CN116836739A - Preparation method of three-layer core-shell structure boron-based composite fuel - Google Patents
Preparation method of three-layer core-shell structure boron-based composite fuel Download PDFInfo
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- CN116836739A CN116836739A CN202311039637.7A CN202311039637A CN116836739A CN 116836739 A CN116836739 A CN 116836739A CN 202311039637 A CN202311039637 A CN 202311039637A CN 116836739 A CN116836739 A CN 116836739A
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 title claims abstract description 174
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 136
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 239000011258 core-shell material Substances 0.000 title claims abstract description 46
- 239000000446 fuel Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 114
- 238000011065 in-situ storage Methods 0.000 claims abstract description 63
- 239000010410 layer Substances 0.000 claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- 239000002184 metal Substances 0.000 claims abstract description 50
- 229910052742 iron Inorganic materials 0.000 claims abstract description 48
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000011248 coating agent Substances 0.000 claims abstract description 37
- 238000000576 coating method Methods 0.000 claims abstract description 37
- 230000008021 deposition Effects 0.000 claims abstract description 29
- 239000007791 liquid phase Substances 0.000 claims abstract description 29
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 23
- 239000010941 cobalt Substances 0.000 claims abstract description 23
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 22
- 230000008569 process Effects 0.000 claims abstract description 15
- 238000002604 ultrasonography Methods 0.000 claims abstract description 13
- 238000005253 cladding Methods 0.000 claims abstract description 12
- 239000011247 coating layer Substances 0.000 claims abstract description 8
- 230000003064 anti-oxidating effect Effects 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 108
- 238000003756 stirring Methods 0.000 claims description 61
- 239000008367 deionised water Substances 0.000 claims description 44
- 229910021641 deionized water Inorganic materials 0.000 claims description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 239000012279 sodium borohydride Substances 0.000 claims description 33
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 33
- 238000002485 combustion reaction Methods 0.000 claims description 28
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 27
- 239000003513 alkali Substances 0.000 claims description 27
- 229910052708 sodium Inorganic materials 0.000 claims description 27
- 239000011734 sodium Substances 0.000 claims description 27
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 26
- 229940095064 tartrate Drugs 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 21
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 11
- 230000004048 modification Effects 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- 239000012266 salt solution Substances 0.000 claims description 11
- 230000008859 change Effects 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 241000080590 Niso Species 0.000 claims description 9
- 238000003860 storage Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 230000006911 nucleation Effects 0.000 claims description 4
- 238000010899 nucleation Methods 0.000 claims description 4
- 238000005070 sampling Methods 0.000 claims description 4
- 238000012764 semi-quantitative analysis Methods 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 238000002474 experimental method Methods 0.000 claims description 3
- 238000012544 monitoring process Methods 0.000 claims description 3
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- 238000001595 flow curve Methods 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 238000005191 phase separation Methods 0.000 claims description 2
- 230000036632 reaction speed Effects 0.000 claims description 2
- 238000012360 testing method Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 6
- 229960002167 sodium tartrate Drugs 0.000 description 6
- 239000001433 sodium tartrate Substances 0.000 description 6
- 235000011004 sodium tartrates Nutrition 0.000 description 6
- 230000006872 improvement Effects 0.000 description 5
- GDDNTTHUKVNJRA-UHFFFAOYSA-N 3-bromo-3,3-difluoroprop-1-ene Chemical compound FC(F)(Br)C=C GDDNTTHUKVNJRA-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000011246 composite particle Substances 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010301 surface-oxidation reaction Methods 0.000 description 2
- 235000014653 Carica parviflora Nutrition 0.000 description 1
- 241000243321 Cnidaria Species 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/12—Inorganic compounds
Abstract
The application discloses a preparation method of a three-layer core-shell structure boron-based composite fuel, which comprises the following steps: s1, preparing an amorphous boron solution; s2, primary coating modified nano iron liquid phase in-situ deposition based on composite variable frequency ultrasound; s3, liquid-phase in-situ deposition of nano nickel or nano cobalt of a secondary antioxidation coating modified layer based on composite variable frequency ultrasound; s4, separating the nano metal in-situ cladding modified amorphous boron with the three-layer core-shell structure; s5, detecting the modified amorphous boron coated with the nano metal with the three-layer core-shell structure in situ. The method has the advantages of simple and controllable process, safety, low cost and suitability for industrial mass production, the three-layer core-shell structure composite boron powder treated by the method, which takes amorphous boron powder as a core and nano metal as a coating layer, is easy to store, has short ignition delay time and can be directly used as a boron-based energetic material.
Description
Technical Field
The application belongs to the technical field of boron powder modification, and particularly relates to a nano metal coating modification technology of an amorphous boron functionalized three-layer core-shell structure based on liquid phase reduction composite variable frequency ultrasound.
Background
Metal fuels are important means of increasing the energy level of energetic materials as additives. Boron is in group IIIA of the second period of the periodic Table of elements, atomic number 5, relative atomic mass 10.81, and belongs to nonmetallic elements, but is often treated as a metal fuel in the field of energetic materials. Compared with the common metal fuel, the boron has higher mass combustion heat (58.9 kJ/g) and volume combustion heat (137.8 kJ/cm 3), is 1.9 times of aluminum mass combustion heat and 1.6 times of volume combustion heat, has obvious energy advantage when being used as the metal fuel, and is widely applied to solid rocket ramjet engines.
