CN105177517A

CN105177517A - Nanometer thermite and preparing method thereof

Info

Publication number: CN105177517A
Application number: CN201510611102.1A
Authority: CN
Inventors: 张文超; 程佳; 秦志春; 焦阳; 叶家海; 田桂蓉
Original assignee: Nanjing University of Science and Technology
Current assignee: Nanjing University of Science and Technology
Priority date: 2015-09-23
Filing date: 2015-09-23
Publication date: 2015-12-23

Abstract

The invention discloses nanometer thermite and a preparing method thereof. The preparing method comprises the specific steps that a substrate is vertically immersed in PS macromolecule micro-ball dispersion liquid, and directional arrangement of PS macromolecule micro-balls is carried out through a bent liquid level formed through solvent evaporation for self-assembling to form a colloidal crystal template; nano-composite metal oxide precursor is prepared; the PS colloidal crystal template is placed in the prepared precursor and immersed for 3-5 min to be taken out, and then the colloidal crystal template is transferred into an oven to be dried to obtain a PS/precursor composite film; the PS/precursor composite film is placed in a muffle furnace for program temperature rising roasting, and after the PS colloidal crystal template is removed, three-dimensional orderly macropore nano-composite metal oxide is generated; and aluminum is deposited in a duct of the nano-composite metal oxide through a magnetron sputtering method, and the nanometer thermite with the substrate loaded with the nano-composite metal oxide thermit film is obtained. The operation is easy, and the nanometer thermite with the beneficial effects of being high in energy density, small in three-dimensional scale, capable of achieving compatibility between the preparing technology and the MEMS manufacturing technology and the like can be prepared under the mild condition.

Description

Nano aluminum thermit powder and preparation method thereof

Technical field

The invention belongs to the technical field of Nanocomposite Energetic Materials, particularly several nano aluminum thermit powder and preparation method thereof.

Background technology

MEMS (MicroElectro-mechanicalSystem) priming system refers to based on MEMS technology or the priming system technology with MEMS technology compatibility, it not only possesses the function such as control, work done, igniting of traditional priming system, also there is the advantages such as miniaturization, integrated, digitizing, intellectuality, more can meet following pyrotechnics system space flight, ammunition, medical in application.But along with the continuous reduction of MEMS chip size, the output energy of priming system is more and more difficult to the igniting requirement meeting some device, thus make igniting integrity problem increasingly outstanding.Nanocomposite Energetic Materials is owing to having the advantages such as energy density is high, energy release rate is fast, three dimension scale is little, and therefore, scientists considers Nanocomposite Energetic Materials to be integrated in MEMS.Nano aluminum thermit powder as the typical Nanocomposite Energetic Materials of one, because its toxicity is low, thermal discharge is high, preparation is simple, so become the study hotspot in MEMS Nanocomposite Energetic Materials field.

Nano aluminum thermit powder, also known as metastable state intermolecular complex, compared with conventional aluminum thermit powder, because oxygenant and fuel are combined closely under nanoscale, reduce the distance of mass transfer between material, thus have the advantages such as higher energy output, faster energy release rate.At present, the method mainly ultrasonic physics mixing of nano aluminum thermit powder, sol-gel, physical vapor deposition and molecular self-assembling method is prepared both at home and abroad.Such as:

Document 1 (Bockmon, B.S, Pantoya, M.L, et.al.Combustionvelocitiesandpropagationmechanismsofmeta stableinterstitialcomposites [J] .JournalofAppliedPhysics, 2005,98 (6): 064903) by three kinds of different-grain diameter Al Nanoparticles and nanometer MoO ₃ultrasonic physics mixes.Test result shows that nano aluminum thermit powder combustionvelocity slowly increases along with the reduction of nanometer Al size of particles; But when nanometer Al particle dia exceedes a certain numerical value, the particle diameter of combustionvelocity and Al Nanoparticles has nothing to do.

Document 2 (TillotsonT.M, GashA.E, et.al.Nanostructuredenergeticmaterialsusingsol-gelmethod ologies [J] .JournalofNon-CrystallineSolids, 2001,285 (1-3): 338-345) the nanometer Al/Fe that adopted sol-gel method to prepare ₂o ₃thermite, thermal analyses result shows its thermal discharge up to 1.5kJ/g, and this is nanometer Al/Fe on to a certain degree increasing ₂o ₃the ignition ability of thermite.In addition, because sensitivity test shows nanometer Al/Fe ₂o ₃thermite is to shock, electrostatic, friction ratio comparatively insensitiveness, and thus the security of product is higher.

Document 3 (ZhangK.L, CaroleR, et.al.Developmentofanano-Al/CuObasedenergeticmaterialons iliconsubstrate [J] .AppliedPhysicsLetters, 2007,91 (11): 113117) by physical vaporous deposition by the thin film deposition of multi-layer nano Al/CuO aluminothermy in silicon base.The feature of the method is that the Contact of component is tight, product size is evenly adjustable and effectively can reduces the oxidation of impurity and nanometer Al.In addition, utilize physical vapor deposition can be incorporated in silicon base by nano aluminum thermit powder, this provides a kind of new method for Nanocomposite Energetic Materials is integrated in the MEMS based on silicon, thus forms the new functional nano portfire of a class.

