Energetic thin film material and manufacturing method thereof

Abstract

The invention relates to the field of energetic materials, in particular to an energetic thin film material which comprises a first layer (1) containing an A elementary substance and a second layer (2) containing a B elementary substance, the A elementary substance and the B elementary substance can generate an exothermic reaction, and the first layer (1) and the second layer (2) are alternately stacked to form at least most of a multi-layer modulation structure. The multi-layer modulation structure further comprises an energy storage component, after the exothermic reaction is initiated, the energy storage component absorbs and stores part of heat generated by the exothermic reaction, and after the exothermic reaction is finished, the energy storage component releases the stored heat. According to the energy-containing thin film material, on the premise that the overall heat release amount is not affected, the heat release temperature of the energy-containing thin film material can be regulated and controlled, and therefore heat damage, such as ablation damage, caused by the heat release reaction of the energy-containing thin film material to a heated object is avoided.

Description

Technical Field

[0001] The embodiments of the present application relate to the field of energetic materials, and specifically to an energetic thin film material and a method for manufacturing the same. Background Art

[0002] The energetic thin film material is usually formed by two or more materials A and B that are chemically reactive with each other and has a multilayer modulation structure, which has extremely high reactivity and exothermic characteristics. Under the induction of external energy, the energetic thin film material can undergo a self-propagating exothermic reaction and instantly generate a high amount of heat, thereby meeting the application requirements of different scenarios. It is an excellent material for fuze thermal batteries and a brazing heat source energetic material. Such a combination of material A and material B can be, for example, a Ni-Al combination, a Ti-Al combination, etc.

[0003] However, the exothermic temperature of the film cannot be regulated, and the excessively high temperature caused by the released heat may cause ablation damage to the heated object (e.g., the workpiece to be welded in a welding scenario) in the thermal field formed by the energetic film material. Summary of the invention

[0004] The object of the present application is to provide an improved energetic thin film material which can reduce the prior art.

[0005] According to the first aspect of the present application, there is provided an energy-containing thin film material, comprising a first layer containing a single substance A and a second layer containing a single substance B, wherein single substance A and single substance B can undergo an exothermic reaction, and the first layer and the second layer are alternately stacked to form at least a portion of a multilayer modulation structure, wherein the multilayer modulation structure further comprises an energy storage component, after the exothermic reaction is initiated, the energy storage component absorbs and stores part of the heat generated by the exothermic reaction, and after the exothermic reaction ends, the energy storage component releases the stored heat.

[0006] According to an optional embodiment of the present application, the energy storage component includes or is elemental A or elemental B; or the energy storage component includes or is an elemental metal or compound that does not react with elemental A or elemental B.

[0007] According to an optional embodiment of the present application, the energy storage component is designed to absorb heat through a melting process during the exothermic reaction and release heat through a solidification process after the exothermic reaction ends; or the energy storage component is designed to absorb heat through a heating process during the exothermic reaction and release heat through a cooling process after the exothermic reaction ends.

[0008] According to an optional embodiment of the present application, the energy storage component is formed as a continuous layer sandwiched between a first layer containing element A and a second layer containing element B in the multi-layer modulation structure.

[0009] According to an optional embodiment of the present application, the continuous layer of the energy storage component is the same in composition and structure as the first layer containing element A or the second layer containing element B.

[0010] According to an optional embodiment of the present application, the continuous layer of the energy storage component is located in at least one of the middle region, the top region and the bottom region of the multi-layer modulation structure along the thickness direction.

[0011] According to an optional embodiment of the present application, the multi-layer modulation structure includes at least one continuous layer of the energy storage component.

[0012] According to an optional embodiment of the present application, the continuous layer of the energy storage component has a thickness in the range of 500 nm to 5000 nm.

[0013] According to an optional embodiment of the present application, element A and element B can undergo an exothermic reaction to generate an intermetallic compound.

[0014] According to an optional embodiment of the present application, A is Ni, Ti, Fe or Pt, and B is Al; or A is Ti or Nb, and B is Si.

[0015] According to an optional embodiment of the present application, the thickness of the first layer and the second layer are both on the nanometer scale.

