Composite structure polymeric coh energetic material and method of synthesis thereof
By using a noble metal catalyst to reduce pressure and employing a high-pressure reaction method, a composite polymeric COH energetic material was prepared, solving the problem of high-pressure synthesis, improving the energy density and stability of the material, and enabling mass production at lower pressures.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- INSTITUTE OF PHYSICS CHINESE ACADEMY OF SCIENCES
- Filing Date
- 2021-12-15
- Publication Date
- 2026-07-03
Smart Images
Figure CN116333269B_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of energetic materials technology, and specifically relates to a composite structure polymeric COH energetic material and its synthesis method. Background Technology
[0002] Current research on disruptive energetic materials mainly includes metallic hydrogen, all-nitrogen compounds, and high-stretch bond energy release materials. Theoretical predictions indicate that the energy density of metallic hydrogen is approximately 2.16 x 10⁻⁶. 5 Hydrogen, with its high energy density (J / g), is the highest-energy chemical explosive known to date. Due to its high energy density, metallic hydrogen can be used as an ultra-high-powered explosive, with an equivalent yield 50 times that of TNT, making it highly valuable for both military and civilian applications. Unfortunately, the synthesis of metallic hydrogen currently requires extremely high pressures (above ~400 GPa), and there is still no direct evidence of its existence. All-nitrogen compounds, as high-energy-density energetic materials, face the challenge of recovering energy at atmospheric pressure. High-strength bond energy release materials refer to solid polymers formed from gaseous molecular compounds under condensed-state physics. Currently, there is limited research on polymeric COH energetic materials. However, current technologies require high pressures to synthesize polymeric COH materials, generally at least 5 GPa. While this pressure is relatively easy to obtain in the laboratory, it limits the mass production of polymeric COH materials. Researchers are focusing on finding methods to synthesize polymeric COH materials at lower pressures for engineering applications. Summary of the Invention
[0003] Based on the above analysis, the present invention aims to provide a composite structure polymeric COH energetic material and its synthesis method to solve one of the following technical problems: (1) The synthesis technology of polymeric COH materials in the prior art requires high pressure and harsh synthesis conditions, which are not easy to achieve; (2) The polymeric COH energetic material in the prior art has poor stability and is not easy to preserve.
[0004] The objective of this invention is mainly achieved through the following technical solutions:
[0005] On one hand, the present invention provides a composite structure polymeric COH energetic material, which includes polymeric CO and polymeric H / CO; wherein, polymeric CO coats polymeric H / CO to form a composite structure, and polymeric H / CO is formed by H-doped polymeric CO.
[0006] On the other hand, the present invention also provides the application of a catalyst in the synthesis of composite structure polymeric COH energetic materials. The catalyst includes a noble metal or a noble metal-supported copper oxide or cerium dioxide material. Using the catalyst in the synthesis of composite structure polymeric COH energetic materials reduces the pressure required for the synthesis of composite structure polymeric COH energetic materials.
[0007] Furthermore, precious metals include palladium, platinum, ruthenium, rhodium, or gold.
[0008] On the other hand, the present invention also provides a method for synthesizing a composite structure polymeric COH energetic material, which is used to prepare the above-mentioned composite structure polymeric COH energetic material. The synthesis method involves adding a catalyst during a high-pressure reaction. The catalyst includes a noble metal or a noble metal-supported copper oxide or cerium dioxide material to reduce the pressure required to synthesize the composite structure polymeric COH energetic material.
[0009] Preferred precious metals include palladium, platinum, ruthenium, rhodium, or gold.
[0010] Furthermore, the synthesis method includes the following steps:
[0011] S1. H2 and CO gases are loaded into the high-pressure chamber, and then the high-pressure chamber is sealed; a catalyst is placed inside the high-pressure chamber.
[0012] S2. Pressurize the H2 and CO gases in the high-pressure chamber until the target pressure is reached, maintain it for a period of time, then unload the pressure, open the high-pressure chamber, and obtain the polymerized H / CO material.
[0013] S3. Place the above-mentioned polymerized H / CO material into the high-pressure chamber; wherein, the high-pressure chamber contains a catalyst;
[0014] S4. Liquefy carbon monoxide gas and fill the high-pressure chamber in S3, then seal the high-pressure chamber.
[0015] S5. Pressurize the material in the high-pressure chamber in S4 until the target pressure is reached, maintain it, then unload the pressure and open the high-pressure chamber to obtain the composite structure polymeric COH energetic material.
[0016] Furthermore, S1 includes:
[0017] S11. Complete the preparation of pressurization accessories for the high-pressure device;
[0018] S12. Assemble the high-pressure device pressurizing accessory into the thermostat cavity and seal the thermostat cavity.
[0019] S13. Load the mixture of carbon monoxide and hydrogen into the high-pressure chamber, and then seal the high-pressure chamber by adjusting the relative positions of the upper and lower anvils of the high-pressure device.
[0020] S14. Release the remaining carbon monoxide and hydrogen in the thermostat chamber and remove the pressurization accessory of the high-pressure device.
[0021] Furthermore, in S13, H2 accounts for 5% to 95% of the molar ratio of the mixed gas.
[0022] Furthermore, in S1 and S3, the catalyst is deposited into the high-pressure chamber in the form of a thin film.
[0023] Furthermore, in S1 and S3, the thickness of the catalyst film is 5 nm to 50 μm.
[0024] Furthermore, the composite polymeric COH energetic material prepared by the synthesis method is a solid with a density of 2 g / cm³. 3 ~6g / cm 3 .