Document 4 (SeveracF, AlphonseP, etal.High-EnergyAl/CuONanocompositesObtainedbyDNA-Direct edAssembly [J] .AdvancedFunctionalMaterials, 2012,22 (2): 323-329) utilize DNA self-assembly to prepare nanometer Al/CuO thermite, by test find the ignition temperature of this nano aluminum thermit powder be low to moderate 410 DEG C and thermal discharge up to 1.8kJg ^-1, and by change nano-aluminium particle size thus adjust its ignition temperature and exothermic heat of reaction amount.

From the above, in order to improve the preparation technology of nano aluminum thermit powder further, there is following defect in existing preparation method:

Document 1: ultrasonic physics hybrid system and MEMS preparation technology are difficult to compatibility, and there is very high surface energy due to nanoparticle, therefore in the process of ultrasonic mixing, particle is very easily reunited.In addition, nanometer aluminium powder is fully contacted by ultrasonic being difficult to nano-oxide, and this can have a strong impact on the reactive behavior of nano aluminum thermit powder.

Document 2: a large amount of organic solvent will be used in the process of preparation nano aluminum thermit powder, thus inevitably introduce organic impurity, thus cause the energy density of product to reduce.In addition, sol-gel process required time is longer, is unfavorable for large-scale industrial production.

Document 3: physical gas-phase deposition takes time and effort, cost is high, narrow application range.

Document 4: self-assembly method and MEMS manufacturing technology incompatible, and cost is higher, and will use polymkeric substance in the process of preparation, and this will certainly reduce the energy density of nano aluminum thermit powder.

Summary of the invention

Nano aluminum thermit powder that the object of the present invention is to provide a kind of novel structure, excellent performance and preparation method thereof.

The technical solution realizing the object of the invention is: a kind of nano aluminum thermit powder, comprise substrate and be attached to suprabasil nano composite metal oxide aluminothermy film, described aluminothermy film is by being formed in al deposition to nano composite metal oxide, wherein, nano composite metal oxide is CoFe ₂o ₄or NiFe ₂o _4,nano composite metal oxide has three-dimensional ordered macroporous (3DOM) structure.

Preferably, described substrate is glass, quartz, silicon chip etc.

Prepare the method for above-mentioned nano aluminum thermit powder, comprise the steps:

Step 1: polystyrene (PS) polymer microsphere is made dispersion liquid;

Step 2: substrate is dipped vertically in the dispersion liquid that step 1 prepares, the self-assembly that aligns that the curved liquid surface formed carries out PS polymer microsphere forms glue crystal template to utilize solvent to evaporate;

Step 3: the glue crystal template in step 2 is placed in nano composite metal oxide precursor liquid, soaks after 3 ~ 5 minutes and takes out, obtain PS/ precursor liquid laminated film after drying;

Step 4: the PS/ precursor liquid laminated film in step 3 is carried out intensification calcining, generate 3DOM nano composite metal oxide after removing PS glue crystal template;

Step 5: in the duct of the nano composite metal oxide adopting magnetron sputtering method to be prepared to step 4 by al deposition, obtain described nano aluminum thermit powder.

Preferably, in step 1, the diameter of described PS polymer microsphere is 20 ~ 600nm; The concentration of described PS polymer microsphere dispersion liquid is 1 ~ 25wt%.

Preferably, in step 3, nano composite metal oxide precursor liquid is CoFe ₂o ₄, CoFe ₂o ₄precursor liquid is by Fe (NO ₃) ₃9H ₂o and Co (NO ₃) ₂6H ₂o is dissolved in the mixed solvent of methyl alcohol and ethylene glycol obtained after stirring and dissolving; Wherein, the volume ratio of methyl alcohol, ethylene glycol is 1: 2; Fe (NO ₃) ₃9H ₂o, Co (NO ₃) ₂6H ₂the mol ratio of O is 2: 1; Fe (NO ₃) ₃9H ₂the addition of O is 0.08 ~ 0.57 times of methyl alcohol and ethylene glycol mixed solvent quality; Co (NO ₃) ₂6H ₂o adds 0.02 ~ 0.21 times that quality is methyl alcohol and ethylene glycol mixed solvent quality.