[0016] According to an optional embodiment of the present application, the thickness of the first layer is 10 nm to 200 nm, and / or the thickness of the second layer is 10 nm to 200 nm.

[0017] According to an optional embodiment of the present application, the energetic thin film material is made by a physical vapor deposition process, in particular, magnetron sputtering, arc ion plating, electron beam physical vapor deposition or thermal evaporation process.

[0018] According to a second aspect of the present application, a method for manufacturing an energetic thin film material according to the present application is provided, comprising:

[0019] - Step 1: installing the workpiece into a device, wherein the device comprises a first target source for providing element A and a second target source for providing element B,

[0020] - Step 2: adjusting the workpiece to a first working position, in which the surface of the workpiece to be deposited faces the first target source,

[0021] - Step 3: energizing the first target source to deposit the first layer,

[0022] - Step 4: adjusting the workpiece to a second working position, in which the surface to be deposited of the workpiece faces a second target source,

[0023] - Step 5: energizing the second target source to deposit the second layer,

[0024] - Step 6: Repeat steps 2 to 5 for multiple times to form a multi-layer modulation structure of the energetic thin film material.

[0025] According to an optional embodiment of the present application, in step 3 and step 5, the method includes regulating working parameters of the first target source and the second target source and / or a position of the workpiece relative to the first target source and the second target source.

[0026] According to an optional embodiment of the present application, during the rotation of the workpiece, the first layer, the second layer and the energy storage component are continuously deposited and formed, and the energy storage component is specifically deposited and formed as a continuous layer.

[0027] According to an optional embodiment of the present application, during the manufacturing process of the energetic thin film material, the workpiece rotates continuously without interruption.

[0028] The energetic thin film material according to the present application can realize the regulation of the exothermic temperature of the energetic thin film material without affecting the overall heat release, thereby preventing the exothermic reaction of the energetic thin film material from causing thermal damage to the heated object, such as ablation damage. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The present invention will be described in more detail below with reference to the accompanying drawings, so that the principles, features and advantages of the present invention can be better understood. In the accompanying drawings:

[0030] Figure 1 A schematic diagram showing a multilayer modulation structure of an energetic thin film material according to an exemplary embodiment of the present application is shown;

[0031] Figure 2 A schematic diagram showing a multilayer modulation structure of an energetic thin film material according to another exemplary embodiment of the present application is shown;

[0032] Figure 3 A schematic diagram showing a multilayer modulation structure of an energetic thin film material according to another exemplary embodiment of the present application is shown;

[0033] Figure 4 A schematic diagram of an apparatus for manufacturing an energetic thin film material according to the present application is shown;

[0034] Figure 5 A microstructure diagram of an energetic thin film material according to a specific example of the present application is shown; and

[0035] Figure 6 for Figure 5 DSC curve of reaction heat test of an example of energetic thin film material shown in . DETAILED DESCRIPTION

[0036] In order to make the technical problems, technical solutions and beneficial technical effects to be solved by the present application clearer, the present application will be further described in detail below in conjunction with the accompanying drawings and multiple exemplary embodiments. It should be understood that the specific embodiments described herein are only used to explain the principles of the present application, rather than to limit the scope of protection of the present application.

[0037] In the various figures of the present application, features with the same structure or similar functions are represented by the same reference numerals.

[0038] like Figure 1 to Figure 3 As shown, the energetic thin film material according to the present application includes a first layer 1 containing a single substance A and a second layer 2 containing a single substance B, and the first layer 1 and the second layer 2 are alternately stacked to form at least a portion of a multilayer modulation structure. Here, the single substance A and the single substance B can undergo an exothermic reaction. In particular, the single substance A and the single substance B can undergo an exothermic reaction to generate an intermetallic compound.

[0039] According to some optional embodiments, the energetic thin film material based on A element and B element can be an aluminum-based energetic thin film material. In this case, Al-containing compounds, in particular Al-containing intermetallic compounds, can be formed by Al and an element capable of exothermic reaction with Al, in particular a metal, more particularly a transition metal. For example, in some embodiments, B element can be Al, and A element can be Ni, Ti, Fe or Pt. Alternatively, in addition to aluminum-based energetic thin film materials, it can also be implemented as a silicon-based energetic thin film material. For example, in some embodiments, B element can be Si, in which case A element can be Ti or Nb.

