CN110759800A - High-energy high-mechanical-property electronic control solid propellant - Google Patents
High-energy high-mechanical-property electronic control solid propellant Download PDFInfo
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- CN110759800A CN110759800A CN201810840736.8A CN201810840736A CN110759800A CN 110759800 A CN110759800 A CN 110759800A CN 201810840736 A CN201810840736 A CN 201810840736A CN 110759800 A CN110759800 A CN 110759800A
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- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
- C06B33/12—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide the material being two or more oxygen-yielding compounds
- C06B33/14—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide the material being two or more oxygen-yielding compounds at least one being an inorganic nitrogen-oxygen salt
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0008—Compounding the ingredient
- C06B21/0025—Compounding the ingredient the ingredient being a polymer bonded explosive or thermic component
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
- C06B21/00—Apparatus or methods for working-up explosives, e.g. forming, cutting, drying
- C06B21/0033—Shaping the mixture
- C06B21/0058—Shaping the mixture by casting a curable composition, e.g. of the plastisol type
-
- C—CHEMISTRY; METALLURGY
- C06—EXPLOSIVES; MATCHES
- C06D—MEANS FOR GENERATING SMOKE OR MIST; GAS-ATTACK COMPOSITIONS; GENERATION OF GAS FOR BLASTING OR PROPULSION (CHEMICAL PART)
- C06D5/00—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets
- C06D5/06—Generation of pressure gas, e.g. for blasting cartridges, starting cartridges, rockets by reaction of two or more solids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
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Abstract
The invention discloses an electric control solid propellant with high energy and high mechanical property, belonging to the field of special solid propellants, wherein the electric control solid propellant comprises the following raw materials in percentage: a main oxidant: 55% -65%, auxiliary oxidant: 2% -4%, stabilizer: 2% -4%, binder: 12% -15%, cross-linking agent: 1% -2%, crosslinking assistant: 0.4% -0.8%, thickening fuel powder: 5% -8%, metal powder: 0% -5%, high explosive: 6 to 10 percent; the crosslinking assistant is adipic acid dihydrazide, and the high-energy explosive is one or more of hexogen, octogen and CL-20. The theoretical specific impulse stability of the electric control solid propellant is more than 260s under 6.86 MPa; the actual measurement compressive strength reaches more than 3.55MPa at 25 ℃, the technical problems of low energy and poor mechanical property of the electric control solid propellant are solved, and the technical requirements of high energy and high mechanical property of the electric control solid propellant are met.
Description
Technical Field
The invention relates to an electric control solid propellant formula with high energy and good mechanical property and a preparation process thereof, belonging to the field of special solid propellants.
Background
In the future development of aerospace and military, especially the development of missile weaponry towards high maneuverability and rapid defense penetration, the missile engine is required to have multiple starting and thrust adjusting capabilities. Conventional solid propellants consist of a binder (nitroglycerin, hydroxyl-terminated polybutadiene, etc.), an oxidizer (ammonium perchlorate, ammonium nitrate, etc.), and other components. Therefore, when the traditional solid propellant is ignited by the ignition powder, the engine can stop working only after the propellant grains are completely combusted, and the controllable flameout, multiple starting and thrust-adjustable operation are difficult to perform. Compared with the traditional solid propellant, the electric control solid propellant has the characteristics of no need of ignition powder for ignition due to different components and proportions, multiple times of ignition and flameout under the action of an external electric field, instantaneous combustion speed regulation and control, adjustable thrust and controllable output energy. This feature highlights the advantages of electrically controlled solid propellants and also distinguishes them from conventional solid propellants.
Therefore, the electrically-controlled solid propellant can replace liquid attitude control and end-repair engines for active missiles, the development of the electrically-controlled solid propellant towards high energy is a necessary choice, and the addition of metal combustion agents such as aluminum, magnesium, boron and the like to a propellant formula is inevitably involved. The metal has high combustion heat, although a large amount of heat can be released during combustion, the explosion heat and the combustion temperature of the propellant can be obviously improved, and further the specific impulse of the propellant is improved. However, since the content of the metal powder in the propellant is more than 5%, the condensed metal oxide (such as Al) is generated during combustion2O3MgO, etc.) easily produces primary smoke, causes high characteristic signals, and greatly reduces the effective stealth effect of the missile weapon.