Preferably, in step 3, nano composite metal oxide precursor liquid is NiFe ₂o ₄precursor liquid, NiFe ₂o ₄precursor liquid is by Fe (NO ₃) ₃9H ₂o and Ni (NO ₃) ₂6H ₂o is dissolved in the mixed solvent of methyl alcohol and ethylene glycol obtained after stirring and dissolving; Wherein, the volume ratio of methyl alcohol, ethylene glycol is 2: 3; Fe (NO ₃) ₃9H ₂o, Ni (NO ₃) ₂6H ₂the mol ratio of O is 2: 1; Fe (NO ₃) ₃9H ₂the addition of O is 0.08 ~ 0.57 times of methyl alcohol and ethylene glycol mixed solvent quality; Ni (NO ₃) ₂6H ₂o adds 0.02 ~ 0.21 times that quality is methyl alcohol and ethylene glycol mixed solvent quality.

Preferably, in step 4, the parameter of the calcining that heats up is: from room temperature, with 1 DEG C of min ^-1ramp to 500 DEG C ~ 600 DEG C, be incubated 1 ~ 10 hour, be then cooled to room temperature.

Preferably, in step 5, deposition of aluminum adopts magnetron sputtering method, and its parameter is: argon flow amount is 30Sccm, and sputtering power is 60W, and vacuumometer registration is 0.4Pa, and sedimentation rate is about 10nmmin ^-1; The time of aluminizing is 10 ~ 60min.

The present invention compared with prior art, has the following advantages: (1) fuel and oxygenant, at nanoscale close contact, reduce mass transfer and heat conducting distance, and its speed of reaction is greatly improved; (2) cost is low, simple to operate, and foreign matter content is few, and product postprocessing is convenient, environmental protection; (3) equipment is convenient, and security is high, and preparation cycle is short, and preparation technology is mutually compatible with MEMS manufacturing technology, is applicable to prepare most metal oxide.

Accompanying drawing explanation

Fig. 1 is the structural representation of nano aluminum thermit powder of the present invention.

Fig. 2 is preparation method's schematic flow sheet of nano aluminum thermit powder of the present invention.

Fig. 3 is 3DOM nano Co Fe in example 1 in the present invention ₂o ₄the SEM figure of skeleton, the SEM that wherein (a) is amplification 60000 times schemes, and (b) is amplification 20000 times of SEM figure.

Fig. 4 is nanometer Al/CoFe in example 1 in the present invention ₂o ₄the SEM figure of aluminothermy film, the SEM that wherein (a) is amplification 80000 times schemes, and the SEM that (b) is amplification 20000 times schemes.

Fig. 5 is nanometer Al/CoFe in example 1 in the present invention ₂o ₄the DSC figure of aluminothermy film.

Fig. 6 is 3DOM nano-Ni/Fe in example 16 in the present invention ₂o ₄the SEM figure of skeleton film, the SEM that wherein (a) is amplification 50000 times schemes, and the SEM that (b) is amplification 80000 times schemes.

Fig. 7 is nanometer Al/NiFe in example 16 in the present invention ₂o ₄the figure of aluminothermy film SEM, the SEM that wherein (a) is amplification 20000 times schemes, and the SEM that (b) is amplification 80000 times schemes.

Fig. 8 is nanometer Al/NiFe in example 16 in the present invention ₂o ₄the DSC figure of aluminothermy film.

Embodiment

Below in conjunction with accompanying drawing and specific examples, the present invention will be further described.

Composition graphs 1, nano aluminum thermit powder of the present invention, the nano composite metal oxide aluminothermy film comprising substrate and adhere in substrate, described aluminothermy film is by being formed in al deposition to nano composite metal oxide, and wherein, nano composite metal oxide is CoFe ₂o ₄or NiFe ₂o ₄, nano composite metal oxide has three-dimensional ordered macroporous structure, and described substrate is glass, quartz, silicon chip, oxide compound etc.By integrated nanometer complex metal oxides aluminothermy film preparation nano aluminum thermit powder in substrate, utilize film to react the energy output of the heat gain MEMS priming system of a large amount of chemistry of releasing, thus improve MEMS priming system ignition ability.

Composition graphs 2, the preparation method of nano aluminum thermit powder of the present invention, comprises the steps:

Step 1: preparation PS polymer microsphere, the diameter of described PS polymer microsphere is 20 ~ 600nm, is then mixed with PS polymer microsphere dispersion liquid with deionized water, and the concentration of described PS polymer microsphere dispersion liquid is 1 ~ 25wt%;

Step 2: substrate is dipped vertically in the PS polymer microsphere dispersion liquid that step 1 prepares, the self-assembly that aligns that the curved liquid surface formed carries out PS polymer microsphere forms glue crystal template to utilize solvent to evaporate;

Step 3: preparation of nano complex metal oxides precursor liquid; Comprise following two kinds of nano composite metal oxide precursor liquids, as follows respectively:

(1) preparation of nano complex metal oxides precursor liquid, wherein nano composite metal oxide is CoFe ₂o ₄, precursor liquid process for preparation is as follows: accurately take Fe (NO with analytical balance ₃) ₃9H ₂o and Co (NO ₃) ₂6H ₂o, then adds methyl alcohol and ethylene glycol and carries out magnetic agitation, until Fe (NO ₃) ₃9H ₂o and Co (NO ₃) ₂6H ₂o dissolves completely; Wherein the volume ratio of methyl alcohol, ethylene glycol is 1: 2; Fe (NO ₃) ₃9H ₂o, Co (NO ₃) ₂6H ₂the mol ratio of O is 2: 1; Fe (NO ₃) ₃9H ₂the interpolation quality of O is 0.08 ~ 0.57 times of methyl alcohol and ethylene glycol mixed solvent quality; Co (NO ₃) ₂6H ₂o adds 0.02 ~ 0.21 times that quality is methyl alcohol and ethylene glycol mixed solvent quality.

