CN109678630B - Preparation method of Al/NiO flaky thermite - Google Patents

Preparation method of Al/NiO flaky thermite Download PDF

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CN109678630B
CN109678630B CN201910021708.8A CN201910021708A CN109678630B CN 109678630 B CN109678630 B CN 109678630B CN 201910021708 A CN201910021708 A CN 201910021708A CN 109678630 B CN109678630 B CN 109678630B
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nio
substrate
flaky
sheet
precursor
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CN109678630A (en
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黎学明
郭晓刚
王琪辉
王雅丽
陶志
徐鹏
陈金
杨晟博
何苗
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Chongqing University
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    • C—CHEMISTRY; METALLURGY
    • C06—EXPLOSIVES; MATCHES
    • C06B—EXPLOSIVES OR THERMIC COMPOSITIONS; MANUFACTURE THEREOF; USE OF SINGLE SUBSTANCES AS EXPLOSIVES
    • C06B33/00—Compositions containing particulate metal, alloy, boron, silicon, selenium or tellurium with at least one oxygen supplying material which is either a metal oxide or a salt, organic or inorganic, capable of yielding a metal oxide
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides

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  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The preparation method of the Al/NiO flaky thermite comprises the following steps: providing a sheet-form peelable metal substrate; preparing a hydro-thermal synthesis reaction solution; performing a hydrothermal synthesis reaction to obtain a precursor on a substrate; roasting the precursor to form a NiO sheet layer on the substrate; and finally, carrying out magnetron sputtering on the NiO layer to form a nano aluminum film, thereby obtaining the flaky Al/NiO nano energetic material composite film. The thermite is convenient to store and carry, low in production cost, environment-friendly and excellent in combustion heat release performance.