[0025] Compared with the prior art, the present invention can achieve at least one of the following technical effects:
[0026] 1) The composite structure polymeric COH energetic material of the present invention (hereinafter referred to as p-COH) comprises polymeric CO and polymeric H / CO; wherein, polymeric CO coats polymeric H / CO to form a core-shell composite structure with polymeric CO as the shell and polymeric H / CO as the core, and polymeric H / CO is formed by H-doped polymeric CO. The composite structure polymeric COH material of the present invention improves the energy density and stability of polymeric CO. The density of the composite structure polymeric COH energetic material of the present invention is approximately 2.3–6 g / cm³. 3 It belongs to high energy density materials and is a new type of material with high energy content, which has broad application prospects in many fields.
[0027] 2) The synthesis method of the composite structure polymeric COH energetic material of the present invention promotes the polymerization reaction of the polymeric COH energetic material through the action of a catalyst (e.g., noble metals such as palladium, platinum, ruthenium, rhodium, gold, and copper oxide and cerium dioxide supported on noble metals), reducing the pressure required for the polymerization reaction of carbon monoxide and hydrogen. Compared with the polymerization reaction of carbon monoxide and hydrogen without the addition of a catalyst, the synthesis pressure of different crystal phases of p-COH (different crystal phases refer to different products obtained under different pressures while controlling the same raw materials) is reduced from the existing 5-80 GPa to 3-60 GPa, a reduction of 2-20 GPa. For example, the synthesis pressure of recyclable p-COH-I is reduced from about 5-20 GPa to 3-9 GPa, the synthesis pressure of p-COH-II is reduced from about 7-30 GPa to 4-20 GPa, and the synthesis pressure of p-COH-III is reduced from about 50-80 GPa to 25-60 GPa. By reducing the synthesis pressure, the preparation difficulty of polymeric COH energetic materials can be greatly reduced, providing technical support for the mass production of polymeric COH energetic materials.
[0028] 3) The synthesis method of the composite structure polymeric COH energetic material of the present invention first realizes the polymerization of hydrogen and carbon monoxide mixed gas by high pressure loading; then, the polymeric H / CO material prepared in the first step is coated by low temperature liquefaction or high pressure compression; therefore, the p-COH prepared by this technology can achieve the control of carbon-hydrogen ratio of different components.
[0029] 4) In the p-COH energetic material prepared by the present invention, due to the catalytic cracking effect, hydrogen enters the polymeric carbon monoxide lattice in atomic form, forming a composite structure with polymeric H / CO core and polymeric CO coating on the outside; the atomic hydrogen in the p-COH energetic material lattice increases the energy density of the polymeric carbon monoxide material, and the polymeric COH material with composite structure of the present invention improves the energy density and stability of polymeric CO.
[0030] 5) Compared with pure polymerized carbon monoxide, the atomic hydrogen in the lattice of the p-COH energetic material prepared by this invention plays a certain passivation role on the polymerized carbon monoxide material, which improves the stability of the polymerized COH energetic material. It can be placed in the air for 2 to 5 days without deterioration, and its stability to light, heat and water vapor is significantly improved.
[0031] Other features and advantages of the invention will be set forth in the following description, and in part will be obvious from the description or may be learned by practicing the invention. The objects and other advantages of the invention may be realized and obtained by means of the structures particularly pointed out in the written description and the accompanying drawings. Attached Figure Description
[0032] The accompanying drawings are for illustrative purposes only and are not intended to limit the invention. Throughout the drawings, the same reference numerals denote the same parts.
[0033] Figure 1 The image shows the Raman spectrum of the H2 and CO mixture under normal pressure conditions in Example 1 of this invention.
[0034] Figure 2 The Raman spectrum of the pH / CO material at 5 GPa in Example 1 of this invention;
[0035] Figure 3 The Raman spectra of liquid CO and pH / CO material as a function of pressure in Example 1 of the present invention are shown.
[0036] Figure 4 This is a diagram showing the laser detonation effect of the p-COH-II material in Example 1 of the present invention. Detailed Implementation
[0037] The following detailed description of a polymeric COH energetic material and its synthesis method, with reference to specific embodiments, is provided. These embodiments are for comparative and illustrative purposes only, and the present invention is not limited to these embodiments.
[0038] Through in-depth research, the inventors applied a catalyst to the synthesis process of polymerized COH energetic materials in order to reduce the pressure required for the synthesis of polymerized COH energetic materials.
[0039] This invention provides a method for synthesizing a composite-structured polymeric COH energetic material, comprising the following steps:
[0040] S1. Hydrogen (H2) and carbon monoxide (CO) gas are loaded into a high-pressure chamber, and then the high-pressure chamber is sealed; wherein, hydrogen accounts for 5% to 95% of the mixed gas, and a catalyst is placed in the high-pressure chamber;
[0041] S2. Pressurize the hydrogen and carbon monoxide mixture in the high-pressure chamber until the target pressure is reached, and maintain it for 5 minutes to several days (e.g., 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, etc.) to prepare the polymeric H / CO material. Then slowly unload the pressure and open the high-pressure chamber to obtain the polymeric H / CO material (hereinafter referred to as pH / CO).
[0042] S3. Place the above-mentioned pH / CO energetic material into the high-pressure chamber; wherein the volume of the pH / CO material is 5% to 95% of the volume of the high-pressure chamber; wherein the high-pressure chamber contains a catalyst;
[0043] S4. Liquefy carbon monoxide gas and fill the high-pressure chamber in S3, then seal the high-pressure chamber.
[0044] S5. Pressurize the material in the high-pressure chamber until the target pressure is reached, maintain it for 15-30 minutes, then slowly unload the pressure and open the high-pressure chamber to obtain the composite structure polymeric COH energetic material (p-COH).
[0045] It should be noted that the catalysts mentioned above include precious metals such as palladium, platinum, ruthenium, rhodium, and gold, as well as materials such as copper oxide and cerium dioxide supported on precious metals.
[0046] Specifically, the catalyst is deposited in the high-pressure chamber in the form of a thin film.
