Energetic thin film materials and methods of making same

Abstract

The application relates to the field of energetic materials, in particular to an energetic film material, which comprises a first layer (1) containing A element and a second layer (2) containing B element, wherein the A element and the B element can have an exothermic reaction, the first layer (1) and the second layer (2) are alternately stacked to form at least a part of a multilayer modulation structure, characterized in that the multilayer modulation structure further comprises an energy storage component, after the exothermic reaction is triggered, 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. According to the energetic film material, the exothermic temperature of the energetic film material can be regulated without affecting the overall exothermic quantity, so that the exothermic reaction of the energetic film material can avoid causing thermal damage, such as ablation damage, to a heated object.

Description

Technical Field

[0001] This application relates to the field of energetic materials, specifically to an energetic thin film material and its manufacturing method. Background Technology

[0002] Energetic thin film materials typically employ two or more chemically reactive materials, A and B, forming a multilayered modulated structure with extremely high reactivity and exothermic properties. Under external energy induction, these materials can undergo a self-propagating exothermic reaction, instantly generating a high amount of heat, thus meeting the application requirements of various scenarios. They are excellent materials for fuze thermal batteries and brazing heat sources. Such combinations of materials A and B can include, for example, Ni-Al or Ti-Al combinations.

[0003] However, the exothermic temperature of the thin film cannot be controlled, and the excessively high temperature caused by the released heat may cause ablation damage to the heated object (such as the part to be welded in a welding scenario) in the thermal field formed by the energetic thin film material. Summary of the Invention

[0004] The purpose of this application is to provide an improved energetic thin film material that can reduce the limitations of existing technologies.

[0005] According to a first aspect of this application, an energetic thin film material is provided, comprising a first layer containing element A and a second layer containing element B, wherein element A and element B are capable of undergoing an exothermic reaction, and the first and second layers are alternately stacked to form at least most of a multilayer modulation structure, the multilayer modulation structure further comprising an energy storage component, wherein after the exothermic reaction is initiated, the energy storage component absorbs and stores a portion 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 this application, the energy storage component may include either element A or element B; or the energy storage component may include or not react with element A or element B, such as elemental metals or compounds.

[0007] According to an optional embodiment of this 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 alternative embodiment of this 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 multilayer modulation structure.

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

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

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

[0012] According to an optional embodiment of this 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 this application, element A and element B can undergo an exothermic reaction to generate an intermetallic compound.

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

[0015] According to an optional embodiment of this application, the thicknesses of both the first and second layers are on the nanometer scale.

[0016] According to an optional embodiment of this 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 alternative embodiment of this application, the energetic thin film material is prepared by physical vapor deposition process, particularly magnetron sputtering, arc ion plating, electron beam physical vapor deposition, or thermal evaporation process.

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

[0019] Step 1: Install the workpiece into the device, wherein the device includes a first target source for providing element A and a second target source for providing element B.

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

[0021] Step 3: Excite the first target source to deposit the first layer.

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

[0023] Step 5: Excite the second target source to deposit the second layer.

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

[0025] According to an optional embodiment of this application, in steps 3 and 5, the method includes adjusting the operating parameters of the first target source and the second target source and / or the position of the workpiece relative to the first target source and the second target source.

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

[0027] According to an optional embodiment of this 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 this application can achieve the control of the exothermic temperature of the energetic thin film material without affecting the overall exothermic heat, thereby avoiding thermal damage, such as ablation damage, to the heated object caused by the exothermic reaction of the energetic thin film material. Attached Figure Description

[0029] The principles, features, and advantages of this application will be better understood below with reference to the accompanying drawings. In the drawings:

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

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

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

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

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

[0035] Figure 6 for Figure 5 The reaction heat test DSC curve of the energetic thin film material example shown. Detailed Implementation

[0036] To make the technical problems to be solved, the technical solutions, and the beneficial technical effects of this application clearer, the application will be further described in detail below with reference to the accompanying drawings and several exemplary embodiments. It should be understood that the specific embodiments described herein are only for explaining the principles of this application and are not intended to limit the scope of protection of this application.