(2) preparation of nano complex metal oxides precursor liquid, wherein nano composite metal oxide is NiFe ₂o ₄, precursor liquid process for preparation is as follows: accurately take Fe (NO with analytical balance ₃) ₃9H ₂o and Ni (NO ₃) ₂6H ₂o, then adds methyl alcohol and ethylene glycol and carries out magnetic agitation, until Fe (NO ₃) ₃9H ₂o and Ni (NO ₃) ₂6H ₂o dissolves completely; Wherein the volume ratio of methyl alcohol, ethylene glycol is 2: 3; Fe (NO ₃) ₃9H ₂o, Ni (NO ₃) ₂6H ₂the mol ratio of O is 2: 1; Fe (NO ₃) ₃9H ₂the interpolation quality of O is 0.08 ~ 0.57 times of methyl alcohol and ethylene glycol mixed solvent quality; Ni (NO ₃) ₂6H ₂o adds 0.02 ~ 0.21 times that quality is methyl alcohol and ethylene glycol mixed solvent quality.

Step 4: the PS glue crystal template in step 2 is put into the precursor liquid that step 4 is prepared, soaks after 3 ~ 5 minutes and takes out, then transfer to drying in baking oven and obtain PS/ precursor liquid laminated film;

Step 5: the PS/ precursor liquid laminated film in step 4 is put into retort furnace and carries out temperature programming calcining, generate 3DOM nano composite metal oxide after removing PS glue crystal template, the parameter of described retort furnace temperature programming calcining is: from room temperature, with 1 DEG C of min ^-1ramp to 500 DEG C ~ 600 DEG C, be incubated 1 ~ 10 hour, be then cooled to room temperature;

Step 6: utilize magnetron sputtering method by the duct of the nano composite metal oxide prepared by al deposition to step 5, obtain the nano aluminum thermit powder that substrate is loaded with nano composite metal oxide aluminothermy film, wherein the parameter of magnetron sputtering is: argon flow amount is 30Sccm, sputtering power is 60W, vacuumometer registration is 0.4Pa, and sedimentation rate is about 10nmmin ^-1; The time of aluminizing is 10 ~ 60min.

Example 1:

Step 1: preparation smooth surface, good dispersity, particle diameter are the PS polymer microsphere of 300nm, are then mixed with deionized water the PS polymer microsphere dispersion liquid that concentration is 1.5wt%;

Step 3: accurately take 24.24gFe (NO with analytical balance ₃) ₃9H ₂o and 8.73gCo (NO ₃) ₂6H ₂o, then adds 20mL methyl alcohol and 40mL ethylene glycol, and obtains nano composite metal oxide precursor liquid with magnetic agitation 9h;

Step 4: the PS glue crystal template in step 2 is put into the precursor liquid that step 4 is prepared, soaks after 3 ~ 5 minutes and takes out, and remove unnecessary precursor liquid, then transfer in baking oven after 50 DEG C of dry 24h, obtain PS/ precursor liquid laminated film;

Step 5: the PS/ precursor liquid laminated film in step 4 is put into retort furnace, from room temperature, with 1 DEG C of min ^-1ramp to 500 DEG C, 500 DEG C insulation 3h, be then cooled to room temperature, after removing PS glue crystal template, obtain 3DOM nano Co Fe ₂o ₄skeleton;

Step 6: utilize the 3DOM nano Co Fe that al deposition is prepared to step 5 by magnetron sputtering method ₂o ₄in the duct of skeleton, wherein the parameter of magnetron sputtering is: argon flow amount is 30Sccm, and sputtering power is 60W, and vacuumometer registration is 0.4Pa, and sedimentation rate is about 10nmmin ^-1; The time of aluminizing is 60min, obtains substrate and is loaded with nanometer Al/CoFe ₂o ₄the nano aluminum thermit powder of aluminothermy film.

Fig. 3 is 3DOM nano Co Fe in example 1 ₂o ₄the SEM figure of skeleton, as can be seen from Fig. 3-(a) and 3-(b), after high-temperature calcination, the completely dissolve of PS polymer microsphere, the space between polymer microsphere is by nano Co Fe ₂o ₄crystal grain filled, and whole skeleton is rendered as porous network structure, and pore wall thickness is about 30nm, and the shape approximation in hole is circular, and aperture is homogeneous is about 200nm, and aperture has shunk 33% compared with before.In addition, can also observe framework local and occur fracture from figure, this situation is inevitable in calcination process.