Description

Preparation method of Al/NiO flaky thermite
Technical Field
The invention relates to a preparation method of a nano energetic material composite film.
Background
The traditional thermit is only prepared by simply mixing aluminum powder and metal oxide, so that the thermit surface reaction rate is slow, the ignition temperature is high, the actual heat release is low, and the requirements of military and other special industries on higher requirements are difficult to meet. Although some existing laboratory thermite preparation methods are improved in many aspects, the existing laboratory thermite preparation methods are still unsatisfactory in aspects of mass transfer rate, process design, environmental friendliness, use convenience, industrial production and the like of thermite reaction.
Disclosure of Invention
The invention aims to provide a thermite with better performance.
According to a first aspect of the invention, a preparation method of an Al/NiO flaky thermite is provided, which comprises the following steps:
providing a sheet metal substrate;
mixing nickel sulfate and sodium hydroxide according to a molar ratio of about 1:2 to form a mixed solution;
regulating the pH value of the mixed solution to 5-9 by using sulfuric acid;
the mixed solution after the pH value is adjusted is displaced into a reaction kettle;
then putting a substrate into the reaction kettle;
keeping the temperature of the reaction kettle at 150-260 ℃ and reacting for 12-24 h, so as to form a (light green) precursor on the substrate;
taking out the substrate attached with the precursor, and respectively carrying out ultrasonic cleaning on the precursor by using distilled water and ethanol;
roasting the cleaned precursor to form a NiO sheet layer on the substrate, wherein the roasting temperature is 300-400 ℃, and the roasting time is 2 hours;
then cooling the NiO sheet layer formed on the substrate to room temperature;
and finally, carrying out magnetron sputtering on the NiO layer to form a nano aluminum film, thereby obtaining the flaky Al/NiO nano energetic material composite film.
The method according to the invention may further comprise: and carrying out vacuum drying and cooling on the obtained flaky Al/NiO nano energetic material composite film. Thereafter, the method may further include: and removing or stripping the metal substrate from the obtained flaky Al/NiO nano energetic material composite film.
The method according to the invention may further comprise: 1, 4-butynediol and polyethylene glycol (PEG) are added into a mixed solution formed by nickel sulfate and sodium hydroxide, wherein the molar ratio of the 1, 4-butynediol to the PEG is about 1:1, and the molar ratio of the 1, 4-butynediol to the nickel sulfate is about 1: 2000. In the invention, 1, 4-butynediol is helpful to improve compactness and brightness, and polyethylene glycol realizes the generation of flaky NiO by improving the surface charge condition.
In the present invention, PEG2000 is preferably used.
According to the invention, the magnetron sputtering parameters are preferably: negative bias voltage 1.6 x 103V, the inter-polar distance is 0.07m, and the pressure of protective gas (argon) is 0.70 Pa; the sputtering plating time is 0.2-0.5 h.
According to the present invention, the metal substrate may be a Ti sheet, a Cu sheet, a stainless steel sheet, or a Ni sheet, and preferably a Ni sheet is used.
According to a second aspect of the present invention, there is provided a thermite, prepared by the above method.
The invention simplifies the collection work of the precursor and facilitates the subsequent processing and storage by using the metal substrate.
The sheet metal base of the present invention is preferably further provided with a break line to form a suitably sized sheet region to facilitate subsequent peeling of the metal base. Furthermore, only the required number of sections may be peeled off (e.g. by performing a simple snapping action along the break line) as required, thereby facilitating storage and carrying of the remaining thermite.
The invention also has at least the following advantages:
the Al/NiO flaky thermite nano energetic material composite film prepared by the invention has uniform surface distribution, greatly improves the contact area and uniformity of aluminum powder and oxide, and hardly has agglomeration phenomenon;
the Al/NiO flaky thermite nano energetic material composite film prepared by the invention has good exothermic property and combustion property;
the method has the advantages of simple operation, low preparation cost and high film forming speed, and is very suitable for industrial production; and
the method has the advantages of simple process, environmental friendliness and great advantages in industrial mass production application.
Drawings
FIG. 1 is a schematic illustration of a metal substrate provided in accordance with the present invention;
FIGS. 2(a) and 2(b) are a scanning electron micrograph and a transmission electron micrograph, respectively, of an Al/NiO flaky thermite prepared according to the present invention;
FIG. 3 is a DSC exotherm for Al/NiO flake thermites made according to the present invention; and
FIG. 4 is a combustion flame diagram of Al/NiO flake thermites made in accordance with the present invention.
Detailed Description
The invention is further illustrated by the following examples. It will be appreciated by those skilled in the art that the following examples are only for better understanding and realization of the present invention, and are not intended to limit the present invention.
As shown in FIG. 1, the present invention begins by providing a sheet substrate 10, such as a nickel sheet, of suitable size. The substrate 10 is provided or formed with break lines 11 and 12 to facilitate a subsequent peeling operation.
The invention prepares a hydrothermal synthesis reaction solution as follows: mixing nickel sulfate and sodium hydroxide in a molar ratio of 1:2 to form a mixed solution, and then adding 1, 4-butynediol and polyethylene glycol (PEG), wherein the molar ratio of 1, 4-butynediol to PEG is 1:1, and the molar ratio of 1, 4-butynediol to nickel sulfate is 1: 2000; then, the pH value of the mixed solution is properly adjusted by using sulfuric acid.
The reaction liquid or mixed liquid after the configuration is then displaced into a hydrothermal synthesis reaction kettle (not specifically shown), and the substrate 10 is also placed in the reaction kettle. The hydrothermal reaction temperature is kept at 150-260 ℃, and the reaction time is 12-24 hours until a light green precursor is attached to the substrate 10.
Then, the substrate 10 to which the precursor is attached is taken out, and the precursor is ultrasonically cleaned using distilled water and ethanol, respectively.
And then roasting the precursor to form a NiO sheet layer on the substrate 10, wherein the roasting temperature is 300-700 ℃, and the roasting time is 2 hours.
The NiO lamellae formed on substrate 10 were then cooled to room temperature. Performing a rapid cooling, for example, at least 50 ℃ per minute, will significantly reduce the bonding force of the thermite material to the substrate 10 and thus greatly facilitate subsequent peeling of the substrate 10.
Then, magnetron sputtering is carried out on the NiO layer to obtain the flaky Al/NiO nano energetic materialAnd (3) compounding the film. The magnetron sputtering parameters are as follows: negative bias voltage 1.6 x 103V, the inter-polar distance is 0.07m, and the pressure of protective gas (argon) is 0.70 Pa; the sputtering plating time is 0.2-0.5 h.
And then carrying out vacuum drying and cooling on the obtained flaky Al/NiO nano energetic material composite film. The substrate 10 may then be removed or peeled from the resulting laminar Al/NiO nanoenergetic composite film. For example, the upper right quarter shown in fig. 1 is broken off along the fracture lines 11 and 12, and the substrate attached thereto is peeled off.
The invention uses a Field Emission Scanning Electron Microscope (FESEM), a Differential Scanning Calorimeter (DSC), a high-speed camera and the like to research, analyze, characterize and analyze the surface appearance and the performance of the composite film product.
Example 1
PEG2000 is used as PEG; the hydrothermal reaction temperature is kept at 160 ℃, the reaction time is 12 hours, and the pH is adjusted to 7; the roasting temperature is 350 ℃; the sputter coating time was 0.2 h.
The surface appearance and performance of the composite film product are researched, analyzed and characterized by using a Field Emission Scanning Electron Microscope (FESEM), a Differential Scanning Calorimeter (DSC), a high-speed camera and the like. FIGS. 2(a) and 2(b) are a scanning electron micrograph and a transmission electron micrograph, respectively, of an Al/NiO flaky thermite prepared according to example 1; FIG. 3 is a corresponding DSC exotherm with an exotherm up to 1.5MJ Kg-1(ii) a FIG. 4 is a combustion flame diagram of the thermite.
Comparative example 2
Otherwise, in the same way as in example 1, PEG1000 was used instead of the surfactant, and compared with example 1, NiO obtained by the preparation method is irregular and uneven, and the later preparation of the novel flaky thermite Al/NiO with uniform distribution cannot be realized.
Comparative example 3
Otherwise, as in example 1, the pH was adjusted to 5. Compared with example 1, the thickness of the prepared Al/NiO flaky thermite is slightly reduced, and the heat release of the flaky thermite is slightly reduced to about 1.43MJ Kg-1。
Comparative example 4
Otherwise, as in example 1, the hydrothermal reaction temperature was maintained at 140 ℃. Compared with the example 1, the prepared Al/NiO flaky thermite has poor uniformity and blocked heat release, and at the moment, the heat release amount of the flaky thermite is greatly reduced, and the heat release time is greatly delayed.
Comparative example 5
Otherwise as in example 1, the calcination temperature was raised to 450 ℃. Compared with example 1, the exothermic amount of the flaky thermite is about 85% of that of the sample in example 1, and in addition, the prepared Al/NiO flaky thermite has the defects of cracking phenomenon, unstable structure and difficult practical use.
Comparative example 6
Otherwise, as in example 1, the magnetron sputtering time was halved. Compared with example 1, the flaky thermite has larger deviation of the stoichiometric ratio of the component reactive substances from the molar ratio of the actual thermite reaction, so that larger surplus and waste of NiO in the sample occur, and the energy output capacity of the sample is greatly reduced to about 45 percent of that of the sample of example 1.
As mentioned above, the method adopts the combination of the NiO precursor hydrothermally synthesized on the strippable substrate and the magnetron sputtering nano aluminum film, so that the flaky Al/NiO nano energetic material composite film with excellent performance is obtained.