[0040] It is worth noting that the atomic ratio of A and B in the compound formed by the exothermic reaction of element A and element B, especially the intermetallic compound, is not limited and can be a single value or a value within a specific range.

[0041] The energy-containing thin film material according to the present application is characterized in that the multilayer modulation structure also includes an energy storage component. After the exothermic reaction is initiated, the energy storage component absorbs and stores part of the heat generated by the exothermic reaction, and after the exothermic reaction ends, the energy storage component releases the stored heat.

[0042] By introducing the energy storage component, part of the heat released in the early stage of the exothermic reaction can be stored, thereby reducing the ambient temperature increment caused by the released heat, that is, the highest temperature in the exothermic process is reduced, so that the temperature rise of the heated object in the thermal field formed by the energetic film material is limited, and part of the stored heat can be released again after the end of the exothermic reaction, so that the total heat released by the triggered energetic film material can be basically the same as that of the existing energetic film material without the introduction of the energy storage component. In this way, it can be ensured that the temperature rise of the heated object during the exothermic reaction will not cause ablation damage to it, and the heat release capacity of the energetic film material can be maintained to maintain functional effectiveness, so that the heat release temperature of the energetic film material can be regulated without affecting the overall heat release.

[0043] Optionally, in some embodiments, the energy storage component may include either element A or element B. This can simplify the composition of the energetic thin film material without introducing other additional components, and therefore there is no need to worry that other additional components may have a negative impact on the overall performance of the material.

[0044] Specifically, after the exothermic reaction is triggered, the A and B elements in the multilayer modulation structure of the energetic film material react to release heat and generate an AB compound that meets the stoichiometric ratio of the components; while the excess A or B elements that do not participate in the exothermic reaction remain in a single state, and will absorb heat during the exothermic process and increase in temperature, and in some cases melt, thereby absorbing heat. After the exothermic reaction ends, the B element with a temperature rise or melt state will cool down or solidify accordingly, thereby releasing heat.

[0045] Alternatively, in some embodiments, the energy storage component may include or be a single metal or compound that does not react with the A element or the B element.

[0046] Alternatively, the energy storage component can be designed to absorb heat through a melting process during the exothermic reaction and release heat through a solidification process after the exothermic reaction ends, thereby achieving corresponding heat absorption and release through a reversible melting-solidification process, which will involve a change in the morphology of the energy storage component. For example, the energy storage component can be a low melting point component, and after absorbing heat, a melting phase change occurs, thereby achieving phase change energy storage.

[0047] Alternatively, the energy storage component can also be designed to absorb heat by heating during the exothermic reaction and release heat by cooling after the exothermic reaction, thereby achieving the corresponding heat absorption and release through the reversible process of heating and cooling, during which the energy storage component does not undergo phase change. For example, the energy storage component can be a high melting point component.

[0048] The energy storage component may be dispersed in the form of phases at any position in the multilayer modulation structure, for example, dispersed in the first layer 1 , in the second layer 2 , and / or at the interface between the first layer 1 and the second layer 2 .

[0049] However, optionally and preferably, the energy storage component can be formed as a continuous layer 3 sandwiched between the first layer 1 containing the A element and the second layer 2 containing the B element in the multilayer modulation structure. In this way, it is possible to allow the preparation of the continuous layer 3 to be achieved while depositing the first layer 1 and the second layer 2. Here, the "continuous" in the continuous layer 3 means that the layer formed by the energy storage component is a layer that is stacked together with the first layer 1 and the second layer 2, thereby extending within the radial extension range of the first layer 1 and the second layer 2.

[0050] Furthermore, the continuous layer 3 of the energy storage component is the same in composition and structure as the first layer 1 containing element A or the second layer 2 containing element B. In this way, the energetic thin film material according to the present application can be conveniently manufactured by increasing the thickness of the specific first layer 1 or the specific second layer 2.