Fig. 4 is nanometer Al/CoFe in example 1 ₂o ₄the SEM figure of aluminothermy film, 3DOM nano Co Fe as we can see from the figure ₂o ₄skeleton use magnetron sputtering is aluminized after 60min, polynuclear plane disappears, skeleton surface cover by one deck nano aluminum, this illustrates that inside, duct has loaded full nano aluminum, which ensure that the abundant contact at nanoscale between reactant, thus reduce the distance of mass transfer between material, add Al and CoFe ₂o ₄between the activity of thermite reaction.

Fig. 5 is nanometer Al/CoFe in example 1 ₂o ₄the DSC figure of aluminothermy film, can find out has an obvious exothermic peak between 500 DEG C ~ 650 DEG C, and thermal discharge is up to 1857Jg ^-1; In addition, occur an endotherm(ic)peak at 660 DEG C, this is the melting hump of aluminium.These illustrate Al and CoFe above ₂o ₄reaction mainly concentrate on reaction between solid phase and solid phase, i.e. solid-solid reaction.It should be noted that the exothermic peak that appearance one is small between 250 DEG C ~ 400 DEG C, thermal discharge is 83.79Jg ^-1, this may be due to 3DOM nano Co Fe ₂o ₄in a small amount of Co (OH) ₂caused by decomposes.

Example 2:

Step 1: preparation smooth surface, good dispersity, particle diameter are the PS polymer microsphere of 20nm, are then mixed with deionized water the PS polymer microsphere dispersion liquid that concentration is 1.5wt%;

Step 4: the PS glue crystal template in step 2 is put into the precursor liquid that step 4 is prepared, takes out after soaking 3 ~ 5min, and removes unnecessary precursor liquid, then transfer in baking oven after 50 DEG C of dry 24h, obtain PS/ precursor liquid laminated film;

Example 3:

Step 1: preparation smooth surface, good dispersity, particle diameter are the PS polymer microsphere of 600nm, are then mixed with deionized water the PS polymer microsphere dispersion liquid that concentration is 1.5wt%;

Example 4:

Step 1: preparation smooth surface, good dispersity, particle diameter are the PS polymer microsphere of 300nm, are then mixed with deionized water the PS polymer microsphere dispersion liquid that concentration is 1wt%;

Example 5:

Step 1: preparation smooth surface, good dispersity, particle diameter are the PS polymer microsphere of 300nm, are then mixed with deionized water the PS polymer microsphere dispersion liquid that concentration is 25wt%;

Example 6:

Example 7:

Example 8:

Step 3: accurately take 33.936gFe (NO with analytical balance ₃) ₃9H ₂o and 12.222gCo (NO ₃) ₂6H ₂o, then adds 20mL methyl alcohol and 40mL ethylene glycol, and obtains nano composite metal oxide precursor liquid with magnetic agitation 9h;

Example 9:

Step 3: accurately take 4.848gFe (NO with analytical balance ₃) ₃9H ₂o and 1.746gCo (NO ₃) ₂6H ₂o, then adds 20mL methyl alcohol and 40mL ethylene glycol, and obtains nano composite metal oxide precursor liquid with magnetic agitation 9h;

Example 10:

Step 5: the PS/ precursor liquid laminated film in step 4 is put into retort furnace, from room temperature, with 1 DEG C of min ^-1ramp to 500 DEG C, 500 DEG C insulation 1h, be then cooled to room temperature, after removing PS glue crystal template, obtain 3DOM nano Co Fe ₂o ₄skeleton;

Step 6: utilize magnetron sputtering method by the 3DOM nano Co Fe prepared by al deposition to step 5 ₂o ₄in the duct of skeleton, wherein the parameter of magnetron sputtering is: argon flow amount is 30Sccm, and sputtering power is 60W, and vacuumometer registration is 0.4Pa, and sedimentation rate is about 10nmmin ^-1; The time of aluminizing is 60min, obtains substrate and is loaded with nanometer Al/CoFe ₂o ₄the nano aluminum thermit powder of aluminothermy film.

Example 11:

Step 5: the PS/ precursor liquid laminated film in step 4 is put into retort furnace, from room temperature, with 1 DEG C of min ^-1ramp to 500 DEG C, 500 DEG C insulation 10h, be then cooled to room temperature, after removing PS glue crystal template, obtain 3DOM nano Co Fe ₂o ₄skeleton;

Example 12:

Step 5: the PS/ precursor liquid laminated film in step 4 is put into retort furnace, from room temperature, with 1 DEG C of min ^-1ramp to 500 DEG C, 500 DEG C insulation 5h, be then cooled to room temperature, after removing PS glue crystal template, obtain 3DOM nano Co Fe ₂o ₄skeleton;

Example 13:

Step 2: glass or other substrate are dipped vertically in the PS polymer microsphere dispersion liquid that step 1 prepares, the self-assembly that aligns that the curved liquid surface formed carries out PS polymer microsphere forms glue crystal template to utilize solvent to evaporate;

Example 14:

Step 6: utilize the 3DOM nano Co Fe that al deposition is prepared to step 5 by magnetron sputtering method ₂o ₄in the duct of skeleton, wherein the parameter of magnetron sputtering is: argon flow amount is 30Sccm, and sputtering power is 60W, and vacuumometer registration is 0.4Pa, and sedimentation rate is about 10nmmin ^-1; The time of aluminizing is 10min, obtains substrate and is loaded with nanometer Al/CoFe ₂o ₄the nano aluminum thermit powder of aluminothermy film.

