CN114835538B - Bimetal oxide modified boron fuel and preparation method thereof - Google Patents
Bimetal oxide modified boron fuel and preparation method thereof Download PDFInfo
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Abstract
The invention provides a bimetal oxide modified boron fuel and a preparation method thereof, wherein the method adopts a dipping-precipitation deposition method or a precipitation deposition-dipping method to modify bimetal oxide on the surface of boron powder to form the bimetal oxide modified boron fuel; the bimetallic oxide is a composite binary bimetallic oxide of bismuth oxide and vanadium oxide; the contents of bismuth oxide and vanadium oxide in the bimetal oxide modified boron fuel are respectively 0.1-5 wt.%. The invention adopts a precipitation deposition-impregnation method and an impregnation-precipitation deposition method to load two metal oxides of bismuth oxide and vanadium oxide on the surface of boron powder to form the bimetal oxide modified boron fuel with high reaction activity. Compared with pure boron powder, the boron powder has the advantages of lower oxidation exothermic peak temperature and shorter ignition delay time, and the ratio of the two metal oxide components is very low, so that the ignition and combustion performances of the boron powder can be effectively improved on the premise of not influencing the energy density of the boron powder, and the boron powder has larger application potential.
Description
Technical Field
The invention belongs to the technical field of high-energy solid propellants, relates to boron fuel, and particularly relates to bimetal oxide modified boron fuel and a preparation method thereof.
Background
The thermite reaction is a metal to metalThe reaction between oxide or non-metal oxide has wide application in explosion, pyrotechnical, thermal battery, micro actuator, material synthesis and process, etc. because of the characteristic of high exothermicity and self-sustaining property of aluminothermic reaction. The current research on aluminum-based thermite mainly focuses on Al/CuO and Al/WO 3 、Al/Fe 2 O 3 And the like. Although boron (B) has a higher volumetric and gravimetric energy density thermodynamically than aluminum, research on boron-based thermites has received much less attention than aluminum-based thermites. The main reason is that boron powder as fuel has the defects of difficult ignition, slow combustion and the like. The liquefaction temperature of the boron oxide layer on the surface of the boron powder under one atmosphere is 723K, the evaporation temperature of the boron oxide layer under one atmosphere is 2130K, the ignition temperature of the boron particles is 1400-2000K, therefore, the boron oxide layer on the surface of the boron particles obviously hinders the ignition of the boron particles, and meanwhile, the boron particles have a higher melting point (2349K) and a higher boiling point (4200K), so the oxidation process of the boron particles occurs in a condensed phase, therefore, the reaction of the process is slow, a lot of combustion residues exist, the combustion efficiency is low, and the high heat value of the boron powder cannot be exerted. Boron becomes one of the most potential fuel-rich solid propellant additives with high mass calorific value and volume calorific value, so that the ignition performance of boron powder is improved, and the improvement of the combustion efficiency of the boron powder is the first premise for accelerating the application of the boron powder in the fields of propellants and explosives and is also the target pursued in the field of boron powder modification research at present.
Extensive research on combustion over the years has shown that high combustion efficiencies can be achieved by improving the combustion environment of boron particles in boron-containing propellants using appropriate methods. The energy release of B can be effectively promoted by using the additive to pertinently improve various limiting factors in the ignition combustion process of B, wherein the oxide can be used as a catalyst to effectively catalyze the combustion of boron powder. Thermal gravimetric/differential scanning calorimetry (TGA/DSC) is adopted by researchers to explore the influence of NiO and CuO with nanometer sizes coated on boron particles on the combustion performance of the boron particles. At the same time, the researchers also studied the initial reaction temperature of B-based fuel after adding a series of oxides, including MgO and Al, by using TGA/DSC 2 O 3 、CeO 2 、Fe 2 O 3 、CuO、SnO 2 And Bi 2 O 3 They found B/Bi 2 O 3 With the lowest starting temperature. The above studies demonstrate that metal oxide modified boron fuels have excellent properties. However, the modification of boron fuels by bimetallic oxides has not been reported in the prior art.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a bimetal oxide modified boron fuel and a preparation method thereof, and solve the technical problem that ignition and combustion performances of the boron fuel in the prior art need to be further improved on the basis of ensuring high reaction activity.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing bimetal oxide modified boron fuel, which adopts dipping-deposition method or deposition-dipping method to modify bimetal oxide on the surface of boron powder to form bimetal oxide modified boron fuel;
the bimetallic oxide is a composite binary bimetallic oxide of bismuth oxide and vanadium oxide;
the dipping-precipitation deposition method comprises the following steps: firstly, completely soaking boron powder particles by taking a solution of pentavalent vanadium salt as a soaking solution, and drying and calcining to prepare a vanadium oxide-loaded boron fuel; then using BiCl 3 Taking NaOH as a precipitator as a bismuth source, precipitating on the surface of the boron fuel loaded with vanadium oxide to obtain a precipitation intermediate product, calcining and depositing the precipitation intermediate product to finally obtain the boron fuel loaded with vanadium oxide and deposited with bismuth oxide, namely the bimetal oxide modified boron fuel;
the precipitation deposition-impregnation method comprises the following steps: firstly, biCl is added 3 The bismuth source is adopted, naOH is adopted as a precipitator, precipitation is carried out on the surface of boron powder to obtain a precipitation intermediate product, and the precipitation intermediate product is calcined and deposited to obtain the bismuth oxide deposited boron fuel; then completely soaking the boron fuel particles for depositing the bismuth oxide by taking a solution of pentavalent vanadium salt as an impregnation solution, drying and calcining to finally obtain the vanadium oxide-loaded boron fuel for depositing the bismuth oxide, namely the vanadium oxide-loaded boron fuelPreparing the bimetal oxide modified boron fuel;
the contents of bismuth oxide and vanadium oxide in the bimetal oxide modified boron fuel are respectively 0.1-5 wt.%.