[0051] Additionally or alternatively, the continuous layer 3 of the energy storage component is located at least one of the middle region, the top region and the bottom region of the multilayer modulation structure in the thickness direction.The multilayer modulation structure may also include at least one continuous layer 3 of the energy storage component. Figure 1 A continuous layer 3 of an energy storage component is shown in the middle region of the multilayered tuning structure, Figure 2 A continuous layer 3 is shown in the bottom region, while Figure 3 Two continuous layers 3 located in the middle area and the bottom area are shown. That is, the energetic thin film material according to the present application may include at least one continuous layer 3, and its position in the multi-layer modulation structure is flexibly adjustable.

[0052] Additionally or alternatively, the continuous layer 3 of the energy storage component has a thickness in the range of 500 nm to 5000 nm. In case there are a plurality of continuous layers 3, each continuous layer 3 may have a different thickness.

[0053] Optionally, the thickness of the first layer 1 and the second layer 2 can both be on the nanometer scale, so that a nano energetic thin film material can be formed. In particular, in some embodiments, the thickness of the first layer 1 can be 10nm to 200nm. Alternatively or additionally, the thickness of the second layer 2 can also be 10nm to 200nm.

[0054] Optionally, the energetic thin film material according to the present application can be made by a physical vapor deposition process, in particular magnetron sputtering, arc ion plating, electron beam physical vapor deposition or thermal evaporation process.

[0055] The present application also provides a method for manufacturing the above-mentioned energetic thin film material. Figure 4 The method is described with reference to a schematic diagram of an apparatus 100 for manufacturing an energetic thin film material according to the present application.

[0056] It is worth mentioning that Figure 4 Only a portion of the device 100 is shown highly schematically, while other relevant components of the deposition device known to those skilled in the art are omitted, such as a working cabin with a vacuum chamber and a gas supply system included in the device 100.

[0057] like Figure 4 As shown, the device 100 may include a first target source 101 for providing an A element and a second target source 102 for providing a B element. Here, the first target source 101 and the second target source 102 are arranged on both sides of the device 100 relative to each other, but are not limited thereto. The first target source 101 and the second target source 102 may be arranged at different positions of the device 100 according to actual design requirements. To this end, in some embodiments, corresponding mounting positions for receiving the first target source 101 and the second target source 102 may be provided on the working cabin of the device 100. During operation, the workpiece 200, in particular the surface to be deposited of the workpiece 200, may be moved to a first working position corresponding to the first target source 101 or a second working position corresponding to the second target source 102, for example, by a controller or an additional motion actuator, so as to deposit a first layer containing an A element or a second layer containing a B element accordingly. Here, the movement of the workpiece 200, in particular the surface to be deposited of the workpiece 200, to the first working position or the second working position may be a translational movement, a rotational movement, or a combination thereof.

[0058] Optionally, in some embodiments, the workpiece 200 may be Figure 4 The support structure 210 shown is installed in the deposition device 100. The support structure 210 can be controlled by the controller of the device 100 to drive the workpiece 200 to move, so as to move the workpiece 200, especially the surface to be deposited of the workpiece 200, to the first working position or the second working position. In particular, the support structure 210 can rotate around the rotation axis R, so that the workpiece 200 can also rotate around the rotation axis R and switch between the first working position and the second working position.

[0059] In such Figure 4 In the preferred embodiment shown, the first target source 101 and the second target source 102 are arranged opposite to each other on both sides of the device 100, and the workpiece 200 switches the working position by turning 180° around the rotation axis R. This realizes particularly convenient continuous deposition.

[0060] The method for manufacturing the above-mentioned energetic thin film material according to the present application may include:

[0061] Step 1: Install the workpiece 200 into the deposition device 100,

[0062] Step 2: Adjust the workpiece 200 to a first working position, where the surface to be deposited of the workpiece 200 faces the first target source 101.

[0063] Step 3: Excite the first target source 101 to deposit the first layer 1,

[0064] Step 4: Adjust the workpiece 200 to a second working position, where the surface to be deposited of the workpiece 200 faces the second target source 102.