Example 15:

Step 6: utilize the 3DOM nano Co Fe that al deposition is prepared to step 5 by magnetron sputtering method ₂o ₄in the duct of skeleton, wherein the parameter of magnetron sputtering is: argon flow amount is 30Sccm, and sputtering power is 60W, and vacuumometer registration is 0.4Pa, and sedimentation rate is about 10nmmin ^-1; The time of aluminizing is 30min, obtains substrate and is loaded with nanometer Al/CoFe ₂o ₄the nano aluminum thermit powder of aluminothermy film.

Example 16:

Step 3: accurately take 20.2gFe (NO with analytical balance ₃) ₃9H ₂o and 7.275gNi (NO ₃) ₂6H ₂o, then adds 20mL methyl alcohol and 30mL ethylene glycol, and obtains nano composite metal oxide precursor liquid with magnetic agitation 9h;

Step 4: the PS glue crystal template in step 2 is put into the precursor liquid that step 4 is prepared, takes out after soaking 3 ~ 5min, and with removing unnecessary precursor liquid, then transferring in baking oven after 50 DEG C of dry 24h, obtaining PS/ precursor liquid laminated film;

Step 5: the PS/ precursor liquid laminated film in step 4 is put into retort furnace, from room temperature, with 1 DEG C of min ^-1ramp to 600 DEG C, 600 DEG C insulation 3h, be then cooled to room temperature, after removing PS glue crystal template, obtain 3DOM nano-Ni/Fe ₂o ₄skeleton;

Step 6: utilize the 3DOM nano-Ni/Fe that al deposition is prepared to step 5 by magnetron sputtering method ₂o ₄₄in the duct of skeleton, wherein the parameter of magnetron sputtering is: argon flow amount is 30Sccm, and sputtering power is 60W, and vacuumometer registration is 0.4Pa, and sedimentation rate is about 10nmmin ^-1; The time of aluminizing is 60min, obtains substrate and is loaded with nanometer Al/CoFe ₂o ₄the nano aluminum thermit powder of aluminothermy film.

Fig. 6 is 3DOM nano-Ni/Fe in example 16 ₂o ₄the SEM figure of skeleton, as can be seen from Figure 6 3DOM nano-Ni/Fe ₂o ₄skeleton presents honeycomb reticulated structure, and PS polymer microsphere decomposes completely after high-temperature calcination, and the space between ball and ball is occupied by skeleton.In addition, skeleton pore wall thickness is about 40nm, and hole shape is approximately regular hexagon, and catercorner length is about 200nm, and total copies the perfection of PS glue crystal template.

Fig. 7 is nanometer Al/NiFe in example 16 ₂o ₄the figure of aluminothermy film SEM, similar with Fig. 4, the completely dissolve of honeycomb reticulated structure, whole skeleton cover by one deck nanometer Al, skeletal internal has loaded full nanometer Al, which ensure that oxygenant and fuel fully contacting at nanoscale, thus improves Al and NiFe ₂o ₄between the activity of thermite reaction.

Fig. 8 is nanometer Al/NiFe in example 16 ₂o ₄the DSC figure of aluminothermy film, have two exothermic peaks as we can clearly see from the figure, first exothermic peak is between 300 DEG C ~ 450 DEG C, and thermal discharge is 274.2Jg ^-1, this may be owing to there is a small amount of Ni (OH) in skeleton ₂caused by decomposition; Second exothermic peak is between 500 DEG C ~ 650 DEG C, and by integrating peak areas, thermal discharge is up to 1149Jg ^-1, therefore, the total thermal discharge of whole thermite reaction is 1423.2Jg ^-1.In addition, have an obvious endotherm(ic)peak at 660 DEG C, this melts heat absorption by aluminium and causes.

Example 17:

Step 6: utilize NiFe ₂o ₄the 3DOM nano Co Fe that al deposition is prepared to step 5 by magnetron sputtering method ₂o ₄in the duct of skeleton, wherein the parameter of magnetron sputtering is: argon flow amount is 30Sccm, and sputtering power is 60W, and vacuumometer registration is 0.4Pa, and sedimentation rate is about 10nmmin ^-1; The time of aluminizing is 60min, obtains substrate and is loaded with nanometer Al/NiFe ₂o ₄the nano aluminum thermit powder of aluminothermy film.