The invention also has the following technical characteristics:
preferably, the content of bismuth oxide and vanadium oxide in the bimetallic oxide modified boron fuel is 1wt.% to 5wt.%, respectively.
Preferably, the BiCl 3 Using BiCl 3 Or BiCl 3 The ethanol solution of (a); the NaOH adopts NaOH aqueous solution.
Preferably, the impregnation liquid is NH 4 VO 3 An aqueous solution.
Specifically, the impregnation-precipitation deposition method specifically comprises the following steps:
step 101, adding boron powder into a reaction container, and then testing the saturated water absorption capacity of the boron powder by using water to obtain the volume of impregnation liquid required by the boron powder;
102, weighing boron powder, pouring the boron powder into a reaction container, and adding magnetons;
103, using a liquid transfer gun to transfer the prepared soaking liquid with the concentration of 0.001-1 mol/L, and adding deionized water to dilute the soaking liquid to the volume of the soaking liquid required by the boron powder;
step 104, dropwise adding the dipping solution diluted in the step 103 into the boron powder obtained in the step 102 to completely soak the boron powder, and ultrasonically stirring;
105, placing the boron fuel in an oven to be dried and calcined at the temperature of 60-80 ℃ to prepare boron fuel loaded with vanadium oxide;
step 201, adding the boron fuel loaded with vanadium oxide prepared in step 105 into a reaction container, then adding deionized water, and adding magneton for ultrasonic continuous stirring;
202, measuring BiCl 3 Or BiCl 3 Adding the ethanol solution into a reaction vessel, and fully stirring;
step 203, adding NaOH aqueous solution to adjust the pH value of the solution to 7-8, adjusting the reaction temperature to be within the range of 30-100 ℃, and continuously stirring for 2-12 hours to carry out reaction to obtain a precipitate intermediate product;
and 204, centrifugally collecting the precipitation intermediate product, washing the precipitation intermediate product for a plurality of times by using deionized water until no anion corresponding to the bismuth source can be detected in the supernatant, and finally drying the precipitation intermediate product in an oven and then calcining and depositing the dried precipitation intermediate product at the temperature of 60-80 ℃ to obtain the bimetal oxide modified boron fuel.
Specifically, the precipitation deposition-impregnation method specifically comprises the following steps:
step 101, adding boron powder into a reaction container, then adding deionized water, and adding magnetons for ultrasonic continuous stirring;
102, measuring BiCl 3 Or BiCl 3 Adding the ethanol solution into a reaction container, and fully stirring;
103, adding NaOH aqueous solution to adjust the pH value of the solution to 7-8, adjusting the reaction temperature to be within the range of 30-100 ℃, and continuously stirring for 2-12 hours for reaction to obtain a precipitate intermediate product;
step 104, centrifugally collecting a precipitation intermediate product, washing the precipitation intermediate product for a plurality of times by using deionized water until no anion corresponding to the bismuth source can be detected in a supernatant, and finally drying the precipitation intermediate product in an oven and then calcining and depositing the precipitation intermediate product at the temperature of 60-80 ℃ to obtain the bismuth oxide deposited boron fuel;
step 201, adding the boron fuel deposited with bismuth oxide prepared in step 104 into a reaction container, and then testing the saturated water absorption capacity of the boron fuel with water to obtain the volume of an impregnation liquid required by the boron fuel deposited with bismuth oxide;
202, weighing boron fuel for depositing bismuth oxide, pouring the boron fuel into a reaction container, and adding magnetons;
step 203, using a liquid transfer gun to transfer the prepared impregnation liquid with the concentration of 0.001-1 mol/L, and adding deionized water to dilute the impregnation liquid to the volume of the impregnation liquid required by the bismuth oxide deposited boron fuel;
step 204, dropwise adding the impregnation liquid diluted in the step 203 into the boron fuel for depositing the bismuth oxide in the step 202 to completely soak the boron fuel for depositing the bismuth oxide, and ultrasonically stirring;
and step 205, placing the boron fuel in an oven to be dried and calcined at the temperature of 60-80 ℃ to obtain the bimetal oxide modified boron fuel.