The elementary boron has two forms, one is crystalline boron, is gray crystals with metallic luster, has stable chemical property and extremely high physical hardness, and is difficult to use as fuel; the other is amorphous boron, which is brownish red powder with very active chemical property and is extremely easy to oxidize in air. The amorphous boron has a high melting point (2177 ℃) and a high boiling point (3658 ℃) and has an initial oxide layer on the surface, so that ignition is very difficult. Meanwhile, because the oxygen consumption is high during combustion, and the oxidation product B2O3 has low melting point (475 ℃) and high boiling point (2043 ℃), the oxidation product B2O3 is wrapped on the surface of boron particles in a molten liquid film form in the combustion process, is difficult to evaporate, prevents external oxygen from penetrating, causes low combustion efficiency of boron powder, and influences the oxidation heat release capacity of the boron powder.
In order to solve the above problems, a method of adding inflammable metal powder or fluoride, coating with AP (ammonium perchlorate) or the like is currently adopted to eliminate the influence of boron oxide on ignition performance. However, because amorphous boron is of a non-uniform lamellar coral structure, the added solid inflammable metal cannot be effectively and tightly combined with the amorphous boron abnormal structure, so that serious uneven distribution of two-phase structures of the amorphous boron and the inflammable metal is caused, the ignition combustion performance of the boron is directly restricted, the combustion heat of materials such as fluoride, AP (ammonium perchlorate) and the like is low, and the total combustion heat of the composite boron powder can be seriously influenced although the combustion performance of the boron can be improved after the materials are coated. Iron is used as transition metal, nano iron coating can effectively improve the combustion performance of boron, but as nano iron is easy to oxidize, the prepared nano iron coated boron-based composite particles are easy to generate surface oxidation when stored under the condition of natural air, and seriously influence the service performance, and an amorphous boron modification technical method capable of effectively and uniformly improving the ignition combustion performance of amorphous boron and simultaneously keeping good storage stability is needed.
Disclosure of Invention
Aiming at the problems in the prior art, the application aims to solve the problems that a liquid oxidation layer generated by the combustion of boron powder can cause difficult ignition, slow combustion speed, low energy release rate and serious agglomeration, and the boron-based composite fuel with a core-shell structure prepared by coating nano iron is easy to oxidize due to the iron layer and is easy to generate surface oxidation under the natural air storage condition to influence the material performance, and provides a three-layer core-shell structure amorphous boron nano metal in-situ uniform coating modification technology which can improve the combustion performance of the boron powder and ensure the storage performance of the composite boron powder.
In order to achieve the above purpose, the present application adopts the following technical scheme:
the preparation method of the three-layer core-shell structure boron-based composite fuel comprises the following steps:
s1, preparing an amorphous boron solution:
placing a proper amount of amorphous boron powder into a deionized water container, placing the container into a normal pressure ultrasonic workbench, and obtaining amorphous boron mixed liquid through ultrasonic stirring;
s2, primary coating modified nano iron liquid phase in-situ deposition based on composite variable frequency ultrasound:
preparing an Fe metal salt aqueous solution with a certain concentration, adding a complexing agent with a certain mass into the Fe metal salt aqueous solution, preparing a reducing agent with a certain concentration, dripping the corresponding salt aqueous solution and the reducing agent into an amorphous boron mixed liquid container of an ultrasonic workbench through a constant flow pump, adjusting the in-situ deposition rate of nano Fe taking amorphous boron as a nucleation core by combining the control of the dripping speed, the stirring speed and the variable frequency ultrasonic frequency, and controlling the concentration of a reaction liquid to realize the effective control of the thickness and the quality of an in-situ nano Fe coating layer of the amorphous boron so as to obtain an amorphous boron mixed solution uniformly coated by nano Fe once;
s3, liquid-phase in-situ deposition of nano nickel or nano cobalt of a secondary antioxidation coating modified layer based on composite variable frequency ultrasound:
preparing a nickel or cobalt metal salt aqueous solution with a certain concentration, adding a complexing agent with a certain mass into the nickel or cobalt metal salt aqueous solution, preparing a reducing agent with a certain concentration, dripping the nickel or cobalt salt aqueous solution and the reducing agent into an amorphous boron mixed solution which is placed on an ultrasonic workbench and is coated with nano iron once through a constant flow pump, adjusting nano nickel or cobalt to carry out secondary in-situ deposition coating by taking the amorphous boron coated with nano iron once as a nucleation core through combining with the control of dripping speed, stirring speed and variable frequency ultrasonic frequency, and obtaining a three-layer core-shell structure modified amorphous boron mixed solution with nano nickel or cobalt as an outermost coating layer, wherein the nano nickel or cobalt is a middle coating layer and the amorphous boron is a core through controlling the concentration and the reaction speed of a nickel salt and cobalt salt reaction solution;
s4, separating the nano metal in-situ coating modified amorphous boron with the three-layer core-shell structure:
placing the nano metal coated three-layer core-shell structure amorphous boron mixed solution obtained after the reaction in a centrifuge, and carrying out two-phase separation on the composite boron powder and deionized water through centrifugation to obtain three-layer core-shell structure nano metal in-situ coated amorphous boron powder;
s5, detecting the modified amorphous boron coated with the nano metal with the three-layer core-shell structure in situ.