[0037] In the accompanying drawings of this application, features with the same structure or similar function are indicated by the same reference numerals.

[0038] like Figures 1-3 As shown, the energetic thin film material according to this application includes a first layer 1 containing element A and a second layer 2 containing element B, wherein the first layer 1 and the second layer 2 are alternately stacked to form at least most of a multilayer modulated structure. Here, element A and element B can undergo an exothermic reaction. In particular, element A and element B can undergo an exothermic reaction to form an intermetallic compound.

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

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

[0041] The energetic thin film material according to this application is characterized in that the multilayer modulation structure further includes an energy storage component, which absorbs and stores a portion of the heat generated by the exothermic reaction after the exothermic reaction is initiated, and releases the stored heat after the exothermic reaction ends.

[0042] By introducing energy storage components, some of the heat released in the early stages of the exothermic reaction can be stored, thereby reducing the increase in ambient temperature caused by the released heat. In other words, the maximum temperature during the exothermic process is lowered, limiting the temperature rise of the heated object within the thermal field formed by the energetic thin film material. The stored heat can be released again after the exothermic reaction ends, ensuring that the total heat released by the energetic thin film material is essentially the same as that of existing energetic thin film materials without energy storage components. This ensures that the temperature rise of the heated object during the exothermic reaction does not cause ablation damage, while maintaining the exothermic capacity of the energetic thin film material to preserve its functional effectiveness. Thus, the exothermic temperature of the energetic thin film material can be controlled without affecting the overall heat release.

[0043] Optionally, in some embodiments, the energy storage component may include either element A or element B. This simplifies the composition of the energetic thin film material, eliminating the need to introduce other additional components and thus avoiding concerns that these additional components might negatively impact the overall performance of the material.

[0044] Specifically, after initiating the exothermic reaction, elemental A and elemental B in the multilayer modulated structure of the energetic thin film material react exothermically, generating an AB compound with stoichiometric proportions. Excess elemental A or B that did not participate in the exothermic reaction remains in its elemental state and will absorb heat as the exothermic process continues, potentially melting in some cases. After the exothermic reaction ends, elemental B, which has reached a temperature rise or is in a molten state, will cool down or solidify accordingly, releasing heat.

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

[0046] Optionally, 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. This allows for the corresponding heat absorption and release through a reversible melting-solidification process, which involves a change in the morphology of the energy storage component. For example, the energy storage component can be a low-melting-point component that undergoes a melting phase change after absorbing heat, thereby achieving phase change energy storage.

[0047] Alternatively, the energy storage component can be designed to absorb heat during the exothermic reaction by heating and release heat by cooling after the reaction ends. This allows for the reversible process of heat absorption and release without a phase change in the energy storage component. For example, the energy storage component can be a high-melting-point component.

[0048] The energy storage components can be dispersed in phases at any location in the multilayer modulation structure, such as within the first layer 1, the second layer 2, and / or at the interface between the first layer 1 and the second layer 2.

[0049] Optionally and preferably, the energy storage component can be formed as a continuous layer 3 sandwiched between a first layer 1 containing element A and a second layer 2 containing element B in a multilayer modulation structure. This allows the continuous layer 3 to be prepared simultaneously with the deposition of the first layer 1 and the second layer 2. Here, "continuous" in continuous layer 3 means that the layer formed by the energy storage component is stacked 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 identical in composition and structure to the first layer 1 containing element A or the second layer 2 containing element B. Thus, the energetic thin film material according to this application can be conveniently manufactured by increasing the thickness of a specific first layer 1 or a specific second layer 2.

[0051] Additionally or alternatively, the continuous layer 3 of the energy storage component is located in at least one of the middle region, top region, and bottom region along the thickness direction of the multilayer modulation structure. The multilayer modulation structure may also include at least one continuous layer 3 of the energy storage component. Figure 1 The continuous layer 3 of the energy storage components located in the middle region of the multi-layered adjustment structure is shown. Figure 2 A continuous layer 3 located in the bottom region is shown, while Figure 3 Two continuous layers 3 located in the middle and bottom regions are shown. That is, the energetic thin film material according to this application may include at least one continuous layer 3, and its position in the multilayer 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 the case of multiple continuous layers 3, each continuous layer 3 may have a different thickness.