The invention also protects the bimetal oxide modified boron fuel, and the bimetal oxide modification is carried out on the surface of the boron powder to form the bimetal oxide modified boron fuel;
the bimetallic oxide is a composite binary bimetallic oxide of bismuth oxide and vanadium oxide;
the contents of bismuth oxide and vanadium oxide in the bimetal oxide modified boron fuel are respectively 0.1-5 wt.%.
Preferably, the content of bismuth oxide and vanadium oxide in the bimetallic oxide modified boron fuel is 1wt.% to 5wt.%, respectively.
Further preferably, the content of bismuth oxide and vanadium oxide in the double metal oxide modified boron fuel is 1wt.% to 3.5wt.%, respectively.
Preferably, the bimetal oxide modified boron fuel is prepared by the preparation method of the bimetal oxide modified boron fuel.
Compared with the prior art, the invention has the following technical effects:
the invention adopts a precipitation deposition-impregnation method and an impregnation-precipitation deposition method to load two metal oxides of bismuth oxide and vanadium oxide on the surface of boron powder to form the bimetal oxide modified boron fuel with high reaction activity. Compared with pure boron powder, the bimetal oxide modified boron fuel prepared by the invention has lower oxidation exothermic peak temperature and shorter ignition delay time, and the proportion of the two metal oxide components is very low, so that the ignition and combustion performances of the boron powder can be effectively improved on the premise of not influencing the energy density of the boron powder, and the bimetal oxide modified boron fuel has larger application potential.
The bimetallic oxide modified boron fuel prepared by the invention has good ignition performance (the laser ignition delay time can be advanced by 14-26 ms at most compared with unmodified boron powder), and the initial oxidation temperature is low (the initial oxidation temperature can be advanced by 150-200 ℃ at most compared with unmodified boron powder).
The preparation method of the invention adopts a mode of combining a liquid phase chemical method, has simple operation flow and high preparation efficiency, and compared with a single metal oxide, the bimetal oxide can be uniformly loaded on the surface of the boron powder to form a highly dispersed bimetal interface, and the ignition performance of the boron powder can be greatly improved only by loading a small amount of the bimetal oxide.
(IV) in the boron fuel modified by the bimetal oxide prepared by the invention, the inert component proportion of the bimetal oxide is very low, the influence on the energy density of the boron powder fuel is small, and the boron fuel modified by the bimetal oxide has good application prospect in the field of high-energy solid fuels.
Drawings
FIG. 1 is a 3.5wt.% -Bi representation of a dual metal oxide modified boron fuel prepared based on a dip-precipitation deposition process 2 O 3 /1wt.％-V 2 O 5 XPS spectrum of/B: b1s, (B) Bi 4f, (C) V2 p, and (D) O1 s.
FIG. 2 is a 3.5wt.% -V representation of a dual metal oxide modified boron fuel prepared based on a precipitation deposition-impregnation process 2 O 5 /1wt.％-Bi 2 O 3 XPS spectrum of/B: b1s, (B) V2 p, (C) Bi 4f, and (D) O1 s.
FIG. 3 is a 3.5wt.% -Bi representation of a dual metal oxide modified boron fuel prepared based on a dip-precipitate deposition process 2 O 3 /1wt.％-V 2 O 5 SEM and Mapping (B, bi, O, V element distribution diagram) of/B.
FIG. 4 is a 3.5wt.% -V bimetallic oxide modified boron fuel prepared based on a precipitation deposition-impregnation process 2 O 5 /1wt.％-Bi 2 O 3 SEM and Mapping (B, O, bi, V element distribution diagram) pictures of/B.
FIG. 5 is a graph of DSC data for pure boron powder and a dual metal oxide modified boron fuel prepared based on an immersion-precipitation deposition process; wherein A1 is 1wt.% to V 2 O 5 B; a2 is 3.5wt.% -Bi 2 O 3 B; a3 is 3.5wt.% -Bi 2 O 3 /1wt.％-V 2 O 5 /B。
FIG. 6 is a graph of DSC data for pure boron powder and a dual metal oxide modified boron fuel prepared based on a precipitation deposition-impregnation process; it is composed ofWherein B1 is 1wt.% -Bi 2 O 3 B; a2 is 3.5wt.% -V 2 O 5 B; b3 is 3.5wt.% to V 2 O 5 /1wt.％-Bi 2 O 3 /B。
FIG. 7 is a graph of ignition delay data for pure boron powder and a dual metal oxide modified boron fuel prepared based on a dip-precipitate deposition process; wherein A1 is 1wt.% to V 2 O 5 B; a2 is 3.5wt.% Bi 2 O 3 B; a3 is 3.5wt.% Bi 2 O 3 /1wt.％-V 2 O 5 /B。
FIG. 8 is a graph of ignition delay data for pure boron powder and a dual metal oxide modified boron fuel prepared based on a precipitation deposition-impregnation process; wherein 1wt.% -Bi 2 O 3 B, performing the reaction; a2 is 3.5wt.% to V 2 O 5 B, performing the reaction; b3 is 3.5wt.% to V 2 O 5 /1wt.％-Bi 2 O 3 /B。
The present invention will be explained in further detail with reference to examples.