Example 18:

Step 5: the PS/ precursor liquid laminated film in step 4 is put into retort furnace, from room temperature, with 1 DEG C of min ^-1ramp to 600 DEG C, 600 DEG C insulation 3h, be then cooled to room temperature, after removing PS glue crystal template, obtain 3DOM nano Co Fe ₂o ₄skeleton;

Step 6: utilize magnetron sputtering magnetron sputtering method by the 3DOM nano Co Fe prepared by al deposition to step 5 ₂o ₄in the duct of skeleton, wherein the parameter of magnetron sputtering is: argon flow amount is 30Sccm, and sputtering power is 60W, and vacuumometer registration is 0.4Pa, and sedimentation rate is about 10nmmin ^-1; The time of aluminizing is 60min, obtains substrate and is loaded with nanometer Al/CoFe ₂o ₄the nano aluminum thermit powder of aluminothermy film.

Example 19:

Step 6: utilize the 3DOM nano Co Fe that al deposition is prepared to step 5 by magnetron sputtering magnetron sputtering method ₂o ₄in the duct of skeleton, wherein the parameter of magnetron sputtering is: argon flow amount is 30Sccm, and sputtering power is 60W, and vacuumometer registration is 0.4Pa, and sedimentation rate is about 10nmmin ^-1; The time of aluminizing is 60min, obtains substrate and is loaded with nanometer Al/CoFe ₂o ₄the nano aluminum thermit powder of aluminothermy film.

Example 20:

Step 1: preparation smooth surface, good dispersity, particle diameter are the PS polymer microsphere of 600nm, are then mixed with deionized water the PS polymer microsphere dispersion liquid that concentration is 1wt%;

Example 21:

Step 1: preparation smooth surface, good dispersity, particle diameter are the PS polymer microsphere of 600nm, are then mixed with deionized water the PS polymer microsphere dispersion liquid that concentration is 25wt%;

Step 6: utilize the 3DOM nano-Ni/Fe that al deposition is prepared to step 5 by magnetron sputtering magnetron sputtering method ₂o ₄in the duct of skeleton, wherein the parameter of magnetron sputtering is: argon flow amount is 30Sccm, and sputtering power is 60W, and vacuumometer registration is 0.4Pa, and sedimentation rate is about 10nmmin ^-1; The time of aluminizing is 60min, obtains substrate and is loaded with nanometer Al/NiFe ₂o ₄the nano aluminum thermit powder of aluminothermy film.

Example 22:

Example 23:

Step 3: accurately take 4.04gFe (NO with analytical balance ₃) ₃9H ₂o and 1.455gNi (NO ₃) ₂6H ₂o, then adds 20mL methyl alcohol and 30mL ethylene glycol, and obtains nano composite metal oxide precursor liquid with magnetic agitation 9h;

Example 24:

Step 3: accurately take 28.28gFe (NO with analytical balance ₃) ₃9H ₂o and 10.185gNi (NO ₃) ₂6H ₂o, then adds 20mL methyl alcohol and 30mL ethylene glycol, and obtains nano composite metal oxide precursor liquid with magnetic agitation 9h;

Example 25:

Example 26:

Step 5: the PS/ precursor liquid laminated film in step 4 is put into retort furnace, from room temperature, with 1 DEG C of min ^-1ramp to 600 DEG C, 600 DEG C insulation 1h, be then cooled to room temperature, after removing PS glue crystal template, obtain 3DOM nano-Ni/Fe ₂o ₄skeleton;

Example 27:

Step 5: the PS/ precursor liquid laminated film in step 4 is put into retort furnace, from room temperature, with 1 DEG C of min ^-1ramp to 600 DEG C, 600 DEG C insulation 10h, be then cooled to room temperature, after removing PS glue crystal template, obtain 3DOM nano-Ni/Fe ₂o ₄skeleton;

Example 28:

Example 29:

Step 6: utilize the 3DOM nano-Ni/Fe that al deposition is prepared to step 5 by magnetron sputtering magnetron sputtering method ₂o ₄in the duct of skeleton, wherein the parameter of magnetron sputtering is: argon flow amount is 30Sccm, and sputtering power is 60W, and vacuumometer registration is 0.4Pa, and sedimentation rate is about 10nmmin ^-1; The time of aluminizing is 10min, obtains substrate and is loaded with nanometer Al/NiFe ₂o ₄the nano aluminum thermit powder of aluminothermy film.

Example 30:

Step 6: utilize the 3DOM nano-Ni/Fe that al deposition is prepared to step 5 by magnetron sputtering magnetron sputtering method ₂o ₄in the duct of skeleton, wherein the parameter of magnetron sputtering is: argon flow amount is 30Sccm, and sputtering power is 60W, and vacuumometer registration is 0.4Pa, and sedimentation rate is about 10nmmin ^-1; The time of aluminizing is 30min, obtains substrate and is loaded with nanometer Al/NiFe ₂o ₄the nano aluminum thermit powder of aluminothermy film.