In addition, due to the requirement of high maneuverability of missile weapon equipment, the electrically-controlled solid propellant is correspondingly required to have excellent mechanical properties in the use environment, and particularly, the propellant is required to have better compressive strength in a special mode of electrode contact and end face combustion of a spring-pushed propellant layer of the electrically-controlled solid engine. While the use of a large amount of metal powder increases the energy of the propellant, the high specific surface area of the metal powder reduces the mechanical properties of the propellant. Electrically controlled Solid Propellants have been reported to have a compressive strength of about 2.5MPa at ambient temperature (Sawka W N, Mcpherson M.electric Solid Propellants: A Safe, Micro to Macro propellant Technology [ C ]// AIAA/ASEM/SAE/ASEE Joint propellant conference.2013.), rendering the Propellants susceptible to deformation under pressure during use, limiting the use of such Propellants.
Therefore, the development of the electrically-controlled solid propellant with high energy, low characteristic signal and excellent mechanical property has very important significance.
Disclosure of Invention
In view of the above disadvantages of the prior art, the technical problem to be solved by the present invention is to provide an electrically controlled solid propellant with high energy and excellent mechanical properties and a preparation process thereof. On the premise of meeting the requirements, the requirements of real-time controllable thrust and repeatable ignition and flameout are met.
The technical scheme for realizing the purpose is as follows:
an electrically-controlled solid propellant with high energy and high mechanical property comprises the following raw materials in percentage:
a main oxidant: 55 to 65 percent
Auxiliary oxidant: 2 to 4 percent of
A stabilizer: 2 to 4 percent of
Adhesive: 12 to 15 percent
A crosslinking agent: 1 to 2 percent
Crosslinking assistant agent: 0.4 to 0.8 percent
Thickening fuel powder: 5 to 8 percent of
Metal powder: 0 to 5 percent
High explosive: 6 to 10 percent.
More preferably, the invention provides a formulation of the electric control solid propellant, which comprises the following components in percentage by weight:
a main oxidant: 56.15-61.37%
Auxiliary oxidant: 2.95 to 3.23 percent
A stabilizer: 2 to 4 percent of
Adhesive: 12 to 15 percent
A crosslinking agent: 1.2 to 1.8 percent
Crosslinking assistant agent: 0.4 to 0.8 percent
Thickening fuel powder: 5 to 8 percent of
Metal powder: 3 to 5 percent
High explosive: 6 to 10 percent.
Further, the primary oxidant is hydroxylamine nitrate.
Further, the auxiliary oxidant is one or more of ammonium nitrate, sodium nitrate and hydrazine nitrate.
Further, the stabilizer is 5-aminotetrazole.
Further, the binder is polyvinyl alcohol.
Further, the cross-linking agent is one or two of boric acid and borax.
Further, the crosslinking assistant is adipic acid dihydrazide.
Further, the thickening fuel powder is one or more of β -cyclodextrin, xylitol, corn starch, sodium alginate and methyl cellulose.
Further, the metal powder is one or more of aluminum powder, magnesium powder and boron powder.
Further, the high-energy explosive is one or more of hexogen, HMX and CL-20.
Further, the mass fraction ratio of the main oxidant to the auxiliary oxidant is 95: 5.
Furthermore, the type of the adhesive polyvinyl alcohol is 1788-2688, and the molar molecular weight of the adhesive polyvinyl alcohol is about 8-14 ten thousand.
The preparation process of the electric control solid propellant comprises the following steps:
①, carrying out decompression rotary evaporation on a hydroxylamine nitrate aqueous solution with the mass fraction of 15% at 50 ℃ to obtain a hydroxylamine nitrate concentrated solution with the mass fraction of more than 85%;
② adding auxiliary oxidant, stabilizer, thickening fuel powder and cross-linking agent into concentrated hydroxylamine nitrate solution at room temperature, and ultrasonic dissolving to form viscous liquid;
③ adding metal powder into the viscous liquid, and stirring under vacuum at 25 deg.C for 30 min;
④ adding the binder, the crosslinking assistant and the high-energy explosive into the ③ liquid, and stirring in vacuum to obtain uniform slurry;
⑤ pouring the obtained slurry into a combustion chamber under normal pressure to eliminate bubbles, placing in a vacuum oven at 35 deg.C, and curing.
Compared with the prior art, the invention has the following advantages:
1) the invention reduces the content of metal powder by adding high-energy explosive, has higher energy, further improves the specific impulse of the propellant and simultaneously reduces characteristic signals.