[0047] It should be noted that the above-mentioned synthesis method of p-COH energetic materials is carried out in a high-pressure device, which can be a multi-face press (such as a six-face press), a two-face press (such as a Paris-Edinburgh (PE) press, a diamond anvil device), or a ring press.
[0048] Specifically, S1 above includes:
[0049] S11. Complete the preparation of pressurization accessories for the high-pressure device;
[0050] S12. Assemble the high-pressure device pressurizing accessory into the thermostat cavity and seal the thermostat cavity.
[0051] S13. Load the mixture of carbon monoxide and hydrogen into the high-pressure chamber, and then seal the high-pressure chamber by adjusting the relative positions of the upper and lower anvils of the high-pressure device.
[0052] S14. Release the remaining carbon monoxide and hydrogen in the thermostat chamber and remove the pressurization accessory of the high-pressure device.
[0053] In S11 above, the preparation work for the pressurization accessories of the high-pressure device includes:
[0054] S111. Select a matching sealing gasket according to the anvil area of the high-pressure device and pre-press it so that an indentation appears in the center of the sealing gasket.
[0055] S112. Drill a round hole at the center of the indentation on the sealing gasket. This round hole serves as a high-pressure chamber for sample encapsulation and reaction.
[0056] S113. Deposit catalyst films on the upper and lower anvil surfaces of the high-pressure anvil, respectively;
[0057] S114. Fix the sealing gasket at the indentation position on the anvil surface under the high-pressure device;
[0058] S115. Tightly close the high-pressure anvil and sealing gasket, and then open a certain distance for sealing a mixture of hydrogen and carbon monoxide gas.
[0059] In S111 above, the gasket material can be T301 stainless steel, rhenium sheet, or tungsten sheet, etc.
[0060] In S112 above, the gasket is punched by laser punching or mechanical punching.
[0061] In S113 above, the catalyst can be deposited onto the surface of the anvil via magnetron sputtering, existing in the form of a thin film. Considering that if the catalyst film thickness is too small, it is easy to fall off during the process, and if the catalyst film thickness is too large, the catalytic effect will be insufficient and it will affect the pressure required for polymerization, the thickness of the catalyst film is controlled to be 5nm-50μm, for example, 5-80nm; in order to avoid oxidation or deterioration of the catalyst during the deposition process, the entire catalyst deposition process is completed in high-purity argon gas.
[0062] In the above S115, the distance between the high-pressure anvil and the sealing gasket should not be too large, preferably 0.3 to 0.5 mm.
[0063] Specifically, in step S12 above, after the high-pressure device pressurizing accessory is installed in the low-temperature thermostat cavity, the gaps in the high-pressure device pressurizing accessory need to be sealed. The conical filler block can effectively occupy the gaps inside the low-temperature thermostat, thereby reducing the volume of carbon monoxide that needs to be liquefied.
[0064] Specifically, in S13 above, if the amount of hydrogen in the mixed gas is too large, the pressure required for the polymerization process will be too high and difficult to achieve. Therefore, the molar ratio of hydrogen in the mixed gas is 5% to 95%.
[0065] Specifically, in S13 above, carbon monoxide and hydrogen are loaded into the high-pressure chamber through cryogenic liquefaction and / or high-pressure compression. The main steps include:
[0066] S131. Close the thermostat's air outlet valve;
[0067] S132. Carbon monoxide and hydrogen are forced into the high-pressure chamber. The mixture of gaseous carbon monoxide and hydrogen is compressed by a high-pressure pump to fill the high-pressure chamber and the thermostat.
[0068] S133. Apply a certain pressure to the high-pressure chamber through the external operating rod of the thermostat to lock the pressurizing accessory of the high-pressure device, thereby sealing carbon monoxide and hydrogen in the high-pressure chamber. Then close the carbon monoxide and hydrogen inlet valves and open the outlet valve.
[0069] Specifically, in S131-S133 above, temperature and pressure sensors are installed inside the thermostat cavity to monitor the temperature and pressure conditions inside the cavity in real time.
[0070] Specifically, in S132 and S133 above, the pressure required for high-pressure compression of carbon monoxide and hydrogen is 0.2 to 2 GPa.
[0071] Specifically, in S2 above, an excessively high pressurization rate can easily generate a pressure gradient, which is detrimental to sample synthesis. Therefore, the pressurization rate is controlled at 0.5–2 GPa / min, and the target pressure is 3–80 GPa. The prepared pH / CO materials with different crystalline phases are solids, exhibiting various appearances such as black, brownish-yellow, and transparent, with a density of 2.3 g / cm³. 3 ~6g / cm 3 .
[0072] It should be noted that in S2 above, the target pressure is related to the molar ratio of carbon monoxide and hydrogen. The more hydrogen there is, the greater the target pressure.
[0073] It should be noted that in S2 and S5 above, the same raw materials are used, and different crystalline phases of products can be obtained under different pressures. In the following text, the products with different crystalline phases will be represented by p-COH-I, p-COH-II, and p-COH-III. Considering that the pressure required to synthesize p-COH-I varies depending on the ratio of CO to H2 in this invention, the controlled variable method needs to be adopted when analyzing the effects of this invention: that is, when comparing the pressure required for the reaction, only the addition of a catalyst is controlled, while other raw material ratios and product conditions are kept the same.
[0074] For example, in S2 above:
[0075] When the molar ratio of carbon monoxide to hydrogen is 9:1, the target pressure is 2–4 GPa (e.g., 2.5 GPa, 3 GPa, 3.5 GPa) if the final product is p-COH-I; 5–7 GPa (e.g., 5.5 GPa, 6 GPa, 6.5 GPa) if the final product is p-COH-II; and 10–60 GPa (e.g., 15 GPa, 20 GPa, 25 GPa, 27 GPa, 30 GPa, 35 GPa, 37 GPa, 40 GPa, 45 GPa, 47 GPa, 50 GPa, 35 GPa, 57 GPa) if the final product is p-COH-III.