Detailed Description
It is to be understood that all materials and devices known in the art may be used in the present invention without specific recitation.
The bimetal oxide has obvious catalytic effect in a plurality of catalytic reactions as a catalyst, is more effective in improving the ignition and combustion performance of boron particles compared with a single metal oxide, and meanwhile, the bi-component metal oxide has obvious improvement on the ignition and combustion performance of other metal fuels such as aluminum powder and the like. Therefore, the surface of the boron particle is loaded with the bimetallic oxide, so that the metal oxides of the two components form a synergistic catalysis effect or form a new active interface structure, the combustion reaction of the boron powder can be effectively catalyzed, the combustion performance of the boron powder is improved, and the application of the boron powder in the field of energetic materials is promoted.
In the invention:
the boron powder is amorphous boron powder and/or crystal boron powder, and the particle size distribution of the boron powder is micron-scale to nanometer-scale.
In the present invention, V 2 O 5 The term/B refers to boron fuel loaded with vanadium oxide。Bi 2 O 3 the/B refers to the boron fuel with deposited bismuth oxide. Bi 2 O 3 /V 2 O 5 B and V 2 O 5 /Bi 2 O 3 Both refer to the bimetallic oxide modified boron fuel.
In the invention, boron fuel V loaded with vanadium oxide is prepared 2 O 5 The reaction equation for/B is:
in the invention, the boron fuel Bi for depositing bismuth oxide is prepared 2 O 3 The reaction equation for/B is:
BiCl 3 +NaOH→Bi(OH) 3 +NaCl (1)
the following embodiments of the present invention are provided, and it should be noted that the present invention is not limited to the following embodiments, and all equivalent changes based on the technical solutions of the present invention are within the protection scope of the present invention.
Example 1:
the embodiment provides a preparation method of a bimetal oxide modified boron fuel, which comprises the steps of carrying out bimetal oxide modification on the surface of boron powder by adopting a dipping-precipitation deposition method to form the bimetal oxide modified boron fuel;
the bimetallic oxide is a composite binary bimetallic oxide of bismuth oxide and vanadium oxide;
the dipping-precipitation deposition method comprises the following steps: firstly, completely soaking boron powder particles by taking a solution of pentavalent vanadium salt as a soaking solution, and drying and calcining to prepare a vanadium oxide-loaded boron fuel; then using BiCl 3 Using NaOH as a precipitator and depositing on the surface of the vanadium oxide-loaded boron fuel to obtain a deposition intermediate product, and calcining and depositing the deposition intermediate product to finally obtain the bismuth oxide-deposited vanadium oxide-loaded boron fuel, namelyPreparing the bimetal oxide modified boron fuel;
the impregnating solution is NH 4 VO 3 An aqueous solution.
BiCl 3 Using BiCl 3 The ethanol solution of (a); naOH is aqueous NaOH.
In this example, the dipping-precipitation deposition method specifically includes the following steps:
step 101, adding boron powder into a small beaker, and then testing the saturated water absorption capacity of the small beaker by using water to obtain the volume of impregnation liquid required by the boron powder;
step 102, weighing 1g of boron powder, pouring the boron powder into a 500ml conical flask, and adding magnetons;
103, using a liquid transfer gun to transfer the prepared NH with the concentration of 0.1mol/L 4 VO 3 Adding deionized water into the aqueous solution to dilute the aqueous solution to the volume of the impregnation liquid required by the boron powder;
step 104, dropwise adding the diluted impregnation liquid obtained in the step 103 into the boron powder obtained in the step 102 to completely soak the boron powder, performing ultrasonic treatment for 10min, continuously performing magnetic stirring for 6h, and setting the temperature of a magnetic stirrer to 65 ℃;
105, placing the boron fuel in an oven to be dried and calcined at the temperature of 80 ℃ to prepare vanadium oxide-loaded boron fuel, namely V 2 O 5 /B。
Step 201, adding the vanadium oxide-loaded boron fuel V prepared in step 105 into a 500ml conical flask 2 O 5 B, then adding 60ml of deionized water, and adding magnetons for ultrasonic continuous stirring;
202, measuring 0.1mol/L BiCl 3 Adding the ethanol solution into a conical flask, and fully stirring for 30min;
step 203, adding 0.5mol/L NaOH aqueous solution to adjust the pH value of the solution to 7-8, adjusting the reaction temperature to 65 ℃, and continuously stirring for 8 hours to perform reaction to obtain a precipitate intermediate product;
step 204, the intermediate product of the precipitation is collected by centrifugation and washed several times with deionized water until the supernatant is AgNO 3 Solution detection of Cl-free - The precipitated intermediate is finally dried in an ovenThen calcining and depositing at the temperature of 80 ℃ to prepare the bimetal oxide modified boron fuel. Thus obtaining Bi 2 O 3 /V 2 O 5 The modified fuel is/B.
Bi obtained in this example 2 O 3 /V 2 O 5 Bi in/B modified fuel 2 O 3 In an amount of 3.5wt.%, V 2 O 5 The content of (b) is 1wt.%.
