CN108456293B - Composite solid propellant grain defect repairing material and preparation method thereof - Google Patents
Composite solid propellant grain defect repairing material and preparation method thereof Download PDFInfo
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- CN108456293B CN108456293B CN201810204208.3A CN201810204208A CN108456293B CN 108456293 B CN108456293 B CN 108456293B CN 201810204208 A CN201810204208 A CN 201810204208A CN 108456293 B CN108456293 B CN 108456293B
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- powder column
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- ammonium perchlorate
- kneader
- polyol
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6204—Polymers of olefins
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/6705—Unsaturated polymers not provided for in the groups C08G18/671, C08G18/6795, C08G18/68 or C08G18/69
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/11—Esters; Ether-esters of acyclic polycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
A composite solid propellant grain defect repairing material comprises the following components: a hydroxyl terminated polybutadiene binder; a toluene diisocyanate curing agent; dioctyl sebacate plasticizer; ammonium perchlorate oxidant; the aluminum powder metal fuel and the polyhydroxy compound reinforcing agent comprise the following components in percentage by weight: 15-18 wt% of hydroxyl-terminated polybutadiene, 55-65 wt% of ammonium perchlorate, 12-16 wt% of aluminum powder, 4-6 wt% of dioctyl sebacate, 1-2.5 wt% of toluene diisocyanate and 0.5-3 wt% of polyhydroxy compound, wherein the polyhydroxy compound is selected from one of trimethylolpropane, trimethylolethane, pentaerythritol, glycerol, mannitol and acrolein pentaerythritol resin. The invention provides a repairing material with better comprehensive performance, which can be used for repairing the defects of cured hydroxyl-terminated polybutadiene composite solid propellant grains.
Description
Technical field
The invention belongs to solid propellant rocket propellant technical fields, and in particular to use to a kind of solid propellant rocket
The preparation method of composite solidpropellant powder column defect mending material and the patching material.
Background technique
Solid propellant rocket motor charge is in solidification cooling, long-term storage, transport, duties treatment process, because by various
Load and Propellant aging effect, it is possible to create the faults of construction such as crackle, stomata.These defects destroy the combustion of raw medicine type design
Burn rule, may cause combustion face increase, combustion chamber pressure quickly increase, it is serious to may cause engine explosions, cause personnel
With the loss of equipment.Since solid propellant rocket cost is high, is scrapped not the defects of should be because of localized cracks, should make every effort to repair
It is utilized after benefit.
Motor grain Crack Repairing material should be compatible with propellant material matrix, to guarantee that it is higher viscous that patching material has
Connect intensity；With good technique levelability, convenient for operation and storage；Energy response will match with powder column, avoid energy big
Amplitude reduction；There is good adhesive property with powder column interface, adhesive strength is close to powder column self-strength, repairing area elongation percentage
It meets the requirements；It should not result in the powder column mechanical properties decrease at intact position after patching material elevated cure.
At present for the composite solidpropellant powder column defect using end hydroxy butadiene (HTPB) adhesive composition, repair
It mends material and mainly uses HTPB adhesive composition.Compared with solid propellant grain, patching material considerably reduces oxidant
The content of ammonium perchlorate (AP) and metal fuel aluminium powder (Al), and some aphlogistic oxides are added to, this causes to repair
The quick-fried calorific value of material is lower than the quick-fried calorific value of propellant charge, so that the specific impulse of solid propellant rocket be made to decline；Has repairing material
Material formula hot setting also results in the raising of propellant charge intensity, elongation percentage decline.
Summary of the invention
Therefore, the purpose of the present invention is to provide a kind of composite solidpropellant powder column defect mending material, consolidated with being directed to
The defect for changing end hydroxy butadiene composite solidpropellant powder column, solving existing patching material formula hot setting causes to promote
The problem that agent powder column intensity increases, elongation percentage decline and patching material energy characteristics are relatively low.