Claims (4)

1. A preparation method of an Al/NiO flaky thermite comprises the following steps:
providing a sheet metal substrate;
mixing nickel sulfate and sodium hydroxide in a molar ratio of 1:2 to form a mixed solution;
adding 1, 4-butynediol and polyethylene glycol PEG2000 into a mixed solution formed by nickel sulfate and sodium hydroxide, wherein the molar ratio of the 1, 4-butynediol to the polyethylene glycol PEG2000 is 1:1, the molar ratio of the 1, 4-butynediol to the nickel sulfate is 1:2000,
regulating the pH value of the mixed solution to 7 by using sulfuric acid;
the mixed solution after the pH value is adjusted is displaced into a reaction kettle;
then putting a substrate into the reaction kettle;
keeping the temperature of the reaction kettle at 160 ℃, and reacting for 12h, so as to attach and form a precursor on the substrate;
taking out the substrate attached with the precursor, and respectively carrying out ultrasonic cleaning on the precursor by using distilled water and ethanol;
roasting the cleaned precursor to form a NiO sheet layer on the substrate, wherein the roasting temperature is 350 ℃, and the roasting time is 2 hours;
then cooling the NiO sheet layer formed on the substrate to room temperature;
and finally, carrying out magnetron sputtering on the NiO sheet layer for 0.2h to obtain the flaky Al/NiO nano energetic material composite film.
2. The method of claim 1, further comprising: and carrying out vacuum drying and cooling on the obtained flaky Al/NiO nano energetic material composite film.
3. The method of claim 2, further comprising: and removing or stripping the metal substrate from the obtained flaky Al/NiO nano energetic material composite film.
4. The method of claim 1, wherein the metal substrate is a Ti sheet, a Cu sheet, a stainless steel sheet, or a Ni sheet.
CN201910021708.8A 2019-01-10 2019-01-10 Preparation method of Al/NiO flaky thermite Active CN109678630B (en)

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CN110357758B (en) * 2019-08-08 2021-07-27 哈尔滨工业大学 Reticular porous NiO/Al nano energetic material and preparation method thereof
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101657553A (en) * 2007-02-14 2010-02-24 表面处理技术公司 The heat deposition of active metal oxide/aluminium lamination and the aluminide of dispersion-strengthened prepared therefrom
CN105016935A (en) * 2014-01-29 2015-11-04 香港城市大学 Structure of energetic materials and the method for preparing thereof

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US9481614B2 (en) * 2013-10-10 2016-11-01 Battelle Energy Alliance, Llc Energetic materials and methods of tailoring electrostatic discharge sensitivity of energetic materials

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101657553A (en) * 2007-02-14 2010-02-24 表面处理技术公司 The heat deposition of active metal oxide/aluminium lamination and the aluminide of dispersion-strengthened prepared therefrom
CN105016935A (en) * 2014-01-29 2015-11-04 香港城市大学 Structure of energetic materials and the method for preparing thereof

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