As a further improvement scheme of the technical scheme: the preparation of the amorphous boron solution comprises the following steps:
25g of amorphous boron powder is taken and placed in a 300ml deionized water container, the container is placed on an ultrasonic workbench, and an amorphous boron mixed liquid is obtained through ultrasonic stirring.
As a further improvement scheme of the technical scheme: s2, primary coating modified nano iron liquid phase in-situ deposition based on composite variable frequency ultrasound, specifically comprises the following steps:
taking 10g FeSO 4 Dissolving in 200ml deionized water, dissolving 10g sodium alkali tartrate in 200ml deionized water, dissolving 5g sodium borohydride in 100ml deionized water, mixing sodium alkali tartrate solution with FeSO 4 Mixing the solutions, standing for 5 min, and mixing sodium alkali tartrate with FeSO by a constant flow pump 4 The solution mixed solution is dripped into the amorphous boron solution prepared by 1.1 at the speed of 0.3ml per minute, meanwhile, sodium borohydride solution is dripped into the amorphous boron solution prepared by 1.1 at the speed of 0.1ml per minute by a constant flow pump, the stirring speed is 90 turns per minute, the ultrasonic frequency is 1000 HZ/minute, the stirring speed is kept for 10 minutes, the stirring speed is increased to 120 turns per minute, the ultrasonic frequency is increased to 2000 HZ/minute, the stirring speed is kept for 10 minutes, the stirring speed is reduced to 90 turns per minute, the ultrasonic frequency is reduced to 1000 HZ/minute, the above rotating speed and the ultrasonic process are kept for 10 minutes, until the Fe salt solution and the sodium borohydride solution are all dripped into the amorphous boron solution, the stirring speed is kept for 90 turns per minute and the ultrasonic frequency is 1000 HZ/minute, and the ultrasonic frequency is kept for 30 minutes, and the nano metal Fe liquid phase in-situ deposition amorphous boron solution is obtained.
As a further improvement scheme of the technical scheme: s3, liquid-phase in-situ deposition of a secondary antioxidation coating modified layer nano nickel or nano cobalt based on composite variable frequency ultrasound, specifically comprises the following steps:
taking 10g CoSO 4 Dissolving in 200ml deionized water, dissolving 10g sodium alkali tartrate in 200ml deionized water, dissolving 5g sodium borohydride in 100ml deionized water, mixing sodium alkali tartrate solution with CoSO 4 Mixing the solutions, standing for 5 min, and mixing sodium alkali tartrate with CoSO by constant flow pump 4 The mixed solution of the solution is dripped into 1.2 of the prepared amorphous boron solution coated with nano iron once at the speed of 0.3ml per minuteSimultaneously dripping sodium borohydride solution into the amorphous boron solution which is prepared by 1.2 and coated by nano iron at the speed of 0.1ml per minute by a constant flow pump, stirring at the speed of 90 turns per minute, maintaining the ultrasonic frequency of 1000HZ per minute for 10 minutes, increasing the stirring speed to 120 turns per minute, increasing the ultrasonic frequency to 2000HZ per minute, maintaining for 10 minutes, reducing the stirring speed to 90 turns per minute, simultaneously reducing the ultrasonic frequency to 1000HZ per minute, maintaining for 10 minutes, circulating the rotating speed and the ultrasonic process until the Co salt solution and the sodium borohydride solution are completely dripped into the amorphous boron solution, maintaining the stirring speed of 90 turns per minute and the ultrasonic frequency of 1000HZ per minute, and continuing for 30 minutes to obtain the amorphous boron solution which is coated by nano metal Co and modified liquid phase in-situ deposition.
As a further improvement scheme of the technical scheme: s3, liquid-phase in-situ deposition of a secondary antioxidation coating modified layer nano nickel or nano cobalt based on composite variable frequency ultrasound, specifically comprises the following steps:
taking 10g of NiSO 4 Dissolving in 200ml deionized water, dissolving 10g sodium alkali tartrate in 200ml deionized water, dissolving 5g sodium borohydride in 100ml deionized water, mixing sodium alkali tartrate solution with NiSO 4 Mixing the solutions, standing for 5 min, and mixing sodium alkali tartrate with NiSO by constant flow pump 4 The mixed solution of the solution is dripped into the amorphous boron solution which is prepared and is coated by nano iron once at the speed of 0.3ml per minute, meanwhile, sodium borohydride solution is dripped into the amorphous boron solution which is prepared and coated by nano iron once at the speed of 0.1ml per minute and is coated by nano iron once at the speed of 1.2 by a constant flow pump, the stirring speed is 90 revolutions per minute, the ultrasonic frequency is 1000 HZ/minute, the stirring speed is kept for 10 minutes, the stirring speed is increased to 120 revolutions per minute, the ultrasonic frequency is increased to 2000 HZ/minute, the stirring speed is reduced to 90 revolutions per minute, the ultrasonic frequency is reduced to 1000 HZ/minute, the ultrasonic frequency is kept for 10 minutes, the rotating speed and the ultrasonic process are circulated until the Ni salt solution and the sodium borohydride solution are all dripped into the amorphous boron solution, the stirring speed is kept to 90 revolutions per minute and the ultrasonic frequency is 1000 HZ/minute, and the ultrasonic frequency is kept for 30 minutes, and the amorphous boron solution which is deposited in situ after the nano metal Ni secondary coating modification liquid phase is obtained.