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

[0054] Alternatively, the energetic thin film material according to this application can be fabricated by physical vapor deposition processes, particularly magnetron sputtering, arc ion plating, electron beam physical vapor deposition, or thermal evaporation processes.

[0055] This application also provides a method for manufacturing the above-mentioned energetic thin film material. The following will be combined with... Figure 4 The method is described in the schematic diagram of the apparatus 100 for manufacturing the energetic thin film material according to this application.

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

[0057] like Figure 4 As shown, the apparatus 100 may include a first target source 101 for providing element A and a second target source 102 for providing element B. Here, the first target source 101 and the second target source 102 are arranged opposite each other on both sides of the apparatus 100, but this is not a limitation. The first target source 101 and the second target source 102 may be positioned at different locations within the apparatus 100 according to actual design requirements. For this purpose, 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 chamber of the apparatus 100. During operation, the workpiece 200, particularly the surface to be deposited on the workpiece 200, may be moved, for example, by a controller or an additional motion actuator, to a first working position corresponding to the first target source 101 or a second working position corresponding to the second target source 102, thereby depositing a first layer containing element A or a second layer containing element B accordingly. Here, the movement of the workpiece 200, particularly the surface to be deposited on the workpiece 200, to the first or second working position may be translational, rotational, or a combination thereof.

[0058] Alternatively, in some embodiments, the workpiece 200 can be... Figure 4 The support structure 210 shown is installed in the deposition apparatus 100. The support structure 210 can be controlled by the controller of the apparatus 100 to move the workpiece 200, in particular the surface of the workpiece 200 to be deposited, to a first working position or a second working position. In particular, the support structure 210 can rotate about the rotation axis R, so that the workpiece 200 can also rotate about the rotation axis R to 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 each other on both sides of the device 100, and the workpiece 200 switches its working position by rotating 180° around the axis of rotation R. This enables particularly convenient continuous deposition.

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

[0061] Step 1: Install the workpiece 200 into the deposition equipment 100.

[0062] Step 2: Adjust the workpiece 200 to the first working position, in which the surface of the workpiece 200 to be deposited 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 the second working position, in which the surface of the workpiece 200 to be deposited 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 multiple times to form an energetic thin film material with a multilayer modulation structure.

[0067] In one specific embodiment, such as 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 of the workpiece 200 to be deposited is adjusted to a first working position facing the first target source 101, and the first target source 101 is excited to deposit the first layer 1. Then the surface of the workpiece 200 to be deposited is adjusted to a second working position facing the second target source 102, and the second target source 102 is excited to deposit the second layer 2.

[0068] In steps 3 and 5, the deposition of the first layer 1 and the second layer 2 is achieved by adjusting the operating 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 operating parameters of the first target source 101 and the second target source 102 may include power and on / off time, etc., while 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 orientation, and optionally include the rotational 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. This allows for the overall deposition of the energetic thin film material, facilitating manufacturing and improving the connectivity between layers within the material, thereby enhancing the overall performance of the energetic thin film material. Specifically, the energy storage component can be deposited as a continuous layer 3. Additionally or alternatively, the workpiece 200 rotates continuously without interruption during the manufacturing process of the energetic thin film material. 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 where the content of the corresponding elements can vary.

[0070] Figure 5 Microstructure diagrams of an energetic thin film material according to a specific example of this application are shown, where (b) is a magnified view of a portion of (a), (c) is a magnified view of a portion of (b), and (d) is a scale measurement diagram. In this example, element A is Ni, and element B is Al. From Figure 5 As can be seen in this example, the modulation period of the multilayer modulation structure is approximately 110 nm, and its structure is similar to Figure 2 The schematic structure shown in the figure has a continuous layer at the bottom, in which an Al layer of a certain thickness is first deposited as a substrate during the preparation process, and the Al layer is used as the energy storage component (continuous layer) in the energetic thin film material according to the present application.