[0076] When the molar ratio of carbon monoxide to hydrogen is 1:1, the target pressure is 4–6 GPa (e.g., 4.5 GPa, 5 GPa, 5.5 GPa) if the final product is p-COH-I; 5–10 GPa (5.5 GPa, 6 GPa, 6.5 GPa, 7 GPa, 7.5 GPa, 8 GPa, 8.5 GPa, 9 GPa, 9.5 GPa) if the final product is p-COH-III; and 15–60 GPa (e.g., 20 GPa, 25 GPa, 27 GPa, 30 GPa, 33 GPa, 35 GPa, 37 GPa, 40 GPa, 45 GPa, 47 GPa, 50 GPa, 55 GPa, 57 GPa) if the final product is p-COH-I.
[0077] When the molar ratio of carbon monoxide to hydrogen is 1:9, the target pressure is 8–9 GPa (e.g., 8 GPa, 8.5 GPa, 9 GPa) if the final product is p-COH-I; 15–20 GPa (e.g., 15.5 GPa, 16 GPa, 16.5 GPa, 17 GPa, 17.5 GPa, 18 GPa, 18.5 GPa, 19 GPa, 19.5 GPa) if the final product is p-COH-III; and 20–60 GPa (e.g., 25 GPa, 27 GPa, 30 GPa, 35 GPa, 40 GPa, 45 GPa, 47 GPa, 50 GPa, 55 GPa, 57 GPa) if the final product is p-COH-I.
[0078] Specifically, S3 above includes the following main steps:
[0079] S31. Complete the preparation of pressurization accessories for the high-pressure device;
[0080] S32. Cut the pH / CO material obtained in S2 above to 5% to 95% of the high-pressure chamber volume;
[0081] S33. Place the pH / CO sample cut in step S32 above into the high-pressure chamber;
[0082] S34. Tightly close the high-pressure anvil and sealing gasket, and then open them a certain distance for carbon monoxide encapsulation.
[0083] In the above S31, the high-pressure device includes multi-face presses (such as six-face presses), two-face presses (such as Paris-Edinburgh (PE) presses, diamond anvil devices) and annular presses.
[0084] In step S31 above, the preparation of the pressurization accessories for the high-pressure device is the same as in step S11.
[0085] In step S4 above, carbon monoxide gas is loaded into the high-pressure chamber through cryogenic liquefaction or high-pressure compression. The specific steps are as follows:
[0086] S41. Assemble the high-pressure device pressurizing accessory into the thermostat cavity and seal the thermostat.
[0087] S42. Introduce carbon monoxide gas into the thermostat;
[0088] S43. Close the carbon monoxide outlet valve: (1) Cool the thermostat together with the introduced carbon monoxide gas to the temperature range between the melting point and boiling point of carbon monoxide, so that the carbon monoxide gas gradually liquefies and fills the high-pressure chamber and thermostat of the high-pressure device; or (2) Compress the gaseous carbon monoxide by a high-pressure pump to fill the high-pressure chamber and thermostat.
[0089] S44. Apply a certain pressure to the pressurizing accessory of the high-pressure device through the external operating rod of the thermostat to lock the high-pressure device, so as to seal carbon monoxide in the high-pressure chamber. Then close the carbon monoxide inlet valve and open the outlet valve.
[0090] S45. Increase the temperature or turn off the high-pressure pump to allow the remaining carbon monoxide in the thermostat to gradually evaporate and be discharged from the thermostat. Then remove the high-pressure device pressurization accessory.
[0091] In S41-S45 above, temperature and pressure sensors are installed inside the thermostat cavity to monitor the temperature and pressure conditions inside the cavity in real time.
[0092] In S43 above, the pressure required for high-pressure compression of carbon monoxide gas is 0.2 to 1 GPa.
[0093] In step S44 above, the pressure required for encapsulating the liquid carbon monoxide is 0.2 to 1 GPa.
[0094] Specifically, in S4 above, liquid carbon monoxide in the high-pressure chamber accounts for 5% to 95% of the volume of the high-pressure chamber.
[0095] Specifically, in S5 above, the pressurization rate is 0.5 to 2 GPa / min, the target pressure is 3 to 80 GPa, and as the target pressure increases, p-COH-I, p-COH-II, and p-COH-III crystal phases are formed respectively.
[0096] Specifically, in S5 above:
[0097] If the final product is p-COH-I, the target pressure is 3 to 9 GPa (e.g., 3.5 GPa, 4 GPa, 4.5 GPa, 5 GPa, 5.5 GPa, 6 GPa, 6.5 GPa, 7 GPa, 7.5 GPa, 8 GPa, 8.5 GPa, 9 GPa).
[0098] If the final product is p-COH-II, the target pressure is 4–20 GPa (e.g., 4.5 GPa, 5 GPa, 6 GPa, 7 GPa, 8 GPa, 9 GPa, 10 GPa, 11 GPa, 12 GPa, 13 GPa, 14 GPa, 15 GPa, 16 GPa, 17 GPa, 18 GPa, 19 GPa).
[0099] If the final product is p-COH-III, the target pressure is 25–60 GPa (e.g., 30 GPa, 35 GPa, 40 GPa, 45 GPa, 50 GPa, 55 GPa).
[0100] Specifically, in S5 above, the p-COH samples with different crystalline phases were prepared as solids, exhibiting various appearances such as black, brownish-yellow, and red, with a density of 2 g / cm³. 3 ~6g / cm 3 .
[0101] Specifically, in S5 above, the obtained p-COH energetic material is composed of three elements: carbon, hydrogen, and oxygen. p-COH is a metastable material, and its structure includes a three-dimensional network structure, a two-dimensional layered structure, and a one-dimensional chain structure formed by CC, C=C, OO, CH, OH, and atomic H. The p-COH material is prepared by a two-step method, and its structural characteristics are: the first step is to prepare pH / CO, and the second step is to achieve the coating of pH / CO with p-CO, forming a composite structure with p-CO as the shell and pH / CO as the core.