As a further improvement scheme of the technical scheme: s5, detecting the nano metal in-situ coating modified amorphous boron with a three-layer core-shell structure, which specifically comprises the following steps:
storing the prepared three-layer core-shell structure powder under the natural air condition, sampling the powder in 1 day, 7 days, 14 days, 30 days, 90 days and 180 days respectively, observing the appearance of a sample and a combustion product by adopting an in-situ ultra-high resolution field emission scanning electron microscope equipped with an energy dispersion X-ray spectrometer, carrying out point scanning and surface scanning semi-quantitative analysis on the sample by using an energy spectrometer, comparing the element content and the distribution change in the three-layer core-shell structure composite boron powder which change along with the storage time, carrying out non-isothermal differential scanning calorimeter by adopting a TGA/DSC thermal analyzer, testing and measuring the peak temperature in the thermal oxidation process of the sample researched after storage, obtaining the change of a heat flow curve, carrying out an ignition combustion experiment by adopting a laser ignition combustion on-line monitoring system, and measuring the ignition delay change characteristic of the three-layer core-shell structure composite boron powder in pure oxygen by using a high-speed camera.
Compared with the prior art, the application has the beneficial effects that:
the method has the advantages of simple and controllable process, safety, low cost and suitability for industrial mass production, the three-layer core-shell structure composite boron powder treated by the method, which takes amorphous boron powder as a core and nano metal as a coating layer, is easy to store, has short ignition delay time and can be directly used as a boron-based energetic material.
The foregoing description is only an overview of the present application, and is intended to provide a better understanding of the present application, as it is embodied in the following description, with reference to the preferred embodiments of the present application and the accompanying drawings. Specific embodiments of the present application are given in detail by the following examples and the accompanying drawings.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application and do not constitute a limitation on the application. In the drawings:
fig. 1 is a schematic diagram of a preparation method of a three-layer core-shell structure boron-based composite fuel.
Detailed Description
The application provides a preparation method of a three-layer core-shell structure boron-based composite fuel, wherein the three-layer core-shell structure boron-based composite fuel comprises Co and Fe double-layer cladding modified amorphous boron and Ni and Fe double-layer cladding modified amorphous boron.
EXAMPLE 1 preparation of Co and Fe double coated modified amorphous boron
1.1 preparation of amorphous boron solution
25g of amorphous boron powder is taken and placed in a 300ml deionized water container, the container is placed on an ultrasonic workbench, and an amorphous boron mixed liquid is obtained through ultrasonic stirring.
1.2 composite variable frequency ultrasonic nano metal Fe one-time cladding modified liquid phase in situ deposition
Taking 10g FeSO 4 Dissolving in 200ml deionized water, dissolving 10g sodium alkali tartrate in 200ml deionized water, dissolving 5g sodium borohydride in 100ml deionized water, mixing sodium alkali tartrate solution with FeSO 4 The solution was mixed and allowed to stand for 5 minutes. Sodium tartrate and FeSO are pumped by a constant flow pump 4 The mixed solution of the solution was dropped into the amorphous boron solution prepared in 1.1 at a rate of 0.3ml per minute, while the sodium borohydride solution was simultaneously dropped into the amorphous boron solution prepared in 1.1 at a rate of 0.1ml per minute by a constant flow pump. Stirring speed is 90 turns per minute, ultrasonic frequency is 1000 HZ/minute, holding for 10 minutes, stirring speed is increased to 120 turns/minute, ultrasonic frequency is increased to 2000 HZ/minute, holding for 10 minutes, stirring speed is reduced to 90 turns per minute, and ultrasonic frequency is reduced to 1000 HZ/minute, holding for 10 minutes. And circulating the rotating speed and the ultrasonic process until the Fe salt solution and the sodium borohydride solution are completely dripped into the amorphous boron solution, maintaining the stirring speed of 90 revolutions per minute and the ultrasonic frequency of 1000 HZ/minute, and continuing for 30 minutes to obtain the nano metal Fe liquid phase in-situ deposition amorphous boron solution.