Example 2:
the embodiment provides a preparation method of a bimetal oxide modified boron fuel, which comprises the steps of carrying out bimetal oxide modification on the surface of boron powder by adopting a precipitation deposition-impregnation method to form the bimetal oxide modified boron fuel;
the bimetallic oxide is a composite binary bimetallic oxide of bismuth oxide and vanadium oxide;
the precipitation deposition-impregnation method comprises the following steps: firstly, biCl is added 3 The bismuth source is adopted, naOH is adopted as a precipitator, precipitation is carried out on the surface of boron powder to obtain a precipitation intermediate product, and the precipitation intermediate product is calcined and deposited to obtain the bismuth oxide deposited boron fuel; and then completely soaking the boron fuel particles for depositing the bismuth oxide by taking a solution of pentavalent vanadium salt as a soaking solution, and drying and calcining to finally obtain the vanadium oxide-loaded boron fuel for depositing the bismuth oxide, namely the double-metal oxide modified boron fuel.
BiCl 3 Using BiCl 3 The ethanol solution of (a); naOH is aqueous NaOH.
The impregnating solution is NH 4 VO 3 An aqueous solution.
In this example, the precipitation deposition-impregnation method specifically includes the following steps:
step 101, adding boron powder into a 500ml conical flask, then adding 60ml deionized water, and adding magnetons for ultrasonic continuous stirring;
102, measuring 0.1mol/L BiCl 3 Adding the ethanol solution into a conical flask, and fully stirring for 30min;
103, adding 0.5mol/L NaOH aqueous solution to adjust the pH value of the solution to 7-8, adjusting the reaction temperature to 65 ℃, and continuously stirring for 8 hours to perform reaction to obtain a precipitate intermediate product;
step 104, centrifugally collecting the intermediate product, washing the intermediate product with deionized water for several times until the supernatant is AgNO 3 Solution detection of Cl-free - And finally, drying the intermediate product in an oven, and calcining and depositing at 80 ℃ to prepare the bismuth oxide deposited boron fuel. Thus obtaining Bi 2 O 3 /B。
Step 201, adding boron fuel Bi for depositing bismuth oxide into a small beaker 2 O 3 B, then testing the saturated water absorption capacity of the boron fuel with water to obtain the boron fuel Bi with deposited bismuth oxide 2 O 3 The volume of the impregnation solution required;
step 202, depositing the bismuth oxide prepared in step 104 into the boron fuel Bi 2 O 3 Pouring the mixture into a 500ml conical flask, and adding magnetons;
step 203, using a liquid transfer gun to transfer the prepared NH with the concentration of 0.1mol/L 4 VO 3 Adding deionized water into the aqueous solution to dilute the aqueous solution until the boron fuel Bi for depositing the bismuth oxide 2 O 3 The volume of the impregnation solution required;
step 204, dropwise adding the diluted impregnation liquid of the step 203 into the bismuth oxide deposited boron fuel Bi in the step 202 2 O 3 In the step B, completely soaking boron powder, performing ultrasonic treatment for 10min, continuously performing magnetic stirring for 6h, and setting the temperature of a magnetic stirrer to 65 ℃;
and step 205, placing the boron fuel in an oven to be dried and calcined at the temperature of 80 ℃ to obtain the bimetal oxide modified boron fuel. Thus obtaining Bi 2 O 3 /V 2 O 5 The modified fuel is/B.
V obtained in this example 2 O 5 /Bi 2 O 3 Bi in/B modified fuel 2 O 3 In an amount of 1wt.%, V 2 O 5 Is present in an amount of 3.5wt.%.
FIG. 1 is a 3.5wt.% -Bi representation of a dual metal oxide modified boron fuel prepared based on a dip-precipitation deposition process 2 O 3 /1wt.％-V 2 O 5 XPS spectrum of/B: (A) B1s, (B)) Bi 4f, (C) V2 p, (D) O1 s. The B1s spectrogram can determine that the surface of boron powder is mainly 0-valent boron, and the V2 p spectrogram can determine that V is V 5+ The spectrum of Bi 4f can determine that Bi is Bi 3+ And the combination of the O1s spectrogram can determine that Bi is deposited on the surface of the boron powder 2 O 3 And V 2 O 5 A binary bimetallic oxide.
FIG. 2 is a 3.5wt.% -V representation of a dual metal oxide modified boron fuel prepared based on a precipitation deposition-impregnation process 2 O 5 /1wt.％-Bi 2 O 3 XPS spectrum of/B: b1s, (B) V2 p, (C) Bi 4f, and (D) O1 s. B1s spectrogram can determine that the surface of boron powder is mainly 0-valent boron and a small amount of B exists 2 O 3 Species, bi can be determined as Bi through the spectrum of Bi 4f 3+ V can be determined as V by the spectrogram of V2 p 5+ And V can be determined to be deposited on the surface of the boron powder by combining the O1s spectrogram 2 O 5 And Bi 2 O 3 A bimetallic oxide.