[0102] Specifically, in S5 above, the obtained p-COH is a blocky solid, exhibiting various appearances including black, brownish-yellow, red, and transparent, with a density of 2.3 g / cm³. 3 ~6g / cm 3 The specific density is determined by the ratio of carbon to hydrogen in the polymer.
[0103] Specifically, in the above-mentioned synthesis method of p-COH energetic materials, Raman spectroscopy can be used to detect and monitor the state transition process of the sample inside the high-pressure cavity.
[0104] Example 1
[0105] This embodiment provides a method for synthesizing a composite structure polymeric COH energetic material, including:
[0106] S1. Hydrogen and carbon monoxide gases are loaded into a high-pressure chamber, and then the high-pressure chamber is sealed; wherein the molar ratio of hydrogen to carbon monoxide is 1:1; wherein the thickness of the palladium film on the anvil surface of the high-pressure chamber is 10 nm.
[0107] S2. Pressurize the hydrogen and carbon monoxide gas in the high-pressure chamber to 5 GPa, maintain for 10 min to prepare pH / CO material, then slowly unload the pressure, open the high-pressure chamber to obtain pH / CO material.
[0108] S3. Place the above-mentioned pH / CO energetic material into the high-pressure chamber; wherein the volume of the pH / CO material is 80% of the volume of the high-pressure chamber; wherein the thickness of the palladium film on the anvil surface of the high-pressure chamber is 10 nm.
[0109] S4. Liquefy carbon monoxide gas and fill the high-pressure chamber of S3, then seal the high-pressure chamber.
[0110] S5. Pressurize the material in the high-pressure chamber to 5 GPa, maintain for 20 minutes, then slowly unload the pressure and open the high-pressure chamber to obtain the composite structure p-COH-II energetic material.
[0111] Specifically, in S1, the mixture of hydrogen and carbon monoxide is introduced into the high-pressure chamber via high-pressure filling. The main steps include:
[0112] S11. Complete the preparation of pressurization accessories for the high-pressure device;
[0113] S12. Assemble the pressurizing accessories of the high-pressure device into the constant temperature chamber and seal the constant temperature chamber.
[0114] S13. Introduce a mixture of carbon monoxide and hydrogen gas with a molar ratio of 1:1 into the constant temperature chamber, and seal it by high pressure loading and pressurization.
[0115] S14. Release the remaining carbon monoxide and hydrogen in the thermostat chamber and remove the pressurization accessory of the high-pressure device.
[0116] In S11 above, the preparation work for the pressurization accessories of the high-pressure device includes:
[0117] S111. Pre-press the gasket with a diamond anvil until an indentation appears in the center.
[0118] S112. Drill a hole at the center of the gasket indentation;
[0119] S113. Deposit palladium films on the upper and lower anvil surfaces of the high-pressure anvil, respectively, with a thickness of 10 nm.
[0120] S114. Secure the sealing gasket to the indentation position on the lower anvil surface;
[0121] S115. Tightly close the upper anvil, sealing gasket and lower anvil, and then open a certain distance (0.5mm) for sealing a mixture of hydrogen and carbon monoxide gas.
[0122] In S111 above, the gasket material is T301 stainless steel.
[0123] In S112 above, the gasket drilling method is laser drilling.
[0124] Specifically, in step S12 above, after the high-pressure device pressurizing accessory is installed inside the thermostat cavity, the gaps in the high-pressure device pressurizing accessory need to be sealed. A conical filler block can effectively occupy the gaps inside the low-temperature thermostat, thereby reducing the volume of carbon monoxide that needs to be liquefied.
[0125] In S13 above, the pressure used to seal the mixture of hydrogen and carbon monoxide is 500 MPa.
[0126] In S2 above, the pressurization rate was 2 GPa / min, and the resulting pH / CO sample was glossy black with a density of approximately 2.7 g / cm³. 3 .
[0127] Specifically, in S4 above, carbon monoxide gas is added to the pressurization accessory of the high-pressure device via cryogenic liquefaction. The main steps include:
[0128] S41. Assemble the high-pressure device pressurizing accessory into the thermostat cavity and seal the thermostat.
[0129] S42. Introduce carbon monoxide gas into the thermostat;
[0130] S43. Cool the thermostat together with the introduced carbon monoxide gas to the temperature range between the melting point and boiling point of carbon monoxide, so that the carbon monoxide gas gradually liquefies and fills the high-pressure chamber and thermostat. Then close the carbon monoxide inlet and outlet valves.
[0131] S44. Apply a certain pressure by using the external operating rod of the thermostat to lock the pressurizing accessory of the high-pressure device, thereby sealing the carbon monoxide liquid in the high-pressure chamber.
[0132] S45. Increase the temperature to gradually vaporize and discharge the remaining carbon monoxide liquid in the thermostat. Then remove the high-pressure device pressurization accessory.
[0133] Specifically, in S41 above, the sealing process is completed by closing and tightening the connecting bolts between the thermostat body and the thermostat top cover.
[0134] Specifically, in step S42 above, the assembled thermostat is connected to the gas line, and the outlet valve of the thermostat is opened; the flow rate of gaseous carbon monoxide is controlled by the pressure reducing valve of the carbon monoxide cylinder and the gas valve of the thermostat, allowing it to slowly enter the chamber of the thermostat; after venting for about 5 minutes, the air in the chamber of the thermostat is expelled; the bolt of the high-pressure device is loosened by using the operating lever on the thermostat, creating a gap between the upper pressure anvil and the gasket, and the original gas in the high-pressure chamber is expelled by the introduced carbon monoxide gas; then the outlet valve of the thermostat is closed.