According to the one aspect of invention, provide a kind of composite solidpropellant powder column defect mending material, it include with
Lower component: end hydroxy butadiene adhesive；Diisocyanate curing agent；Dioctyl sebacate plasticizer；Ammonium perchlorate
Oxidant；Aluminium powder metal fuel, it is even more important that further include reinforcing agent, and the reinforcing agent is polyol.
Further, the content range of above-mentioned each component is as follows: end hydroxy butadiene 15wt%-18wt%, high chlorine
Sour ammonium is 55wt%-65wt%, aluminium powder 12wt%-16wt%, dioctyl sebacate 4wt%-6wt%, toluene diisocyanate
Acid esters is 1wt%-2.5wt%, polyol 0.5wt%-3wt%.
Further, above-mentioned polyol is selected from trimethylolpropane, trimethylolethane, pentaerythrite, the third three
One of alcohol, mannitol and methacrylaldehyde pentaerythritol resin.
Further, above-mentioned polyol is methacrylaldehyde pentaerythritol resin.
Also further, the content range of above-mentioned methacrylaldehyde pentaerythritol resin is 0.5wt%-1.5wt%.
The present invention also provides a kind of preparation method of above-mentioned composite solidpropellant powder column defect mending material, the sides
Method the following steps are included:
A) ammonium perchlorate and aluminium powder are sieved respectively, are put into dry in the vacuum oven that temperature is 50-70 DEG C, vacuum degree
1000Pa, drying time are no less than 2 hours, are cooled to room temperature use naturally；
B) end hydroxy butadiene is weighed into rustless steel container, adds dioctyl sebacate, polyol and step
Pre-composition is added in kneader after premix and mix by rapid aluminium powder a) handled well, and kneader circulator bath temperature is 50 DEG C；
C) the step a) ammonium perchlorate handled well is added in two portions in kneader, is uniformly mixed；
D) toluene di-isocyanate(TDI) is added in kneader, continuously mixes 45min, obtained composite solidpropellant powder column and lack
Fall into patching material.
Solid propellant grain defect mending is carried out using composite solidpropellant powder column defect mending material of the present invention
Method and step is as follows:
Propellant charge rejected region is trimmed to no wedge angle with plastic knife by step 1, patching material medicine slurry is easy to fill out
Propellant charge rejected region is cleaned out with the pure cotton cloth for having impregnated ethyl acetate, is then placed in casting room by the shape filled；
Step 2 lacks the uniformly mixed composite solidpropellant powder column obtained according to preparation method provided by the invention
The medicine slurry vacuum pouring of patching material is fallen into propellant charge rejected region, then vacuum degassing 30min is put propellant charge
Enter in 50 DEG C of solidification case and solidifies 7 days；
Step 3 after propellant charge is naturally cooling to room temperature, carries out Shape correction, defect to the propellant charge of reparation
With dressing blade the extra patching material for being higher by powder column type face is adapted in shaping surface concordant with powder column type face.
Because composite solidpropellant powder column defect mending material homogeneity of the present invention is good, the repairing to defect powder column
Simple process is easy to control than the prior art.
Compared with the prior art, the beneficial effects of the present invention are:
By adding polyol in patching material is formulated, solving patching material formula hot setting causes to push away
Into the problem of the raising of agent powder column intensity, elongation percentage decline；Using ammonium perchlorate and aluminium powder as solid packing, and patching material is matched
Solid packing content is close with defective propellant charge formulation content in side, solves that patching material energy characteristics is relatively low to ask
Topic；The preparation process of patching material is consistent with propellant charge preparation process, ensure that the uniformity and property of patching material mixing
The consistency of energy.
The present invention overcomes the deficiencies of existing solid propellant grain defect mending material, and it is more preferable to provide a kind of comprehensive performance
Patching material, can be used for repairing the defect of cured end hydroxy butadiene composite solidpropellant powder column.
Detailed description of the invention
Fig. 1 is the composite solidpropellant sample of fracture and its photo of the plane of disruption；
Fig. 2 is answering with composite solidpropellant of embodiment of the present invention powder column defect mending materials repairing and after the completion of solidifying
Close solid propellant sample photo；
After composite solidpropellant sample completes uniaxial tensile test after the completion of Fig. 3 is repairing shown in Fig. 2 and solidifies
Photo.