1.3 composite variable frequency ultrasonic nano metal cobalt secondary coating modified liquid phase in situ deposition
Taking 10g CoSO 4 Dissolving in 200ml deionized water, collecting 10g sodium alkali tartrateDissolving in 200ml deionized water, dissolving 5g sodium borohydride in 100ml deionized water, mixing sodium tartrate solution with CoSO 4 The solution was mixed and allowed to stand for 5 minutes. Sodium tartrate and CoSO are pumped by a constant flow pump 4 The mixed solution of the solution is dripped into the amorphous boron solution which is prepared by 1.2 and is coated with nano-iron at a speed of 0.3ml per minute, and simultaneously, the sodium borohydride solution is dripped into the amorphous boron solution which is prepared by 1.2 and is coated with nano-iron at a speed of 0.1ml per minute through a constant flow pump. Stirring speed is 90 turns per minute, ultrasonic frequency is 1000 HZ/minute, holding for 10 minutes, stirring speed is increased to 120 turns/minute, ultrasonic frequency is increased to 2000 HZ/minute, holding for 10 minutes, stirring speed is reduced to 90 turns per minute, and ultrasonic frequency is reduced to 1000 HZ/minute, holding for 10 minutes. And circulating the rotating speed and the ultrasonic process until the Co salt solution and the sodium borohydride solution are completely dripped into the amorphous boron solution, maintaining the stirring speed of 90 revolutions per minute and the ultrasonic frequency of 1000 HZ/minute, and continuing for 30 minutes to obtain the nano metal Co secondary coating modified liquid phase in-situ deposition amorphous boron solution.
1.4 separation of nano cobalt and nano iron composite in-situ coating modified amorphous boron with three-layer core-shell structure
And (3) placing the mixed solution of the nano cobalt and the nano iron composite in-situ coated amorphous boron obtained after the reaction in a centrifuge, and separating the boron powder from deionized water through centrifugation to obtain the nano cobalt and the nano iron composite in-situ coated amorphous boron powder.
1.5 detection of nano cobalt and nano iron composite in-situ coating modified amorphous boron with three-layer core-shell structure
Storing the prepared three-layer core-shell structure nano cobalt/nano iron in-situ cladding modified amorphous boron powder under the natural air condition, sampling for 1 day, 7 days, 14 days, 30 days, 90 days and 180 days respectively, observing the appearance of a sample and a combustion product by adopting an in-situ ultra-high resolution field emission scanning electron microscope equipped with an energy dispersion X-ray spectrometer, and performing point scanning and surface scanning semi-quantitative analysis on the element content and distribution change rule in the nano metal in-situ cladding modified boron powder by using an energy spectrometer.
EXAMPLE 2Ni and Fe double coating modified amorphous boron
2.1 preparation of amorphous boron solution;
25g of amorphous boron powder is taken and placed in a 300ml deionized water container, the container is placed on an ultrasonic workbench, and an amorphous boron mixed liquid is obtained through ultrasonic stirring.
2.2 composite variable frequency ultrasonic nano metal Fe one-time cladding modified liquid phase in situ deposition
Taking 10g FeSO 4 Dissolving in 200ml deionized water, dissolving 10g sodium alkali tartrate in 200ml deionized water, dissolving 5g sodium borohydride in 100ml deionized water, mixing sodium alkali tartrate solution with FeSO 4 The solution was mixed and allowed to stand for 5 minutes. Sodium tartrate and FeSO are pumped by a constant flow pump 4 The mixed solution of the solution was dropped into the amorphous boron solution prepared in 1.1 at a rate of 0.3ml per minute, while the sodium borohydride solution was simultaneously dropped into the amorphous boron solution prepared in 1.1 at a rate of 0.1ml per minute by a constant flow pump. Stirring speed is 90 turns per minute, ultrasonic frequency is 1000 HZ/minute, holding for 10 minutes, stirring speed is increased to 120 turns/minute, ultrasonic frequency is increased to 2000 HZ/minute, holding for 10 minutes, stirring speed is reduced to 90 turns per minute, and ultrasonic frequency is reduced to 1000 HZ/minute, holding for 10 minutes. And circulating the rotating speed and the ultrasonic process until the Fe salt solution and the sodium borohydride solution are completely dripped into the amorphous boron solution, maintaining the stirring speed of 90 revolutions per minute and the ultrasonic frequency of 1000 HZ/minute, and continuing for 30 minutes to obtain the nano metal Fe liquid phase in-situ deposition amorphous boron solution.
2.3 composite variable frequency ultrasonic nano metallic nickel secondary coating modified liquid phase in situ deposition
Taking 10g of NiSO 4 Dissolving in 200ml deionized water, dissolving 10g sodium alkali tartrate in 200ml deionized water, dissolving 5g sodium borohydride in 100ml deionized water, mixing sodium alkali tartrate solution with NiSO 4 The solution was mixed and allowed to stand for 5 minutes. Sodium tartrate and NiSO are pumped by a constant flow pump 4 The mixed solution is dripped into the amorphous boron solution which is prepared by 1.2 and is coated with nano iron at a speed of 0.3ml per minute, and simultaneously the sodium borohydride solution is dripped into the amorphous boron solution which is prepared by 1.2 and is coated with nano iron at a speed of 0.1ml per minute by a constant flow pumpAnd meanwhile, dropwise adding the nano-iron coated amorphous boron solution prepared in 1.2. Stirring speed is 90 turns per minute, ultrasonic frequency is 1000 HZ/minute, holding for 10 minutes, stirring speed is increased to 120 turns/minute, ultrasonic frequency is increased to 2000 HZ/minute, holding for 10 minutes, stirring speed is reduced to 90 turns per minute, and ultrasonic frequency is reduced to 1000 HZ/minute, holding for 10 minutes. And circulating the rotating speed and the ultrasonic process until the Ni salt solution and the sodium borohydride solution are completely dripped into the amorphous boron solution, maintaining the stirring speed of 90 revolutions per minute and the ultrasonic frequency of 1000 HZ/minute, and continuing for 30 minutes to obtain the nano metal Ni secondary coating modified liquid phase in-situ deposition amorphous boron solution.