FIG. 3 is a 3.5wt.% -Bi representation of a dual metal oxide modified boron fuel prepared based on a dip-precipitate deposition process 2 O 3 /1wt.％-V 2 O 5 SEM and Mapping (B, bi, O, V element distribution diagram) of/B. The element distribution of Bi, V and B shows that Bi is deposited 2 O 3 And V 2 O 5 The two oxides are uniformly distributed on the surface of the boron powder.
FIG. 4 is a 3.5wt.% -V bimetallic oxide modified boron fuel prepared based on a precipitation deposition-impregnation process 2 O 5 /1wt.％-Bi 2 O 3 SEM and Mapping (B, O, bi, V element distribution diagram) of/B. The deposited V can be seen by the elemental distribution of V, bi and B 2 O 5 And Bi 2 O 3 The two oxides are uniformly distributed on the surface of the boron powder.
Example 3:
the embodiment provides a combustion performance test method of a bimetal oxide modified boron fuel, which comprises the following steps: taking a proper amount of bimetal oxide modified boron fuel sample in a sample table of a TG-DSC instrument, setting the heating rate to be 10 ℃/min and the testing temperature range to be 50-1000 ℃. The exothermic peak temperature of the bimetal oxide modified boron fuel prepared by the invention is advanced to 525-498 ℃, and is advanced by 150-200 ℃ compared with pure boron powder.
Specifically, a proper amount of bimetal oxide modified boron fuel sample is placed in a sample table of a TG-DSC instrument, the combustion performance of the boron powder loaded bismuth oxide compound is tested by adopting a thermogravimetry method and a differential calorimetry (TG-DSC) method, the heating rate is 10 ℃/min, and the test temperature range is 50-1000 ℃. The exothermic peak temperature of pure boron powder is 677 ℃,3.5wt.% -Bi 2 O 3 /1wt.％-V 2 O 5 The exothermic peak temperature of the/B was advanced to 522 ℃,3.5wt.% -V 2 O 5 /1wt.％-Bi 2 O 3 The exothermic peak temperature of the/B was advanced to 509 ℃.
FIG. 5 is a graph of DSC data for pure boron powder and a dual metal oxide modified boron fuel prepared based on an immersion-precipitation deposition process; wherein A1 is 1wt.% to V 2 O 5 B, performing the reaction; a2 is 3.5wt.% Bi 2 O 3 B; a3 is 3.5wt.% Bi 2 O 3 /1wt.％-V 2 O 5 B; from the DSC data plot, deposit V can be seen 2 O 5 And Bi 2 O 3 The oxidation peak temperature of the boron powder is obviously reduced, and V is deposited 2 O 5 And Bi 2 O 3 Has the effect of obviously reducing the oxidation peak temperature of the boron powder.
FIG. 6 is a graph of DSC data for pure boron powder and a dual metal oxide modified boron fuel prepared based on a precipitation deposition-impregnation process; wherein B1 is 1wt.% Bi 2 O 3 B; a2 is 3.5wt.% to V 2 O 5 B; b3 is 3.5wt.% to V 2 O 5 /1wt.％-Bi 2 O 3 B; from the DSC data chart, it can be seen that Bi is deposited 2 O 3 And V 2 O 5 Obviously reduces the oxidation peak temperature of the boron powder and simultaneously deposits Bi 2 O 3 And V 2 O 5 Has the effect of remarkably reducing the oxidation peak temperature of boron powder compared with a single oxide.
Example 4:
in this embodiment, the ignition performance test of the dual-metal oxide modified boron fuel is given, and the ignition performance test method is as follows: taking a proper amount of bimetal oxide modified boron fuel sample in a sample stage of a laser ignition instrument, and setting instrument parameters as frequency Hz:1000, parts by weight; duty cycle (1-40%): 3; pulse number: 1000, parts by weight; emitting light by a pulse train; power: 40W; pulse energy: 40mJ; pulse width: 30 mus. The ignition delay time of the bimetal oxide modified boron fuel prepared by the invention is shortened to 26ms, and is shortened by more than 26ms compared with pure boron powder.
Specifically, a proper amount of bimetal oxide modified boron fuel sample is taken and placed in a sample stage of a laser ignition instrument, and the instrument parameters are set as frequency Hz:1000, parts by weight; duty cycle (1-40%): 3; pulse number: 1000, parts by weight; emitting light by a pulse train; power: 40W; pulse energy: 40mJ; pulse width: 30 mus. As shown in fig. 5 and 6, the ignition delay time of the dual-metal oxide modified boron fuel prepared by the invention is shortened to 26ms, which is shortened by more than 26ms compared with that of pure boron powder;
FIG. 7 is a graph of ignition delay data for pure boron powder and a dual metal oxide modified boron fuel prepared based on a dip-precipitate deposition process; wherein A1 is 1wt.% to V 2 O 5 B; a2 is 3.5wt.% Bi 2 O 3 B, performing the reaction; a3 is 3.5wt.% Bi 2 O 3 /1wt.％-V 2 O 5 B; it can be seen from the ignition delay time that only V is deposited 2 O 5 And deposition of Bi alone 2 O 3 Significantly less effective in shortening the ignition delay time than simultaneous deposition of V 2 O 5 And Bi 2 O 3 3.5wt.% to Bi in the boron fuel of (a) 2 O 3 /1wt.％-V 2 O 5 The ignition delay time of/B is as low as 26ms.