2) The invention utilizes the synergistic effect of the cross-linking agent and the cross-linking assistant to be combined with a viscous system formed by thickening fuel powder, so that the binder is cross-linked to form a very compact cross-linked network, the binding force among all components of the propellant is improved, the hygroscopicity of the propellant is reduced, and the mechanical property of the propellant is further improved.
3) The invention utilizes the stabilizer to modify the main oxidant, improves the stability of the main oxidant through acting forces such as intermolecular hydrogen bond and the like, and improves the decomposition temperature and the anti-phase change capability of the main oxidant.
4) The mass fraction ratio of the main oxidant to the auxiliary oxidant is 95: 5, and the auxiliary oxidant is added in a proper proportion, so that the crystallization capacity of the main oxidant at normal temperature is reduced, and the combustion performance of the propellant is improved.
5) The invention carries out a large number of experiments, optimizes the components and the content of the propellant, and gives out the optimal components and the proportion, so that the energy and the mechanical property of the propellant are obviously improved and better.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
The embodiment of the invention provides a high-energy high-mechanical-property electric control solid propellant, which comprises the following components in percentage by mass:
a main oxidant: 55% -65%, auxiliary oxidant: 2% -4%, stabilizer: 2% -4%, binder: 12% -15%, cross-linking agent: 1% -2%, crosslinking assistant: 0.4% -0.8%, thickening fuel powder: 5% -8%, metal powder: 0% -5%, high explosive: 6 to 10 percent.
The method comprises the steps of carrying out reduced pressure rotary evaporation on a hydroxylamine nitrate aqueous solution with the mass fraction of 15% at 50 ℃ to obtain a hydroxylamine nitrate concentrated solution with the mass fraction of 89.56%; under the condition of room temperature, adding an auxiliary oxidant, a stabilizer, thickening fuel powder and a cross-linking agent into the concentrated hydroxylamine nitrate solution, and carrying out ultrasonic treatment until the auxiliary oxidant, the stabilizer, the thickening fuel powder and the cross-linking agent are dissolved to form viscous liquid; adding metal powder into the viscous liquid, and stirring for 30 minutes in vacuum at 25 ℃; adding an adhesive, a crosslinking assistant and a high-energy explosive into the liquid, and stirring in vacuum to obtain uniform slurry; and (3) pouring the obtained uniformly stirred slurry into a combustion chamber under the normal pressure condition, eliminating bubbles, placing the slurry into a vacuum oven at 35 ℃, and curing and forming.
Example 1
(1) High-energy high-mechanical-property electric control solid propellant composition
Components | Content (% wt) |
Hydroxylamine nitrate (HAN) | 59.7 |
Ammonium Nitrate (AN) | 4 |
5-aminotetrazole (5-ATZ) | 2.5 |
Polyvinyl alcohol (PVA) | 13 |
Borax (HB) | 1 |
Adipic Acid Dihydrazide (ADH) | 0.8 |
β -Cyclodextrin (β -CD) | 5 |
Aluminium powder (Al) | 4 |
Hexogen (RDX) | 10 |
(2) High-energy high-mechanical-property electric control solid propellant property
Theoretical specific impulse at 6.86 MPa: 272 s.
The actual measured compressive strength at 25 ℃ is: 3.58 MPa.
Example 2
(1) High-energy high-mechanical-property electric control solid propellant composition
Components | Content (% wt) |
Hydroxylamine nitrate (HAN) | 65 |
Ammonium Nitrate (AN) | 2.5 |
5-aminotetrazole (5-ATZ) | 2 |
Polyvinyl alcohol (PVA) | 12.5 |
Boric acid (HB) | 1.5 |
Adipic Acid Dihydrazide (ADH) | 0.5 |
Sodium Alginate (SA) | 6.5 |
Aluminium powder (Al) | 3.5 |
HMX (HMX) | 6 |
(2) High-energy high-mechanical-property electric control solid propellant property
Theoretical specific impulse at 6.86 MPa: 270 s.
The actual measured compressive strength at 25 ℃ is: 3.73 MPa.