2.4 separation of nano nickel and nano iron composite in-situ coating modified amorphous boron with three-layer core-shell structure
And (3) placing the mixed solution of nano nickel and nano iron composite in-situ coated amorphous boron obtained after the reaction in a centrifuge, and separating the composite boron powder from deionized water through centrifugation to obtain the nano nickel and nano iron composite in-situ coated amorphous boron powder.
2.5 detection of nano nickel and nano iron composite in-situ coating modified amorphous boron with three-layer core-shell structure
The prepared three-layer core-shell structure nano nickel and nano iron in-situ cladding modified amorphous boron powder is stored under the natural air condition, sampling is carried out on the three-layer core-shell structure nano nickel and nano iron in-situ cladding modified amorphous boron powder in 1 day, 7 days, 14 days, 30 days, 90 days and 180 days respectively, the appearance of a sample and a combustion product is observed by adopting an in-situ ultra-high resolution field emission scanning electron microscope equipped with an energy dispersion X-ray spectrometer, and the sample is subjected to point scanning and surface scanning semi-quantitative analysis on the element content and distribution change rule in the nano metal in-situ cladding modified boron powder by using an energy spectrometer.
Comparative example 1 nano iron coated boron based composite particles
3.1 preparation of amorphous boron solution;
25g of amorphous boron powder is taken and placed in a 300ml deionized water container, the container is placed on an ultrasonic workbench, and an amorphous boron mixed liquid is obtained through ultrasonic stirring.
3.2 composite variable frequency ultrasonic nano metal Fe primary coating modified liquid phase in situ deposition
Taking 10g FeSO 4 Dissolving in 200ml deionized water, dissolving 10g sodium alkali tartrate in 200ml deionized water, dissolving 5g sodium borohydride in 100ml deionized water, mixing sodium alkali tartrate solution with FeSO 4 The solution was mixed and allowed to stand for 5 minutes. Sodium tartrate and FeSO are pumped by a constant flow pump 4 The mixed solution of the solution was dropped into the amorphous boron solution prepared in 1.1 at a rate of 0.3ml per minute, while the sodium borohydride solution was simultaneously dropped into the amorphous boron solution prepared in 1.1 at a rate of 0.1ml per minute by a constant flow pump. Stirring speed is 90 turns per minute, ultrasonic frequency is 1000 HZ/minute, holding for 10 minutes, stirring speed is increased to 120 turns/minute, ultrasonic frequency is increased to 2000 HZ/minute, holding for 10 minutes, stirring speed is reduced to 90 turns per minute, and ultrasonic frequency is reduced to 1000 HZ/minute, holding for 10 minutes. And circulating the rotating speed and the ultrasonic process until the Fe salt solution and the sodium borohydride solution are completely dripped into the amorphous boron solution, maintaining the stirring speed of 90 revolutions per minute and the ultrasonic frequency of 1000 HZ/minute, and continuing for 30 minutes to obtain the nano metal Fe liquid phase in-situ deposition amorphous boron solution.
The ignition combustion experiments were performed using the laser ignition combustion on-line monitoring system for the pure boron powders of examples 1-2, comparative example 1, and the ignition delay time of the energetic powder in pure oxygen was measured by a high-speed camera, and the results are shown in table 1.
TABLE 1
| Fuel and its production process | Ignition delay time |
| Pure boron powder | 52ms |
| Comparative example 1 | 45.3ms |
| Example 1 | 30.2ms |
| Example 2 | 29.5ms |
As is clear from Table 1, the ignition delay time of the pure boron powder is 52ms, the ignition delay time of comparative example 1 is 45.3ms, the ignition delay time of example 1 is 32.4ms, and the ignition delay time of example 2 is 35.6 ms.
After the modification treatment of the embodiment of the application, the oxidation behavior of the nano iron coating in the nano metal coated boron-based energetic material under the natural air storage condition is effectively controlled, the storage performance of the boron-based composite fuel is effectively improved, the ignition delay time of the material is reduced, the agglomeration of combustion products is reduced, and the energy release rate is improved.
The application can be seen that the three-layer core-shell structure amorphous boron nano metal in-situ coating modification technology solves the problems that the surface is easy to oxidize and is not easy to store for a long time caused by the coating of amorphous boron single-layer nano iron, and simultaneously effectively solves the problems of difficult low-pressure ignition, slow burning speed, low energy release rate and serious agglomeration of combustion products of amorphous boron powder.