[0135] Specifically, in step S43 above, the thermostat is first placed in a liquid nitrogen environment to cool the thermostat equipment; the temperature and pressure of the gas introduced are monitored in real time by temperature and pressure sensors inside the thermostat; when the internal temperature of the thermostat drops below the boiling point of carbon monoxide, the gaseous carbon monoxide begins to gradually liquefy; since the liquefaction of the gas releases a large amount of heat, it causes a large change in the local environment, and the gas pressure will fluctuate violently; after cooling for 20-40 minutes, the temperature sensor shows that the thermostat has reached the boiling point of liquid nitrogen, about 77K, at which point a large amount of gaseous carbon monoxide has liquefied; after waiting for another 20-30 minutes, the liquid carbon monoxide will fill the entire cryogenic thermostat.
[0136] In S44 above, the pressure required to encapsulate liquid carbon monoxide is 500 MPa.
[0137] Specifically, in step S45 above, the inlet valve of the thermostat is closed, the main valve of the gas cylinder is closed, the cooling device below the thermostat is slowly removed to allow the thermostat to gradually heat up, and the outlet valve of the thermostat is opened to slowly release the carbon monoxide. Since the liquid carbon monoxide rapidly vaporizes and produces a large amount of gas when the thermostat's temperature approaches the boiling point of carbon monoxide, the exhaust gas needs to be slowly released by controlling the outlet valve. Once the temperature reaches room temperature and the pressure inside the thermostat returns to normal, the high-pressure device pressurization accessory can be removed.
[0138] In S4 above, the volume ratio of liquid carbon monoxide to pH / CO material in the high-pressure chamber is 1:4.
[0139] In S5 above, the pressure ramp rate is 2 GPa / min. The prepared p-COH-II energetic material is a black solid with a density of approximately 2.6 g / cm³. 3 Without a catalyst, the synthesis pressure of the p-COH-II energetic material is 7 GPa, as shown in Comparative Example 1. In contrast, the synthesis pressure of p-COH-II decreases from 7 GPa to 5 GPa, a reduction of 2 GPa.
[0140] In the synthesis of p-COH-II energetic materials, Raman spectroscopy is used to monitor the phase transition process of the sample, such as... Figure 1 As shown, Raman spectroscopy clearly shows that at atmospheric pressure, 4200 cm⁻¹ -1 The Raman peak, H2, is 2140 cm high. -1 The nearby Raman peak is CO; at 5 GPa ( Figure 2 The Raman peaks for H2 and CO disappear, while the peak at 1600 cm⁻¹ disappears. -1 The presence of a C=O double bond Raman peak nearby indicates the formation of a pH / CO material; a peak at 2140 cm⁻¹ was detected after filling the high-pressure chamber containing the built-in pH / CO material with CO. -1The Raman peak of CO in the vicinity; as the pressure gradually increases, the Raman peak of CO disappears at 5 GPa, and at the same time, the Raman peak of p-CO appears, indicating the formation of p-COH material. Figure 4 This is a diagram illustrating the laser detonation effect of p-COH-II.
[0141] Example 2
[0142] This embodiment provides a method for synthesizing a composite structure polymeric COH energetic material. The steps are largely the same as those in Example 1, with the following differences:
[0143] In S1, the molar ratio of hydrogen to carbon monoxide is 1:2, and the thickness of the gold film on the anvil surface of the high-pressure chamber is 10 nm.
[0144] In S115, the distance within a certain range after opening is 0.5mm.
[0145] In S13, the pressure used to seal the mixture of hydrogen and carbon monoxide is 300 MPa.
[0146] In S2, the pressurization rate is 1 GPa / min, the target pressure is 3 GPa, and it is maintained for 30 min.
[0147] In S2, the prepared pH / CO sample was glossy black with a density of approximately 2.4 g / cm³. 3 ;
[0148] In S3, the volume of the pH / CO material is 20% of the volume of the high-pressure chamber.
[0149] In S44, the pressure required to encapsulate liquid carbon monoxide is 300 MPa.
[0150] In S4, the volume ratio of liquid carbon monoxide to pH / CO material in the high-pressure chamber is 4:1.
[0151] In S5, the pressurization rate is 2 GPa / min; the target pressure is 3 GPa, and it is maintained for 25 min.
[0152] In S5, the prepared p-COH-I energetic material was a black solid with a density of approximately 2.3 g / cm³. 3 .
[0153] In the synthesis of p-COH-I energetic materials, Raman spectroscopy can be used to detect the polymerization of H / CO and the formation of p-COH samples, which will not be elaborated here.
[0154] As shown in Comparative Example 2, the synthesis pressure of the p-COH-I energetic material without a catalyst is 5 GPa. In contrast, the synthesis pressure of p-COH-I is reduced from 5 GPa to 3 GPa, a decrease of 2 GPa.
[0155] Example 3
[0156] This embodiment provides a method for synthesizing a composite structure polymeric COH energetic material. The steps are largely the same as those in Example 1, with the following differences:
[0157] In S1, the molar ratio of hydrogen to carbon monoxide is 1:4, and the thickness of the cerium oxide film on the anvil surface of the high-pressure chamber is 20 nm.
[0158] In S115, the distance within a certain range after opening is 0.5mm.
[0159] In S13, the pressure used to seal the mixture of hydrogen and carbon monoxide is 200 MPa.
[0160] In S2, the pressurization rate is 1 GPa / min, the target pressure is 10 GPa, and the pressure is maintained for 20 min.
[0161] In S2, the prepared pH / CO sample was light yellow with a density of approximately 5.3 g / cm³. 3 ;
[0162] In S3, the volume of the pH / CO material is 80% of the volume of the high-pressure chamber.
[0163] In S44, the pressure required to encapsulate liquid carbon monoxide is 200 MPa.
[0164] In S4, the volume ratio of liquid carbon monoxide to pH / CO material in the high-pressure chamber is 1:4.