FIG. 8 is a graph of ignition delay data for pure boron powder and a dual metal oxide modified boron fuel prepared based on a precipitation deposition-impregnation process; wherein 1wt.% Bi 2 O 3 B; a2 is 3.5wt.% to V 2 O 5 B; b3 is 3.5wt.% to V 2 O 5 /1wt.％-Bi 2 O 3 B, performing the reaction; it can be seen from the ignition delay time that only Bi is deposited 2 O 3 And only deposit V 2 O 5 The effect on shortening the ignition delay time is also significantly lower than that of simultaneously depositing V 2 O 5 And Bi 2 O 3 Boron combustion ofAnd (5) feeding.
Table 1 shows the combustion performance of the bimetallic oxide modified boron fuel of the present invention.
TABLE 1 Combustion Properties of bimetal oxide modified boron fuels
| Sample (I) | T p (℃) | Ignition delay time (ms) |
| Pure B | 677 | 52 |
| 1wt.％-Bi 2 O 3 / |
525 | 50 |
| 3.5wt.％-Bi 2 O 3 / |
515 | 49.6 |
| 1wt.％-V 2 O 5 / |
520 | 43.3 |
| 3.5wt.％-V 2 O 5 /B | 524 | 42.5 |
| 3.5wt.％-Bi 2 O 3 /1wt.％-V 2 O 5 /B | 522 | 26 |
| 3.5wt.％-V 2 O 5 /1wt.％-Bi 2 O 3 /B | 509 | 36.8 |
Compared with the prior art, the bimetal oxide modified boron fuel prepared by the invention has the advantages of good ignition performance, high energy density and the like; the liquid phase chemical preparation method selected by the invention has the advantages of mild conditions, simple operation process and convenience for realizing large-scale preparation, and meanwhile, the method can realize uniform high dispersion of two oxide components on the surface of boron powder, effectively reduce the consumption of the oxide and show good application prospect in the field of high-energy solid fuel.
Claims (9)
1. A preparation method of a bimetal oxide modified boron fuel is characterized in that the method adopts a dipping-precipitation deposition method or a precipitation deposition-dipping method to modify bimetal oxide on the surface of boron powder to form the bimetal oxide modified boron fuel;
the bimetallic oxide is a composite binary bimetallic oxide of bismuth oxide and vanadium oxide;
the dipping-precipitation deposition method comprises the following steps: firstly, completely soaking boron powder particles by taking a solution of pentavalent vanadium salt as a soaking solution, and drying and calcining to prepare a vanadium oxide-loaded boron fuel; then using BiCl 3 Taking NaOH as a precipitator as a bismuth source, precipitating on the surface of the boron fuel loaded with vanadium oxide to obtain a precipitation intermediate product, calcining and depositing the precipitation intermediate product to finally obtain the boron fuel loaded with vanadium oxide and deposited with bismuth oxide, namely the bimetal oxide modified boron fuel;
the precipitation deposition-impregnation method comprises the following steps: firstly, biCl is added 3 As bismuth source, using NaOH asPrecipitating the boron powder by using a precipitator to obtain a precipitation intermediate product, and calcining and depositing the precipitation intermediate product to obtain the bismuth oxide-deposited boron fuel; then completely soaking the boron fuel particles with deposited bismuth oxide by taking a solution of pentavalent vanadium salt as a soaking solution, and drying and calcining to finally obtain the boron fuel with deposited bismuth oxide loaded with vanadium oxide, namely the double-metal oxide modified boron fuel;
the contents of bismuth oxide and vanadium oxide in the bimetal oxide modified boron fuel are respectively 0.1-5 wt.%.
2. The method of claim 1, wherein the bismuth oxide and vanadium oxide are present in the boron fuel in an amount of 1wt.% to 5wt.%, respectively.
3. The method of claim 1, wherein said BiCl is present in a fuel 3 Using BiCl 3 Or BiCl 3 The ethanol solution of (a); the NaOH adopts NaOH aqueous solution.