[0065] Step 5: Excite the second target source 102 to deposit the second layer 2,

[0066] Step 6: Repeat steps 2 to 5 for multiple times to form an energetic thin film material having a multi-layer modulation structure.

[0067] In a specific embodiment, Figure 4 As shown, the first target source 101 and the second target source 102 are arranged on both sides of the workpiece 200 relative to the rotation axis R of the workpiece 200, the surface to be deposited of the workpiece 200 is adjusted to a first working position facing the first target source 101, the first target source 101 is excited to deposit the first layer 1, and then the surface to be deposited of the workpiece 200 is adjusted to a second working position facing the second target source 102, the second target source 102 is excited to deposit the second layer 2.

[0068] In step 3 and step 5, the deposition of the first layer 1 and the second layer 2 is realized accordingly by adjusting the working parameters of the first target source 101 and the second target source 102 and / or the position of the workpiece 200 relative to the first target source 101 and the second target source 102. Here, the working parameters of the first target source 101 and the second target source 102 may include power and opening and closing time, etc., and the position of the workpiece 200 relative to the first target source 101 and the second target source 102 may include at least one of position and posture, and optionally include the rotation speed and angle of the workpiece 200.

[0069] Optionally, during the rotation of the workpiece 200, the first layer 1, the second layer 2 and the energy storage component are continuously deposited. In this way, the overall deposition of the energetic thin film material can be achieved, which can not only facilitate manufacturing, but also improve the connectivity between the layers inside the material, thereby facilitating the overall performance of the energetic thin film material. In particular, the energy storage component can be deposited to form a continuous layer 3. Additionally or alternatively, during the manufacturing process of the energetic thin film material, the workpiece 200 is continuously rotated without interruption. Here, it should be understood that the interface between any two of the first layer 1, the second layer 2 and the continuous layer 3 can be a transition region, in which the content of the corresponding elements can be variable.

[0070] Figure 5 The microstructure diagram of an energetic thin film material according to a specific example of the present application is shown, wherein (b) is a partial enlarged diagram of (a), (c) is a partial enlarged diagram of (b), and (d) is a scale measurement diagram. In this example, element A is Ni and element B is Al. Figure 5 As can be seen from the figure, in this example, the modulation period of the multilayer modulation structure is about 110nm, which is similar in structure to Figure 2 The schematic structure shown in FIG. 1 is that the continuous layer is located at the bottom, that is, during the preparation process, an Al layer of a certain thickness is first deposited as a substrate, and the Al layer is used as the (continuous layer of) the energy storage component in the energetic thin film material according to the present application.

[0071] Figure 6 for Figure 5 The DSC curve of the reaction heat test of the Ni / Al-based energetic thin film material example shown in FIG, wherein the abscissa is temperature and the ordinate is heat flow. Figure 6 It can be seen that the total reaction heat release of this example is 802.2 J / g, and the initial reaction temperature is 207°C, which proves that it has good activity. In addition, the DSC curve has a "double peak" feature, in which the first exothermic process (heat release of about 605.6 J / g) shows that the Al layer as the substrate absorbs and stores part of the reaction heat by endothermic melting, and the second exothermic process (heat release of about 196.6 J / g) shows that after the exothermic reaction, the melted Al substrate layer undergoes exothermic solidification, thereby releasing the stored energy again, making the final total reaction heat roughly the same as that of the energetic thin film material without the introduction of the substrate Al layer (whose DSC curve has a "single peak" feature). In the first exothermic process, the two sub-peaks at about 228°C and about 283°C correspond to the generation of different compounds.

[0072] It is worth noting that in the meaning of this application, element A or element B refers to a substance formed by a deposition process from a corresponding deposition source, which allows the presence of a small amount or trace amount of other substances (such as impurities, etc.) in the corresponding layer, for example due to process reasons.

[0073] It should be understood that, in this document, the expressions "first", "second", etc. are used for descriptive purposes only and should not be understood as indicating or implying relative importance, nor should they be understood as implicitly indicating the number of technical features indicated. Features defined as "first" or "second" may explicitly or implicitly indicate that at least one of the features is included.