[0165] In S5, the pressurization rate is 1 GPa / min; the target pressure is 40 GPa, and it is maintained for 20 min.
[0166] In S5, the prepared p-COH-III energetic material was a black solid with a density of approximately 4.2 g / cm³. 3 .
[0167] In the synthesis of p-COH-III energetic materials, Raman spectroscopy can be used to detect the polymerization of H / CO and the formation process of p-COH energetic materials, which will not be elaborated here.
[0168] As shown in Comparative Example 3, the synthesis pressure of p-COH-III without a catalyst is 60 GPa. In contrast, the synthesis pressure of p-COH-III is reduced from 60 GPa to 40 GPa, a decrease of 20 GPa.
[0169] Example 4
[0170] This embodiment provides a method for synthesizing a composite structure polymeric COH energetic material. The steps are largely the same as those in Example 1, with the following differences:
[0171] In S1, the molar ratio of hydrogen to carbon monoxide is 5:1, and the catalyst on the anvil of the high-pressure chamber is a platinum and copper oxide film with a thickness of 20 nm.
[0172] In S115, the distance within a certain range after opening is 0.5mm;
[0173] In S13, the pressure used to seal the mixture of hydrogen and carbon monoxide is 800 MPa.
[0174] In S2, the pressurization rate is 2 GPa / min, the target pressure is 25 GPa, and the pressure is maintained for 60 min.
[0175] In S2, the prepared pH / CO is bright black and has a density of approximately 5 g / cm³. 3 ;
[0176] In S3, the volume of pH / CO is 90% of the volume of the high-pressure chamber.
[0177] In S44, the pressure required to encapsulate liquid carbon monoxide is 800 MPa.
[0178] In S4, the volume ratio of liquid carbon monoxide to pH / CO material in the high-pressure chamber is 1:9.
[0179] In S5, the pressurization rate is 2 GPa / min; the target pressure is 60 GPa, and it is maintained for 30 min.
[0180] In S5, the prepared p-COH-III energetic material was a black solid with a density of approximately 4.6 g / cm³. 3 .
[0181] In the synthesis of p-COH-III energetic materials, the polymerization of H / CO and the formation of p-COH samples were detected by Raman spectroscopy, which will not be described in detail here.
[0182] As shown in Comparative Example 4, without a catalyst, the synthesis pressure of p-COH-III in S2 was 30 GPa and in S5 was 80 GPa. In contrast, in this example, the synthesis pressure of p-COH-III in S2 decreased from 30 GPa to 25 GPa, a reduction of 5 GPa; in this example, the synthesis pressure of p-COH-III in S5 decreased from 80 GPa to 60 GPa, a reduction of 20 GPa.
[0183] To illustrate the beneficial effect of adding a catalyst to reduce reaction pressure, the inventors conducted the following experiments for comparison.
[0184] Comparative Example 1
[0185] This comparative example provides a method for synthesizing a composite structure polymeric COH energetic material. The steps are largely the same as in Example 1, except that:
[0186] In S1, no palladium film is placed on the anvil surface of the high-pressure cavity.
[0187] In S2, the pressurization rate is 2 GPa / min, the target pressure is 7 GPa, and the pressure is maintained for 30 min.
[0188] In S2, the prepared pH / CO material is glossy black with a density of approximately 2.7 g / cm³. 3 ;
[0189] In S44, the pressure required to encapsulate liquid carbon monoxide is 500 MPa.
[0190] In S5, the pressurization rate is 2 GPa / min; the target pressure is 7 GPa, and it is maintained for 30 min.
[0191] In S5, the prepared p-COH-II energetic material was a black solid with a density of approximately 2.6 g / cm³. 3 .
[0192] Comparative Example 2
[0193] This comparative example provides a method for synthesizing a composite structure polymeric COH energetic material. The steps are largely the same as in Example 2, except that:
[0194] In S1, no gold film is placed on the anvil surface of the high-pressure chamber.
[0195] Therefore, in S13, the pressure used to seal the mixture of hydrogen and carbon monoxide is 300 MPa;
[0196] In S2, the pressurization rate is 1 GPa / min, the target pressure is 5 GPa, and the pressure is maintained for 30 min.
[0197] In S2, the prepared pH / CO material is light yellow and has a density of approximately 2.3 g / cm3.
[0198] In S3, the volume of the pH / CO material is 80% of the volume of the high-pressure chamber.
[0199] In S44, the pressure required to encapsulate liquid carbon monoxide is 200 MPa.
[0200] In S5, the pressurization rate is 1 GPa / min; the target pressure is 5 GPa, and it is maintained for 20 min.
[0201] In S5, the prepared p-COH-I energetic material was a light yellow solid with a density of approximately 2.2 g / cm³. 3 .
[0202] Comparative Example 3
[0203] This comparative example provides a method for synthesizing a composite structure polymeric COH energetic material. The steps are largely the same as in Example 3, except that:
[0204] In S1, no cerium oxide film is placed on the anvil surface of the high-pressure chamber;
[0205] In S2, the pressurization rate is 1 GPa / min, the target pressure is 20 GPa, and the pressure is maintained for 20 min.
[0206] In S2, the prepared pH / CO material is light yellow in color and has a density of approximately 5.3 g / cm³. 3 ;
[0207] In S3, the volume of the pH / CO material is 80% of the volume of the high-pressure chamber;
[0208] In S44, the pressure required to encapsulate liquid carbon monoxide is 200 MPa;
[0209] In S4, the volume ratio of liquid carbon monoxide to pH / CO material in the high-pressure chamber is 1:4;
[0210] In S5, the pressurization rate is 1 GPa / min; the target pressure is 60 GPa, and it is maintained for 20 min.
[0211] In S5, the prepared p-COH-III energetic material was a black solid with a density of approximately 4.2 g / cm³. 3 .