The above description is only of the preferred embodiments of the present application, and is not intended to limit the present application in any way; those skilled in the art will readily appreciate that the present application may be implemented as shown in the drawings and described above; however, those skilled in the art will appreciate that many modifications, adaptations, and variations of the present application are possible in light of the above teachings without departing from the scope of the application; meanwhile, any equivalent changes, modifications and evolution of the above embodiments according to the essential technology of the present application still fall within the scope of the present application.
Claims (6)
1. The preparation method of the three-layer core-shell structure boron-based composite fuel is characterized by comprising the following steps of:
s1, preparing an amorphous boron solution:
placing a proper amount of amorphous boron powder into a deionized water container, placing the container into a normal pressure ultrasonic workbench, and obtaining amorphous boron mixed liquid through ultrasonic stirring;
s2, primary coating modified nano iron liquid phase in-situ deposition based on composite variable frequency ultrasound:
preparing an Fe metal salt aqueous solution with a certain concentration, adding a complexing agent with a certain mass into the Fe metal salt aqueous solution, preparing a reducing agent with a certain concentration, dripping the corresponding salt aqueous solution and the reducing agent into an amorphous boron mixed liquid container of an ultrasonic workbench through a constant flow pump, adjusting the in-situ deposition rate of nano Fe taking amorphous boron as a nucleation core by combining the control of the dripping speed, the stirring speed and the variable frequency ultrasonic frequency, and controlling the concentration of a reaction liquid to realize the effective control of the thickness and the quality of an in-situ nano Fe coating layer of the amorphous boron so as to obtain an amorphous boron mixed solution uniformly coated by nano Fe once;
s3, liquid-phase in-situ deposition of nano nickel or nano cobalt of a secondary antioxidation coating modified layer based on composite variable frequency ultrasound:
preparing a nickel or cobalt metal salt aqueous solution with a certain concentration, adding a complexing agent with a certain mass into the nickel or cobalt metal salt aqueous solution, preparing a reducing agent with a certain concentration, dripping the nickel or cobalt salt aqueous solution and the reducing agent into an amorphous boron mixed solution which is placed on an ultrasonic workbench and is coated with nano iron once through a constant flow pump, adjusting nano nickel or cobalt to carry out secondary in-situ deposition coating by taking the amorphous boron coated with nano iron once as a nucleation core through combining with the control of dripping speed, stirring speed and variable frequency ultrasonic frequency, and obtaining a three-layer core-shell structure modified amorphous boron mixed solution with nano nickel or cobalt as an outermost coating layer, wherein the nano nickel or cobalt is a middle coating layer and the amorphous boron is a core through controlling the concentration and the reaction speed of a nickel salt and cobalt salt reaction solution;
s4, separating the nano metal in-situ coating modified amorphous boron with the three-layer core-shell structure:
placing the nano metal coated three-layer core-shell structure amorphous boron mixed solution obtained after the reaction in a centrifuge, and carrying out two-phase separation on the composite boron powder and deionized water through centrifugation to obtain three-layer core-shell structure nano metal in-situ coated amorphous boron powder;
s5, detecting the modified amorphous boron coated with the nano metal with the three-layer core-shell structure in situ.
2. The method for preparing the three-layer core-shell structure boron-based composite fuel according to claim 1, wherein the preparation of the amorphous boron solution is specifically as follows:
25g of amorphous boron powder is taken and placed in a 300ml deionized water container, the container is placed on an ultrasonic workbench, and an amorphous boron mixed liquid is obtained through ultrasonic stirring.
3. The preparation method of the three-layer core-shell structure boron-based composite fuel according to claim 1, wherein the step S2 is based on primary cladding modified nano iron liquid phase in-situ deposition of composite variable frequency ultrasound, and specifically comprises the following steps:
taking 10g FeSO 4 Dissolving in 200ml deionized water, dissolving 10g sodium alkali tartrate in 200ml deionized water, dissolving 5g sodium borohydride in 100ml deionized water, mixing sodium alkali tartrate solution with FeSO 4 Mixing the solutions, standing for 5 min, and mixing sodium alkali tartrate with FeSO by a constant flow pump 4 The mixed solution of the solution is dripped into the amorphous boron solution prepared by 1.1 at the speed of 0.3ml per minute, simultaneously, the sodium borohydride solution is dripped into the amorphous boron solution prepared by 1.1 at the speed of 0.1ml per minute by a constant flow pump, the stirring speed is 90 revolutions per minute, the ultrasonic frequency is 1000 HZ/minute, the stirring speed is increased to 120 revolutions per minute for 10 minutes, the ultrasonic frequency is increased to 2000 HZ/minute, the stirring speed is reduced to 10 minutes, and the stirring speed is reducedAnd (3) rotating 90 rpm, reducing the ultrasonic frequency to 1000 HZ/min, maintaining for 10 min, and circulating the rotating speed and the ultrasonic process until the Fe salt solution and the sodium borohydride solution are completely dripped into the amorphous boron solution, and maintaining the stirring speed at 90 rpm and the ultrasonic frequency at 1000 HZ/min for 30 min to obtain the nano metal Fe liquid phase in-situ deposition amorphous boron solution.