[0074] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present application. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or N embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0075] Although the specific embodiments of the present application are described in detail herein, they are provided for the purpose of explanation only and should not be considered to limit the scope of the present application. Various substitutions, changes and modifications may be conceived without departing from the spirit and scope of the present application.

Claims

1. An energetic thin film material, comprising a first layer (1) containing a single substance A and a second layer (2) containing a single substance B, wherein: The A element and the B element are capable of exothermic reaction, and the first layer (1) and the second layer (2) are alternately stacked to form at least a portion of the multilayer modulation structure, characterized in that: The multi-layer modulation structure further includes an energy storage component. After the exothermic reaction is initiated, the energy storage component absorbs and stores part of the heat generated by the exothermic reaction, and after the exothermic reaction ends, the energy storage component releases the stored heat.

2. The energetic thin film material according to claim 1, wherein: The energy storage component includes either A element or B element; or The energy storage component includes or is a single metal or compound that does not react with the A single substance or the B single substance.

3. The energetic thin film material according to claim 1 or 2, wherein: The energy storage component is designed to absorb heat through a melting process during the exothermic reaction and release heat through a solidification process after the exothermic reaction ends; or The energy storage component is designed to absorb heat through a temperature increase process during the exothermic reaction and release heat through a temperature decrease process after the exothermic reaction ends.

4. The energetic thin film material according to any one of claims 1 to 3, wherein: The energy storage component is formed as a continuous layer (3) sandwiched between a first layer (1) containing an A element and a second layer (2) containing a B element in the multi-layer modulation structure.

5. The energetic thin film material according to claim 4, wherein: The continuous layer (3) of the energy storage component is identical in composition and structure to the first layer (1) containing the A element or the second layer (2) containing the B element; and / or The continuous layer (3) of the energy storage component is located in at least one of the middle region, the top region and the bottom region of the multilayer modulation structure in the thickness direction; and / or The multilayer modulation structure comprises at least one continuous layer (3) of the energy storage component; and / or The continuous layer (3) of energy storage component has a thickness in the range of 500 nm to 5000 nm.

6. The energetic thin film material according to any one of claims 1 to 5, wherein: A and B can react exothermically to form intermetallic compounds. Specifically, A simple substance is Ni, Ti, Fe or Pt, and B simple substance is Al; or A simple substance is Ti or Nb, and B simple substance is Si.

7. The energetic thin film material according to any one of claims 1 to 6, wherein: The thickness of the first layer (1) and the second layer (2) are both on the nanometer scale. In particular, the first layer (1) has a thickness of 10 nm to 200 nm, and / or the second layer (2) has a thickness of 10 nm to 200 nm.

8. The energetic thin film material according to any one of claims 1 to 7, wherein: The energetic thin film material is made by a physical vapor deposition process, in particular magnetron sputtering, arc ion plating, electron beam physical vapor deposition or thermal evaporation process.

9. A method for manufacturing an energetic thin film material according to any one of claims 1 to 8, comprising: - Step 1: installing a workpiece (200) into a device (100), wherein the device comprises a first target source (101) for providing an A element and a second target source (102) for providing a B element, - Step 2: adjusting the workpiece (200) to a first working position, in which the surface of the workpiece (200) to be deposited faces the first target source (101), - Step 3: energizing the first target source (101) to deposit the first layer (1), - Step 4: adjusting the workpiece (200) to a second working position, in which the surface to be deposited of the workpiece (200) faces a second target source (102), - Step 5: energizing the second target source (102) to deposit the second layer (2), - Step 6: Repeat steps 2 to 5 for multiple times to form a multi-layer modulation structure of the energetic thin film material.

10. The method according to claim 9, wherein: In step 3 and step 5, the method comprises regulating the working parameters of the first target source (101) and the second target source (102) and / or the position of the workpiece (200) relative to the first target source (101) and the second target source (102); and / or During the rotation of the workpiece (200), the first layer (1), the second layer (2) and the energy storage component are continuously deposited, and the energy storage component is particularly deposited to form a continuous layer (3). In particular, during the manufacturing process of the energetic thin film material, the workpiece (200) rotates continuously without interruption.

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