tetraethylene pentamine (TEPAN), and the glycidol reaction product of cyanoethyl substituted tetraethylene pentamine (TEPANOL) is reacted with a stoichiometric ratio of perchloric acid to yield an adduct reaction product having only diluent water from perchloric acid solution that is subsequently stripped from the adduct reaction product.
The method reaction using TEPAN and perchloric acid as the reactants is as set forth under Example I below.
EXAMPLE I
______________________________________
Reactant Weight of Reactant (grams)
______________________________________
(1) TEPAN 25.2 grams
(2) Perchloric acid*
21.3 grams
______________________________________
*60% perchloric acid.
Note:
70% perchloric acid reduces water to less than 3% as compared to less tha
18% water when 60% perchloric acid is reactant (2).
TEPAN, 25.2 grams, is weighed and placed in a glass beaker. Perchloric acid (60%) in an amount of about 21.3 grams is slowly added with stirring to the TEPAN. After mixing for approximately 10 minutes to achieve homogeneity the reactant mixture is transferred to a vessel appropriate for stripping the less than 18% residual or diluent water from the product. In the prior art process, product at this point would be diluted by at least half with water.
IR spectroscopic examination of the above reaction product prepared by this method is the same as that prepared by the old procedure. Compare IR curves, FIGS. 1 and 2. However, the prior method required ammonia and the copious amount of water present to be stripped off by heat, purge, and vacuum. The prior art method involves several additional steps and requires much greater preparation time than the method of this invention.
The disclosed method is applicable to preparation of all amine salt bonding agents described in U.S. Pat. No. 4,493,741 by substituting the corresponding stoichiometric ratio of reactants. Since the finished bonding agent shown by IR spectroscopic examination, as depicted by FIGS. 1 and 2, to be equivalent identites for its intended use, the advantages set forth hereinabove for improved method are readily recognized. Also, the use of this amine bonding agent in a baseline propellant is shown under Example II below. This combination further illustrates the proven performance of an identical amine bonding agent made by the new method of this invention.
EXAMPLE II
______________________________________
BASELINE PROPELLANT COMPOSITION
______________________________________
R45HT - IPDI (56 parts)
9.81-9.61
DOA Dioctyl adipate
2%
Bonding agent* 0.15-0.35
Al 18%
AP 200/17 69%
Fe.sub.2 O.sub.3 1%
TPB, (Triphenyl bismuth)
0.02%
MA (Maleic anhydride)
0.02%
______________________________________
*Reaction adduct product of TEPAN/or TEPANOL and perchloric acid.
An experimental propellant formulation set forth under Example III, below, further compares physical properties of the propellant using TC-18 prepared by prior art process and the new process of this invention, TC-16 new process of this invention, and the parent compound TEPAN. The term TC-18 and TC-16 for identifying the amine salt bonding agent includes the amine TEPAN with about 1.8 and 1.6 equivalent ammonium ion donor per mole of polyamine. In each example there would be a nominal unreacted amine equivalents of about 3.2 and about 3.4 respectively for the TC-18 and TC-16 since prior to reacting there are about five amine equivalents present as secondary and a few tertiary amines (confirmed by IR). For further information and comparison of propellant properties employing the amine salt bonding agents see Example III below and related comments.
EXAMPLE III
______________________________________
EXPERIMENTAL PROPELLANT FORMULATION
______________________________________
Ingredient Weight Percent
______________________________________
R45HT/IPDI hydroxyterminated
9.75
polybutadiene/isophorone
diisocyanate (Binder and
Crosslinking Agent)
Plasticizer 2.00
TC-18 0.25
Fe.sub.2 O.sub.3 1.00
Al 17.00
AP 70.00
______________________________________
Propellant Formulation Physical Properties Values
Strain at (%)
Amine Salt Bonding
Stress Max/Stress/
Modulus
Agent (psi) Break (Psi)
______________________________________
TC-18 Prepared by prior art
process Tested at:
+140° F. 69 25/27 409
70 104 32/34 696
-40 291 39/43 5928
TC-18 prepared by new
process Tested at:
+140° F. 82 34/34 412
70° 99 37/37 563
-40° 311 40/43 3202
TC-16 prepared by new
process Tested at:
+140° F. 77 26/28 442
70° 97 29/29 584
-40° 338 35/36 3117
Parent Compound TEPAN
Tested at:
+140 79 23/23 514
70° 95 26/26 596
-40° 327 29/30 5260
______________________________________
The above data verifies the quality of the amine salt bonding agent by its function in a propellant composition.
Claims (2)
1. A method for preparing an amine salt bonding agent comprising:
(i) adding a predetermined stoichiometric amount of a polyamine compound selected from a cyanoethyl substituted tetraethylene pentamine and the glycidol reaction product of cyanoethyl substituted tetraethylene pentamine to a reaction container;
(ii) slowly adding with stirring a predetermined amount of a stoichiometric amount of perchloric acid to said polyamine compound, and continue stirring to achieve a homogenious mixture;
(iii) transferring said homogenous mixture to a vessel appropriate for stripping diluent water; and,
(iv) stripping diluent water from said reaction mixture and recovering said amine salt bonding agent.
2. The method of claim 1 wherein said polyamine compound selected is cyanoethyl substituted tetraethylene pentamine, said stoichiometric amount of said polyamine compound is about 25.2 grams, said stoichiometric amount of said perchloric acid which is 60% perchloric is about 21.3 grams, and wherein about 18 percent diluent water is stripped from said homogenous mixture and said amine salt bonding agent is recovered.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/874,312 USH306H (en) | 1986-06-09 | 1986-06-09 | Method for preparation of amine salt bonding agents |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US06/874,312 USH306H (en) | 1986-06-09 | 1986-06-09 | Method for preparation of amine salt bonding agents |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| USH306H true USH306H (en) | 1987-07-07 |
Family
ID=25363475
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US06/874,312 Abandoned USH306H (en) | 1986-06-09 | 1986-06-09 | Method for preparation of amine salt bonding agents |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | USH306H (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4493741A (en) | 1983-04-25 | 1985-01-15 | The United States Of America As Represented By The Secretary Of The Army | Amine salts as bonding agents |
-
1986
- 1986-06-09 US US06/874,312 patent/USH306H/en not_active Abandoned
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4493741A (en) | 1983-04-25 | 1985-01-15 | The United States Of America As Represented By The Secretary Of The Army | Amine salts as bonding agents |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AS | Assignment |
Owner name: UNITED STATES OF AMERICA, AS REPRESENTED BY THE SE Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:DUCOTE, MARJORIE E.;CARVER, JAMES G.;REEL/FRAME:004636/0388;SIGNING DATES FROM 19860530 TO 19860602 |
|
| STCF | Information on status: patent grant |
Free format text: PATENTED CASE |