4. The preparation method of the three-layer core-shell structure boron-based composite fuel according to claim 1, wherein the step S3 is characterized by performing liquid-phase in-situ deposition of a secondary antioxidation coating modified layer nano nickel or nano cobalt based on composite frequency conversion ultrasound, and specifically comprises the following steps:
taking 10g CoSO 4 Dissolving in 200ml deionized water, dissolving 10g sodium alkali tartrate in 200ml deionized water, dissolving 5g sodium borohydride in 100ml deionized water, mixing sodium alkali tartrate solution with CoSO 4 Mixing the solutions, standing for 5 min, and mixing sodium alkali tartrate with CoSO by constant flow pump 4 The mixed solution of the solution is dripped into the amorphous boron solution which is prepared and is coated by nano iron once at the speed of 0.3ml per minute, meanwhile, sodium borohydride solution is dripped into the amorphous boron solution which is prepared and coated by nano iron once at the speed of 0.1ml per minute and is coated by nano iron once at the speed of 1.2 by a constant flow pump, the stirring speed is 90 revolutions per minute, the ultrasonic frequency is 1000 HZ/minute, the stirring speed is kept for 10 minutes, the stirring speed is increased to 120 revolutions per minute, the ultrasonic frequency is increased to 2000 HZ/minute, the stirring speed is reduced to 90 revolutions per minute, the ultrasonic frequency is reduced to 1000 HZ/minute, the ultrasonic frequency is kept for 10 minutes, the rotating speed and the ultrasonic process are circulated until the Co salt solution and the sodium borohydride solution are all dripped into the amorphous boron solution, the stirring speed is kept to 90 revolutions per minute and the ultrasonic frequency is 1000 HZ/minute, and the ultrasonic frequency is kept for 30 minutes, and the amorphous boron solution which is deposited in situ after the secondary coating modification liquid phase of nano metal Co is obtained.
5. The preparation method of the three-layer core-shell structure boron-based composite fuel according to claim 1, wherein the step S3 is characterized by performing liquid-phase in-situ deposition of a secondary antioxidation coating modified layer nano nickel or nano cobalt based on composite frequency conversion ultrasound, and specifically comprises the following steps:
taking 10g of NiSO 4 Dissolving in 200ml deionized water, dissolving 10g sodium alkali tartrate in 200ml deionized water, dissolving 5g sodium borohydride in 100ml deionized water, mixing sodium alkali tartrate solution with NiSO 4 Mixing the solutions, standing for 5 min, and mixing sodium alkali tartrate with NiSO by constant flow pump 4 The mixed solution of the solution is dripped into the amorphous boron solution which is prepared and is coated by nano iron once at the speed of 0.3ml per minute, meanwhile, sodium borohydride solution is dripped into the amorphous boron solution which is prepared and coated by nano iron once at the speed of 0.1ml per minute and is coated by nano iron once at the speed of 1.2 by a constant flow pump, the stirring speed is 90 revolutions per minute, the ultrasonic frequency is 1000 HZ/minute, the stirring speed is kept for 10 minutes, the stirring speed is increased to 120 revolutions per minute, the ultrasonic frequency is increased to 2000 HZ/minute, the stirring speed is reduced to 90 revolutions per minute, the ultrasonic frequency is reduced to 1000 HZ/minute, the ultrasonic frequency is kept for 10 minutes, the rotating speed and the ultrasonic process are circulated until the Ni salt solution and the sodium borohydride solution are all dripped into the amorphous boron solution, the stirring speed is kept to 90 revolutions per minute and the ultrasonic frequency is 1000 HZ/minute, and the ultrasonic frequency is kept for 30 minutes, and the amorphous boron solution which is deposited in situ after the nano metal Ni secondary coating modification liquid phase is obtained.
6. The preparation method of the three-layer core-shell structure boron-based composite fuel according to claim 1, wherein the detection of the three-layer core-shell structure nano metal in-situ cladding modified amorphous boron is specifically as follows:
storing the prepared three-layer core-shell structure powder under the natural air condition, sampling the powder in 1 day, 7 days, 14 days, 30 days, 90 days and 180 days respectively, observing the appearance of a sample and a combustion product by adopting an in-situ ultra-high resolution field emission scanning electron microscope equipped with an energy dispersion X-ray spectrometer, carrying out point scanning and surface scanning semi-quantitative analysis on the sample by using an energy spectrometer, comparing the element content and the distribution change in the three-layer core-shell structure composite boron powder which change along with the storage time, carrying out non-isothermal differential scanning calorimeter by adopting a TGA/DSC thermal analyzer, testing and measuring the peak temperature in the thermal oxidation process of the sample researched after storage, obtaining the change of a heat flow curve, carrying out an ignition combustion experiment by adopting a laser ignition combustion on-line monitoring system, and measuring the ignition delay change characteristic of the three-layer core-shell structure composite boron powder in pure oxygen by using a high-speed camera.
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