Specific embodiment
In order to make those skilled in the art more fully understand the present invention, with reference to the accompanying drawings and detailed description to this hair
It is bright to be described in further detail.Here it is to be noted that it in the accompanying drawings, the imparting of identical appended drawing reference is substantially had
The component part of same or like structure and function, and will omit about their repeated description.
A kind of embodiment 1: composite solidpropellant powder column defect mending material
In the present embodiment, the formula composition and each component of a kind of composite solidpropellant powder column defect mending material are provided
Content (each component content is by mass percentage), and formula composition and each component with the defective propellant to be repaired of powder column
Content compares, and is shown in Table 1；It is listed in the following table 1 as composite solidpropellant powder column defect mending material of the present invention
With the formula composition and each component content of propellant to be repaired.
The formula composition and component content of the propellant to be repaired of table 1 and patching material of the present invention
Embodiment 2: the preparation method of composite solidpropellant powder column defect mending material
By patching material formula composition and each component content of the present invention listed in the table 1 of embodiment 1, each component is weighed,
Composite solidpropellant powder column defect mending material is prepared according to the following steps:
A) ammonium perchlorate and aluminium powder are sieved respectively, are put into dry in the vacuum oven that temperature is 50-70 DEG C, vacuum degree
1000Pa, drying time are no less than 2 hours, are cooled to room temperature use naturally；
B) end hydroxy butadiene is weighed into rustless steel container, adds dioctyl sebacate, polyol and step
Pre-composition is added in kneader after premix and mix by rapid aluminium powder a) handled well, and kneader circulator bath temperature is 50 DEG C；
C) the step a) ammonium perchlorate handled well is added in two portions in kneader, is uniformly mixed；
D) toluene di-isocyanate(TDI) is added in kneader, continuously mixes 45min, obtained composite solidpropellant powder column and lack
Fall into patching material.
Embodiment 3: composite solidpropellant powder column defect mending material is uniaxially stretched Effect on Mechanical Properties to propellant
The composite solidpropellant powder column defect mending material obtained according to the formula composition of embodiment 1,2 and method and step
Material, repairs 3 groups of composite solidpropellant samples (as shown in Fig. 1) for being uniaxially stretched fracture using patching material, repairs
Propellant sample photo after benefit is as shown in Fig. 2, to before composite solidpropellant powder column defect mending materials repairing of the present invention
Propellant sample afterwards carries out being uniaxially stretched Mechanics Performance Testing, and by portion mark QJ924-85, " composite solidpropellant is unidirectional for test
Stretching test method " it carries out, test temperature is 25 ± 2 DEG C, and relative humidity is not higher than 70%, rate of extension 100mmmin-1,
Composite solidpropellant sample photo after test is as shown in Fig. 3.Test result is shown in the following table 2.
Before and after 2 composite solidpropellant powder column defect mending materials repairing of table
Propellant is uniaxially stretched mechanical property
As can be seen that after being repaired using composite solidpropellant powder column defect mending material of the present invention, the maximum of propellant
Tensile strength is reduced to 0.55MPa by 0.57MPa, is held essentially constant；Maximum extension rate increases to 15.91% by 5.72%, increases
Add 178.1%, has dramatically increased.
Repairing propellant charge defect scheme in the prior art includes modified HTPB glue, grouting material and medicine slurry gluing
Agent material etc. analyzes and researches to disclosed document, and relatively more modified HTPB glue, grouting material and medicine slurry adhesive material are repaired
That mends front and back propellant charge is uniaxially stretched data of mechanical, it can be seen that repairs it through above-mentioned prior art means
Propellant charge afterwards perhaps significantly reduces the maximum tensile strength of former propellant charge and elongation percentage or only maintains
The maximum tensile strength and elongation percentage data of former propellant charge.
Therefore, the maximum that composite solidpropellant powder column defect mending material of the present invention can significantly increase propellant charge is prolonged
Rate is stretched, the mechanical property of propellant charge after repairing is improved, there is good repairing effect.