From above-described embodiment, the invention provides the nano aluminum thermit powder and preparation method thereof of a kind of novel structure, excellent performance, the three-dimensional ordered macroporous nano composite metal oxide aluminothermy film that energy density is high, three dimension scale is little, preparation technology is compatible mutually with MEMS manufacturing technology can be prepared in a mild condition.This three-dimensional ordered macroporous nano composite metal oxide aluminothermy film can ensure that reactant is at nanoscale close contact, thus shorten the distance of material mass transmission, improve the activity of thermite reaction, and it is low to have cost, simple to operate, foreign matter content is few, product postprocessing is convenient, environmental protection, and equipment is convenient, and security is high, preparation cycle is short, is applicable to the advantage preparing most metal oxide.

Claims

1. a nano aluminum thermit powder, comprise substrate and be attached to suprabasil nano composite metal oxide aluminothermy film, it is characterized in that, described aluminothermy film is by being formed in al deposition to nano composite metal oxide, wherein, nano composite metal oxide is CoFe ₂o ₄or NiFe ₂o ₄, nano composite metal oxide has three-dimensional ordered macroporous structure.

2. nano aluminum thermit powder as claimed in claim 1, it is characterized in that, described substrate is glass, quartz or silicon chip.

3. prepare a method for nano aluminum thermit powder as claimed in claim 1 or 2, it is characterized in that, comprise the steps:

Step 1: polystyrene polymeric microballoon is made dispersion liquid;

Step 2: substrate is dipped vertically in the dispersion liquid that step 1 prepares, forms glue crystal template;

Step 3: the glue crystal template in step 2 is placed in nano composite metal oxide precursor liquid, soaks after 3 ~ 5 minutes and takes out, obtain polystyrene/precursor liquid laminated film after drying;

Step 4: the polystyrene in step 3/precursor liquid laminated film is carried out intensification calcining, generate nano composite metal oxide after removing glue crystal template;

4. prepare the method for nano aluminum thermit powder as claimed in claim 3, it is characterized in that, in step 1, the diameter of described polystyrene polymeric microballoon is 20 ~ 600nm; The concentration of described polystyrene polymeric microballoon dispersion liquid is 1 ~ 25wt%.

5. prepare the method for nano aluminum thermit powder as claimed in claim 3, it is characterized in that, in step 3, nano composite metal oxide precursor liquid is CoFe ₂o ₄precursor liquid, CoFe ₂o ₄precursor liquid is by Fe (NO ₃) ₃9H ₂o and Co (NO ₃) ₂6H ₂o is dissolved in the mixed solvent of methyl alcohol and ethylene glycol obtained after stirring and dissolving; Wherein, the volume ratio of methyl alcohol, ethylene glycol is 1: 2; Fe (NO ₃) ₃9H ₂o, Co (NO ₃) ₂6H ₂the mol ratio of O is 2: 1; Fe (NO ₃) ₃9H ₂the addition of O is 0.08 ~ 0.57 times of methyl alcohol and ethylene glycol mixed solvent quality; Co (NO ₃) ₂6H ₂o adds 0.02 ~ 0.21 times that quality is methyl alcohol and ethylene glycol mixed solvent quality.

6. prepare the method for nano aluminum thermit powder as claimed in claim 3, it is characterized in that, in step 3, nano composite metal oxide precursor liquid is NiFe ₂o ₄precursor liquid, NiFe ₂o ₄precursor liquid is by Fe (NO ₃) ₃9H ₂o and Ni (NO ₃) ₂6H ₂o is dissolved in the mixed solvent of methyl alcohol and ethylene glycol obtained after stirring and dissolving; Wherein, the volume ratio of methyl alcohol, ethylene glycol is 2: 3; Fe (NO ₃) ₃9H ₂o, Ni (NO ₃) ₂6H ₂the mol ratio of O is 2: 1; Fe (NO ₃) ₃9H ₂the addition of O is 0.08 ~ 0.57 times of methyl alcohol and ethylene glycol mixed solvent quality; Ni (NO ₃) ₂6H ₂o adds 0.02 ~ 0.21 times that quality is methyl alcohol and ethylene glycol mixed solvent quality.

7. prepare the method for nano aluminum thermit powder as claimed in claim 3, it is characterized in that, in step 4, the parameter of the calcining that heats up is: from room temperature, with 1 DEG C of min ^-1ramp to 500 DEG C ~ 600 DEG C, be incubated 1 ~ 10 hour, be then cooled to room temperature.

8. prepare the method for nano aluminum thermit powder as claimed in claim 3, it is characterized in that, in step 5, deposition of aluminum adopts magnetron sputtering method, and its parameter is: argon flow amount is 30Sccm, and sputtering power is 60W, and vacuumometer registration is 0.4Pa, and sedimentation rate is about 10nmmin ^-1; The time of aluminizing is 10 ~ 60min.