[0212] Comparative Example 4
[0213] This comparative example provides a method for synthesizing a composite structure polymeric COH energetic material. The steps are largely the same as in Example 4, except that:
[0214] In S1, no platinum and copper oxide films are placed on the anvil surface of the high-pressure chamber;
[0215] In S13, the pressure used to seal the mixture of hydrogen and carbon monoxide is 1 GPa.
[0216] In S2, the pressurization rate is 2 GPa / min, the target pressure is 30 GPa, and the pressure is maintained for 60 min.
[0217] In S2, the prepared pH / CO material is glossy black with a density of approximately 5 g / cm³. 3 ;
[0218] In S3, the volume of the pH / CO material is 90% of the volume of the high-pressure chamber;
[0219] In S44, the pressure required to encapsulate liquid carbon monoxide is 1 GPa;
[0220] In S4, the volume ratio of liquid carbon monoxide to pH / CO material in the high-pressure chamber is 1:9;
[0221] In S5, the pressurization rate is 2 GPa / min; the target pressure is 80 GPa, and it is maintained for 30 min.
[0222] In S5, the prepared p-COH-III energetic material was a black solid with a density of approximately 4.6 g / cm³. 3 .
[0223] Specifically, the p-COH-I, p-COH-II, and p-COH-III energetic materials obtained in Examples 1-4 of the present invention can be stably stored in air for 2-5 days, compared to pure p-CO which can only be stably stored in air for a few hours. The p-COH materials of the present invention have good stability.
[0224] As can be seen from the embodiments and comparative examples of the present invention, by adding a catalyst to the synthesis process of polymeric COH energetic materials, the present invention effectively reduces the pressure required for the synthesis of polymeric COH energetic materials. The pressure is reduced from the existing 5–80 GPa to 3–60 GPa, thus reducing the difficulty of preparing polymeric COH energetic materials and providing technical support for the mass production of polymeric COH energetic materials.
[0225] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.
Claims
1. The application of a catalyst in the synthesis of composite polymeric COH energetic materials, characterized in that, The composite structure polymeric COH energetic material includes polymeric CO and polymeric H / CO; wherein, the polymeric CO coats the polymeric H / CO to form a composite structure, and the polymeric H / CO is formed by H-doped polymeric CO; The catalyst is a palladium film, gold film, cerium oxide film, or platinum and copper oxide film. Using the catalyst in the synthesis of composite structure polymeric COH energetic materials reduces the pressure required for the synthesis of composite structure polymeric COH energetic materials. The method for synthesizing the composite structure polymeric COH energetic material includes the following steps: S1. H2 and CO gases are loaded into the high-pressure chamber, and then the high-pressure chamber is sealed; a catalyst is placed inside the high-pressure chamber. S2. Pressurize the H2 and CO gases in the high-pressure chamber until the target pressure is reached, maintain it for a period of time, then unload the pressure, open the high-pressure chamber, and obtain the polymerized H / CO material. S3. Place the above-mentioned polymerized H / CO material into the high-pressure chamber; wherein, the high-pressure chamber contains a catalyst; S4. Liquefy carbon monoxide gas and fill the high-pressure chamber in S3, then seal the high-pressure chamber. S5. Pressurize the material in the high-pressure cavity described in S4 until the target pressure is reached, maintain it, then unload the pressure and open the high-pressure cavity to obtain the composite structure polymeric COH energetic material. In S1 and S3, the catalyst is deposited into the high-pressure chamber in the form of a thin film; the thickness of the catalyst film is 5nm-50μm.
2. A method for synthesizing a composite-structured polymeric COH energetic material, characterized in that, The synthesis method involves adding a catalyst during a high-pressure reaction. The catalyst is a palladium film, gold film, cerium oxide film, or platinum and copper oxide film, which reduces the pressure required to synthesize the composite structure polymeric COH energetic material. The synthesis method includes the following steps: S1. H2 and CO gases are loaded into the high-pressure chamber, and then the high-pressure chamber is sealed by adjusting the relative positions of the upper and lower anvils of the high-pressure device; wherein, a catalyst is placed in the high-pressure chamber; the catalyst is deposited on the surface of the anvil by magnetron sputtering. S2. Pressurize the H2 and CO gases in the high-pressure chamber until the target pressure is reached, maintain it for a period of time, then unload the pressure, open the high-pressure chamber, and obtain the polymerized H / CO material. S3. Place the above-mentioned polymerized H / CO material into the high-pressure chamber; wherein, the high-pressure chamber contains a catalyst; S4. Liquefy carbon monoxide gas and fill the high-pressure chamber in S3, then seal the high-pressure chamber. S5. Pressurize the material in the high-pressure cavity described in S4 until the target pressure is reached, maintain it, then unload the pressure and open the high-pressure cavity to obtain the composite structure polymeric COH energetic material. In S1 and S3, the catalyst is deposited into the high-pressure chamber in the form of a thin film; the thickness of the catalyst film is 5nm-50μm.
3. The synthesis method according to claim 2, characterized in that, S1 includes: S11. Complete the preparation of pressurization accessories for the high-pressure device; S12. Assemble the high-pressure device pressurizing accessory into the thermostat cavity and seal the thermostat cavity. S13. Load the mixture of carbon monoxide and hydrogen into the high-pressure chamber, and then seal the high-pressure chamber by adjusting the relative positions of the upper and lower anvils of the high-pressure device. S14. Release the remaining carbon monoxide and hydrogen in the thermostat chamber and remove the pressurization accessory of the high-pressure device.
4. The synthesis method according to claim 3, characterized in that, In S13, H2 accounts for 5% to 95% of the molar ratio of the mixed gas.
5. The synthesis method according to any one of claims 2-4, characterized in that, The composite polymeric COH energetic material prepared by the synthesis method is a solid with a density of 2 g / cm³. 3 ~ 6 g / cm 3 .