4. The method of claim 1, wherein the impregnating solution is NH 4 VO 3 An aqueous solution.
5. The method of claim 1, wherein the dip-precipitation deposition process comprises the steps of:
step 101, adding boron powder into a reaction container, and then testing the saturated water absorption capacity of the boron powder by using water to obtain the volume of impregnation liquid required by the boron powder;
102, weighing boron powder, pouring the boron powder into a reaction container, and adding magnetons;
103, using a liquid transfer gun to transfer the prepared soaking liquid with the concentration of 0.001-1 mol/L, and adding deionized water to dilute the soaking liquid to the volume of the soaking liquid required by the boron powder;
step 104, dropwise adding the dipping solution diluted in the step 103 into the boron powder obtained in the step 102 to completely soak the boron powder, and ultrasonically stirring;
105, placing the boron fuel in an oven to be dried and calcined at the temperature of 60-80 ℃ to prepare vanadium oxide-loaded boron fuel;
step 201, adding the boron fuel loaded with vanadium oxide prepared in step 105 into a reaction container, then adding deionized water, and adding magneton for ultrasonic continuous stirring;
202, measuring BiCl 3 Or BiCl 3 Adding the ethanol solution into a reaction vessel, and fully stirring;
step 203, adding NaOH aqueous solution to adjust the pH value of the solution to 7-8, adjusting the reaction temperature to be within the range of 30-100 ℃, and continuously stirring for 2-12 hours to carry out reaction to obtain a precipitate intermediate product;
and step 204, centrifugally collecting the precipitation intermediate product, washing the precipitation intermediate product for a plurality of times by using deionized water until the anion corresponding to the bismuth source cannot be detected in the supernatant, and finally, drying the precipitation intermediate product in an oven, and calcining and depositing the dried precipitation intermediate product at the temperature of 60-80 ℃ to obtain the bimetal oxide modified boron fuel.
6. The method of claim 1, wherein the precipitation deposition-impregnation method comprises the following steps:
step 101, adding boron powder into a reaction container, then adding deionized water, and adding magnetons for ultrasonic continuous stirring;
102, measuring BiCl 3 Or BiCl 3 Adding the ethanol solution into a reaction container, and fully stirring;
103, adding NaOH aqueous solution to adjust the pH value of the solution to 7-8, adjusting the reaction temperature to be within the range of 30-100 ℃, and continuously stirring for 2-12 hours to react to obtain a precipitate intermediate product;
step 104, centrifugally collecting a precipitation intermediate product, washing the precipitation intermediate product for a plurality of times by using deionized water until no anion corresponding to the bismuth source can be detected in a supernatant, and finally drying the precipitation intermediate product in an oven and then calcining and depositing the precipitation intermediate product at the temperature of 60-80 ℃ to obtain the bismuth oxide deposited boron fuel;
step 201, adding the boron fuel deposited with bismuth oxide prepared in step 104 into a reaction container, and then testing the saturated water absorption capacity of the boron fuel with water to obtain the volume of an impregnation liquid required by the boron fuel deposited with bismuth oxide;
step 202, weighing the boron fuel for depositing the bismuth oxide, pouring the boron fuel into a reaction container, and adding magnetons;
step 203, using a liquid transfer gun to transfer the prepared impregnation liquid with the concentration of 0.001-1 mol/L, and adding deionized water to dilute the impregnation liquid to the volume of the impregnation liquid required by the bismuth oxide deposited boron fuel;
step 204, dropwise adding the impregnation liquid diluted in the step 203 into the boron fuel deposited with the bismuth oxide in the step 202 to completely soak the boron fuel deposited with the bismuth oxide, and ultrasonically stirring;
and step 205, placing the boron fuel in an oven to be dried and calcined at the temperature of 60-80 ℃ to obtain the bimetal oxide modified boron fuel.
7. The bimetal oxide modified boron fuel prepared by the method for preparing the bimetal oxide modified boron fuel as claimed in any one of claims 1 to 6, characterized in that the bimetal oxide modification is carried out on the surface of boron powder to form the bimetal oxide modified boron fuel; the bimetallic oxide is a composite binary bimetallic oxide of bismuth oxide and vanadium oxide; the contents of bismuth oxide and vanadium oxide in the bimetal oxide modified boron fuel are respectively 0.1-5 wt.%.
8. The dual metal oxide modified boron fuel of claim 7, wherein the bismuth oxide and vanadium oxide are present in the dual metal oxide modified boron fuel in an amount of 1wt.% to 5wt.%, respectively.
9. The dual metal oxide modified boron fuel of claim 8, wherein the bismuth oxide and vanadium oxide are present in the dual metal oxide modified boron fuel in an amount of 1wt.% to 3.5wt.%, respectively.
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| CN103396275A (en) * | 2013-08-08 | 2013-11-20 | 南京理工大学 | Nanometer bismuth oxide-coated modified boron fuel and preparation methods thereof |
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| US7927437B2 (en) * | 2005-10-28 | 2011-04-19 | The Curators Of The University Of Missouri | Ordered nanoenergetic composites and synthesis method |
| US10017429B2 (en) * | 2013-10-10 | 2018-07-10 | Battelle Energy Alliance, Llc | Methods of reducing ignition sensitivity of energetic materials |
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| FR1375299A (en) * | 1962-09-07 | 1964-10-16 | United Coke And Chemicals Comp | Catalyst manufacturing |
| US4179327A (en) * | 1978-07-13 | 1979-12-18 | Allied Chemical Corporation | Process for coating pyrotechnic materials |
| CN103396275A (en) * | 2013-08-08 | 2013-11-20 | 南京理工大学 | Nanometer bismuth oxide-coated modified boron fuel and preparation methods thereof |
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