Example 3
(1) High-energy high-mechanical-property electric control solid propellant composition
Components | Content (% wt) |
Hydroxylamine nitrate (HAN) | 55 |
Ammonium Nitrate (AN) | 3.1 |
5-aminotetrazole (5-ATZ) | 2.5 |
Polyvinyl alcohol (PVA) | 15 |
Boric acid (HB) | 2 |
Adipic Acid Dihydrazide (ADH) | 0.4 |
Xylitol (Xylitol) | 7 |
Magnesium powder (Mg) | 5 |
Hexogen (RDX) | 10 |
(2) High-energy high-mechanical-property electric control solid propellant property
Theoretical specific impulse at 6.86 MPa: 261 s.
The actual measured compressive strength at 25 ℃ is: 3.69 MPa.
Example 4
(1) High-energy high-mechanical-property electric control solid propellant composition
Components | Content (% wt) |
Hydroxylamine nitrate (HAN) | 59.2 |
Ammonium Nitrate (AN) | 2 |
5-aminotetrazole (5-ATZ) | 4 |
Polyvinyl alcohol (PVA) | 12 |
Borax (HB) | 1.1 |
Adipic Acid Dihydrazide (ADH) | 0.7 |
β -Cyclodextrin (β -CD) | 8 |
Magnesium powder (Mg) | 5 |
HMX (HMX) | 8 |
(2) High-energy high-mechanical-property electric control solid propellant property
Theoretical specific impulse at 6.86 MPa: 267 s.
The actual measured compressive strength at 25 ℃ is: 3.64 MPa.
Example 5
(1) The high-energy high-mechanical-property electric control solid propellant consists of a main oxidant and an auxiliary oxidant, wherein the mass fraction ratio of the main oxidant to the auxiliary oxidant is 95: 5.
(2) High-energy high-mechanical-property electric control solid propellant property
Theoretical specific impulse at 6.86 MPa: 268 s.
The actual measured compressive strength at 25 ℃ is: 3.81 MPa.
Example 6
(1) The high-energy high-mechanical-property electric control solid propellant consists of a main oxidant and an auxiliary oxidant, wherein the mass fraction ratio of the main oxidant to the auxiliary oxidant is 95: 5.
Components | Content (% wt) |
Hydroxylamine nitrate (HAN) | 59.76 |
Ammonium Nitrate (AN) | 3.14 |
5-aminotetrazole (5-ATZ) | 3 |
Polyvinyl alcohol (PVA) | 14 |
Boric acid (HB) | 1.5 |
Adipic Acid Dihydrazide (ADH) | 0.6 |
Xylitol (Xylitol) | 6 |
Magnesium powder (Mg) | 5 |
HMX (HMX) | 7 |
(2) High-energy high-mechanical-property electric control solid propellant property
Theoretical specific impulse at 6.86 MPa: 267 s.
The actual measured compressive strength at 25 ℃ is: 3.84 MPa.
Example 7
(1) The high-energy high-mechanical-property electric control solid propellant consists of a main oxidant and an auxiliary oxidant, wherein the mass fraction ratio of the main oxidant to the auxiliary oxidant is 95: 5.
Components | Content (% wt) |
Hydroxylamine nitrate (HAN) | 56.15 |
Ammonium Nitrate (AN) | 2.95 |
5-aminotetrazole (5-ATZ) | 4 |
Polyvinyl alcohol (PVA) | 13 |
Borax (NB) | 1.2 |
Adipic Acid Dihydrazide (ADH) | 0.7 |
Sodium Alginate (SA) | 7 |
Magnesium powder (Mg) | 5 |
Hexogen (RDX) | 10 |
(2) High-energy high-mechanical-property electric control solid propellant property
Theoretical specific impulse at 6.86 MPa: 266s, respectively.
The actual measured compressive strength at 25 ℃ is: 3.78 MPa.
Example 8
(1) The high-energy high-mechanical-property electric control solid propellant consists of a main oxidant and an auxiliary oxidant, wherein the mass fraction ratio of the main oxidant to the auxiliary oxidant is 95: 5.
Components | Content (% wt) |
Hydroxylamine nitrate (HAN) | 61.37 |
Ammonium Nitrate (AN) | 3.23 |
5-aminotetrazole (5-ATZ) | 3 |
Polyvinyl alcohol (PVA) | 12 |
Borax (NB) | 1.6 |
Adipic Acid Dihydrazide (ADH) | 0.8 |
Methylcellulose (MC) | 7 |
Aluminium powder (Al) | 5 |
HMX (HMX) | 6 |
(2) High-energy high-mechanical-property electric control solid propellant property
Theoretical specific impulse at 6.86 MPa: 271 s.