Various embodiments of the present invention are described above, above description is exemplary, and non-exclusive, and
It is not limited to disclosed each embodiment.Without departing from the scope and spirit of illustrated each embodiment, for this skill
Many modifications and changes are obvious for the those of ordinary skill in art field.Therefore, protection scope of the present invention is answered
This is subject to the protection scope in claims.
Claims (4)
1. a kind of composite solidpropellant powder column defect mending material, it includes following component: end hydroxy butadiene adhesive；
Diisocyanate curing agent；Dioctyl sebacate plasticizer；Ammonium perchlorate oxidiser；Aluminium powder metal fuel, feature exist
In further including reinforcing agent, and the reinforcing agent is polyol；
The content range of each component is as follows: end hydroxy butadiene 15wt%-18wt%, ammonium perchlorate 55wt%-
65wt%, aluminium powder 12wt%-16wt%, dioctyl sebacate 4wt%-6wt%, toluene di-isocyanate(TDI) 1wt%-
2.5wt%, polyol 0.5wt%-3wt%；
The polyol is selected from trimethylolpropane, trimethylolethane, pentaerythrite, glycerine, mannitol and third
One of olefine aldehydr pentaerythritol resin.
2. composite solidpropellant powder column defect mending material as described in claim 1, which is characterized in that described polyhydroxylated
Conjunction object is methacrylaldehyde pentaerythritol resin.
3. composite solidpropellant powder column defect mending material as claimed in claim 2, which is characterized in that the methacrylaldehyde season
The content range of penta 4 alcohol resins is 0.5wt%-1.5wt%.
4. a kind of system of the composite solidpropellant powder column defect mending material as described in any claim in claim 1-3
Preparation Method, which is characterized in that the described method comprises the following steps:
A) ammonium perchlorate and aluminium powder are sieved respectively, are put into dry in the vacuum oven that temperature is 50-70 DEG C, vacuum degree
1000Pa, drying time are no less than 2 hours, are cooled to room temperature use naturally；
B) end hydroxy butadiene is weighed into rustless steel container, adds dioctyl sebacate, polyol and step a)
Pre-composition is added in kneader after premix and mix by the aluminium powder handled well, and kneader circulator bath temperature is 50 DEG C；
C) the step a) ammonium perchlorate handled well is added in two portions in kneader, is uniformly mixed；
D) toluene di-isocyanate(TDI) is added in kneader, continuously mixes 45min, obtains composite solidpropellant powder column defect and repair
Mend material.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810204208.3A CN108456293B (en) | 2018-03-13 | 2018-03-13 | Composite solid propellant grain defect repairing material and preparation method thereof |
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| CN201810204208.3A CN108456293B (en) | 2018-03-13 | 2018-03-13 | Composite solid propellant grain defect repairing material and preparation method thereof |
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| CN108456293B true CN108456293B (en) | 2019-02-22 |
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| CN110907010B (en) * | 2019-12-16 | 2020-12-08 | 中国人民解放军国防科技大学 | Flow-induced resonance-based propellant residual quantity measuring device and measuring method in storage tank |
| KR102575547B1 (en) | 2020-09-04 | 2023-09-11 | 한화에어로스페이스 주식회사 | Solid propellant repair washcoat composition and solid propellant repair method |
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| CN105198681B (en) * | 2014-06-10 | 2017-07-04 | 湖北航天化学技术研究所 | A kind of room temperature curing type cleaning solid propellant |
| CN106632955A (en) * | 2016-12-18 | 2017-05-10 | 内蒙古航天红峡化工有限公司 | Hydroxy terminated polybutadiene propellant grain defect repairing material and application technique thereof |
| CN107420223B (en) * | 2017-07-24 | 2019-03-29 | 湖北三江航天江河化工科技有限公司 | A kind of solid propellant rocket prosthetic device and its restorative procedure |
| CN107512998A (en) * | 2017-07-26 | 2017-12-26 | 湖北航天化学技术研究所 | A kind of cold curing solid propellant |
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