[0071] Figure 6 for Figure 5 The DSC curves for the reaction heat test of an example of a Ni / Al-based energetic thin film material are shown, where the horizontal axis represents temperature and the vertical axis represents heat flow. From Figure 6 As can be seen, the total exothermic reaction heat in this example is 802.2 J / g, and the initial reaction temperature is 207 °C, demonstrating its good activity. Furthermore, the DSC curve exhibits a "double-peak" characteristic. The first exothermic process (approximately 605.6 J / g) indicates that the Al layer serving as the substrate absorbs and stores some of the reaction heat through endothermic melting. The second exothermic process (approximately 196.6 J / g) indicates that after the exothermic reaction, the molten Al substrate undergoes exothermic solidification, releasing the stored energy. This results in the final total reaction heat being roughly equal to that of the energetic thin film material without an Al substrate (whose DSC curve exhibits a "single-peak" characteristic). During the first exothermic process, the two sub-peaks at approximately 228 °C and approximately 283 °C correspond to the formation of different compounds.

[0072] It is worth noting that, in the sense of this application, element A or element B refers to a substance formed by the corresponding sedimentary source through a sedimentation process, which allows for the presence of small or trace amounts of other substances (e.g., impurities) in the corresponding layer, for example, due to process reasons.

[0073] It should be understood that the terms "first," "second," etc., used herein are for descriptive purposes only and should not be construed as indicating or implying relative importance, nor should they be construed as implicitly specifying the number of technical features indicated. Features specified as "first" or "second" may expressly or implicitly indicate that at least one of those features is included.

[0074] In the description of this specification, the references to terms such as "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of this application. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0075] Although specific embodiments of this application are described in detail herein, they are given for illustrative purposes only and should not be construed as limiting the scope of this application. Various substitutions, modifications, and alterations can be conceived without departing from the spirit and scope of this application.

Claims

1. An energetic thin film material, comprising a first layer (1) containing element A and a second layer (2) containing element B, wherein, Element A and element B can undergo an exothermic reaction, and at least most of the first layer (1) and the second layer (2) are alternately stacked to form a multilayer modulated structure, characterized in that... The multilayer modulation structure further includes an energy storage component. After the exothermic reaction is initiated, the energy storage component absorbs and stores a portion of the heat generated by the exothermic reaction. After the exothermic reaction ends, the energy storage component releases the stored heat, so that the total heat released by the energetic thin film material is essentially the same as that of an energetic thin film material without the energy storage component. The energy storage component is designed to absorb heat during the exothermic reaction through a melting process and release heat through a solidification process after the exothermic reaction ends; or The energy storage component is designed to absorb heat during the exothermic reaction through a heating process and release heat after the exothermic reaction ends through a cooling process. The energy storage component includes a single-element metal or compound that does not react with element A or element B, wherein element A is Ni and element B is Al. The energy storage component is formed as a continuous layer (3) sandwiched between a first layer (1) containing element A and a second layer (2) containing element B in the multilayer modulation structure. The multilayer modulation structure includes at least one continuous layer (3) of the energy storage component. The continuous layer (3) of the energy storage component has a thickness in the range of 500 nm to 5000 nm. The thickness of the first layer (1) is 10 nm to 200 nm, and the thickness of the second layer (2) is 10 nm to 200 nm.

2. The energetic thin film material according to claim 1, wherein, The energetic thin film material is fabricated using a physical vapor deposition process.

3. The energetic thin film material according to claim 2, wherein, The physical vapor deposition process includes magnetron sputtering, arc ion plating, electron beam physical vapor deposition, or thermal evaporation.

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

5. The method according to claim 4, wherein, In steps 3 and 5, the method includes adjusting the operating 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 formed.

6. The method according to claim 5, wherein, During the rotation of the workpiece (200), the energy storage component is deposited to form a continuous layer (3); and / or During the manufacturing process of the energetic thin film material, the workpiece (200) rotates continuously without interruption.

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