The actual measured compressive strength at 25 ℃ is: 3.67 MPa.
Example 9
(1) The high-energy high-mechanical-property electric control solid propellant consists of a main oxidant and an auxiliary oxidant, wherein the mass fraction ratio of the main oxidant to the auxiliary oxidant is 95: 5.
Components | Content (% wt) |
Hydroxylamine nitrate (HAN) | 60.14 |
Ammonium Nitrate (AN) | 3.16 |
5-aminotetrazole (5-ATZ) | 2.5 |
Polyvinyl alcohol (PVA) | 14 |
Boric acid (HB) | 1.8 |
Adipic Acid Dihydrazide (ADH) | 0.4 |
Corn Starch (SFC) | 8 |
Aluminium powder (Al) | 3 |
CL-20 | 7 |
(2) High-energy high-mechanical-property electric control solid propellant property
Theoretical specific impulse at 6.86 MPa: 263 s.
The actual measured compressive strength at 25 ℃ is: 3.71 MPa.
Finally, it should be noted that the above-mentioned list is only a specific embodiment of the present invention. It is obvious that the present invention is not limited to the above embodiments, but many variations are possible. All modifications which can be derived or suggested by a person skilled in the art from the disclosure of the present invention are to be considered within the scope of the invention.
Claims (10)
1. The electric control solid propellant with high energy and high mechanical property is characterized in that the electric control solid propellant comprises the following components in percentage by mass:
a main oxidant: 55 to 65 percent
Auxiliary oxidant: 2 to 4 percent of
A stabilizer: 2 to 4 percent of
Adhesive: 12 to 15 percent
A crosslinking agent: 1 to 2 percent
Crosslinking assistant agent: 0.4 to 0.8 percent
Thickening fuel powder: 5 to 8 percent of
Metal powder: 0 to 5 percent
High explosive: 6 to 10 percent.
2. The electric control solid propellant with high energy and high mechanical property is characterized in that the electric control solid propellant comprises the following components in percentage by mass:
a main oxidant: 56.15-61.37%
Auxiliary oxidant: 2.95 to 3.23 percent
A stabilizer: 2 to 4 percent of
Adhesive: 12 to 15 percent
A crosslinking agent: 1.2 to 1.8 percent
Crosslinking assistant agent: 0.4 to 0.8 percent
Thickening fuel powder: 5 to 8 percent of
Metal powder: 3 to 5 percent
High explosive: 6 to 10 percent.
3. An electrically controlled solid propellant according to claim 1 or claim 2 wherein the primary oxidant is hydroxylamine nitrate.
4. An electrically controlled solid propellant according to claim 1 or 2 wherein the auxiliary oxidising agent is one or more of ammonium nitrate, sodium nitrate and hydrazine nitrate.
5. An electrically controlled solid propellant according to claim 1 or claim 2 wherein the stabiliser is 5-aminotetrazole.
6. An electrically controlled solid propellant according to claim 1 or claim 2 wherein the binder is polyvinyl alcohol.
7. An electrically controlled solid propellant according to claim 1 or claim 2 wherein the cross-linking agent is one or both of boric acid or borax.
8. An electrically controlled solid propellant according to claim 1 or 2 wherein the cross-linking co-agent is adipic acid dihydrazide.
9. An electrically controlled solid propellant as claimed in claim 1 or claim 2 wherein the thickened fuel powder is one or more of β -cyclodextrin, xylitol, corn starch, sodium alginate and methyl cellulose.
10. An electrically controlled solid propellant according to claim 1 or 2 wherein the high explosive is one or more of hexogen, octogen and CL-20.
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Cited By (2)
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CN115403432A (en) * | 2022-08-25 | 2022-11-29 | 西安交通大学 | Novel electric control solid propellant and thermal analysis experimental method |
CN117402024A (en) * | 2023-12-13 | 2024-01-16 | 中国科学院大连化学物理研究所 | Spontaneous green liquid propellant and preparation method thereof |
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CN117402024A (en) * | 2023-12-13 | 2024-01-16 | 中国科学院大连化学物理研究所 | Spontaneous green liquid propellant and preparation method thereof |
CN117402024B (en) * | 2023-12-13 | 2024-02-23 | 中国科学院大连化学物理研究所 | Spontaneous green liquid propellant and preparation method thereof |
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