A method for synthesizing boron phosphide polycrystal bulk body in one step with amorphous boron source and phosphorus source

Abstract

The present application is suitable for the technical field of boron phosphide polycrystal synthesis, and provides a method for synthesizing boron phosphide polycrystal blocks by one-step method with amorphous boron source and phosphorus source, comprising the following steps: fully ball-milling and mixing amorphous boron powder and amorphous phosphorus powder; pressing the raw materials into a cylinder; placing the cylinder in a high-pressure assembly, and then placing the high-pressure assembly into the cavity of a cubic press, and heating under the conditions of a pressure of 2-5 GPa and a temperature of 950-1350 DEG C for 60 min. The present application also provides a boron phosphide polycrystal block and its application in preparing high-heat-dissipation devices. The present application adopts a domestic cubic press to synthesize boron phosphide polycrystal ceramic sintered bodies by one-step method under high temperature and high pressure, and has the advantages of low cost, short time, simple process, low pressure and high yield. The synthesized samples have the characteristics of simple process, high hardness and high thermal conductivity, and have very wide application potential, and can be used in super-hard inorganic compounds, refractory materials, high-heat-dissipation devices or ships, and can prevent the corrosion of seawater on the hull and parts.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of boron phosphide polycrystal synthesis, and particularly relates to a method for synthesizing boron phosphide polycrystal blocks by one-step method with amorphous boron source and phosphorus source. BACKGROUND

[0002] With the continuous development of science and technology and the continuous progress of urbanization, the demand for high-performance materials is also increasing, and boron phosphide materials have begun to attract people's attention because of their unique performance. The boron phosphide material has a hardness of 32Gpa under a load of 100g; the density is 2.90g / cm 3 , which is a material with relatively large density; has good thermal conductivity and thermal stability; in the optical aspect, the thin film has good light transmittance in a wide waveband range and good corrosion resistance; and has good chemical stability and generally does not react with concentrated acid and alkali solution.

[0003] Although the boron phosphide material has good performance, it is relatively difficult to synthesize under normal pressure, but it can be relatively simply synthesized under high pressure. Generally, the conventional method for preparing boron phosphide material is as follows:

[0004] The method of thermal decomposition of PCl3·BCl3 can prepare the target material, but the process is relatively complex, and the product quality is unstable;

[0005] The method of boron and zinc phosphide or phosphine reaction is relatively difficult to obtain zinc phosphide and phosphine, and the cost is relatively high, and there may be a problem of generating dangerous gas in the reaction process, which has certain safety hazards;

[0006] The method of using crystalline boron and elemental phosphorus synthesis requires relatively high conditions, higher pressure and temperature to synthesize the target product, and usually needs to use metal nickel as a catalyst, and cannot synthesize polycrystal;

[0007] The chemical vapor deposition method needs to place the silicon substrate with a catalyst in a sealed tube furnace filled with inert gas protection, then vacuumize, raise to a certain temperature, and then introduce boron source and phosphorus source precursor to react to obtain the target product, which has low production efficiency, consumes long time and cost, and has potential hazards of reaction source and tail gas.

[0008] The above conventional methods are difficult to obtain boron phosphide polycrystal ceramic sintered body, and the current preparation method of boron phosphide has many problems, or the performance of the prepared sample is not ideal, and there is a lot of room for improvement in application. Therefore, it is of great practical significance to develop a new preparation method of boron phosphide material and expand its application field. SUMMARY

[0009] The embodiment of the present application aims to provide a method for synthesizing boron phosphide polycrystal bulk body by one-step method with amorphous boron source and phosphorus source, aiming to solve the problems in the background art.

[0010] The embodiment of the present application is implemented in a method for synthesizing boron phosphide polycrystal bulk body by one-step method with amorphous boron source and phosphorus source, comprising the following steps:

[0011] (1) mixing amorphous boron powder and amorphous phosphorus powder by ball milling;

[0012] (2) pressing the raw materials into a cylinder;

[0013] (3) placing the cylinder in a high-pressure assembly, and then placing the high-pressure assembly in the cavity of a cubic anvil press, and heating for 60 min under the conditions of a pressure of 2-5 GPa and a temperature of 950-1350℃.

[0014] Preferably, in step (1), the molar ratio of the amorphous boron powder and the amorphous phosphorus powder is 1:1.

[0015] Preferably, in step (1), the purity of the amorphous boron powder is 90%.

[0016] Preferably, in step (1), the purity of the amorphous boron powder is 99%.

[0017] Preferably, in step (1), the purity of the amorphous phosphorus powder is 98.5%.

[0018] Preferably, in step (2), the raw materials are pressed into a cylinder under the condition of 3 Mpa, with a diameter of 10 mm and a height of 4 mm.

[0019] Another object of the embodiment of the present application is to provide a boron phosphide polycrystal bulk body synthesized by the above method.

[0020] Another object of the embodiment of the present application is to provide an application of the above boron phosphide polycrystal bulk body in preparing high-heat-dissipation devices.

[0021] The method for synthesizing boron phosphide polycrystal bulk body by one-step method with amorphous boron source and phosphorus source provided by the embodiment of the present application adopts domestic cubic anvil press, uses amorphous boron powder (amorphous boron powder) and amorphous phosphorus powder as raw materials, and synthesizes boron phosphide polycrystal ceramic sintering body by one-step method under high temperature and high pressure, which has the characteristics of low cost, short synthesis time, simple synthesis process, low synthesis pressure, low synthesis temperature, and high yield; the synthesized sample has the characteristics of simple process, high hardness, and high thermal conductivity, and has very broad application potential, and can be used in super-hard inorganic compounds, refractory materials, high-heat-dissipation devices, ships, and the like, and can prevent the corrosion of seawater on the hull and parts. BRIEF DESCRIPTION OF DRAWINGS

[0022] Figure 1 A sample picture of the sample prepared for the embodiment 1 of the present application is provided;

[0023] Figure 2 A scanning electron microscope picture of the sample prepared for the embodiment 1 of the present application is provided;

[0024] Figure 3 An X-ray diffraction pattern of the sample prepared for the embodiment 1 of the present application is provided;

[0025] Figure 4 An X-ray diffraction pattern of the sample prepared for the embodiment 8 of the present application is provided;

[0026] Figure 5 An X-ray diffraction pattern of the amorphous boron powder with a purity of 90% used in the embodiment of the present application is provided;

[0027] Figure 6 An X-ray diffraction pattern of the amorphous phosphorus powder used in the embodiment of the present application is provided. DETAILED DESCRIPTION

[0028] In order to make the objects, technical solutions and advantages of the present application clearer, the present application will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and should not be used to limit the present application.

[0029] The embodiment of the present application uses amorphous boron powder (amorphous boron powder) and amorphous phosphorus powder as raw materials, wherein the purity of the amorphous boron powder is 90% or 99%, and the X-ray diffraction pattern of the amorphous boron powder (amorphous boron powder) with a purity of 90% is as shown in Figure 5 The amorphous phosphorus powder can be specifically amorphous red phosphorus powder with a purity of 98.5%, and the X-ray diffraction pattern of the amorphous red phosphorus powder is as shown in Figure 6 .

[0030] The specific implementation of the present application will be described in detail below in combination with specific embodiments.

[0031] Embodiment one, a boron phosphide polycrystal block, a synthesis method thereof includes the following steps:

[0032] (1)Take the purity of 99% amorphous boron powder (amorphous boron powder) and the purity of 98.5% of the initial raw material of non-crystalline red phosphorus with a mole ratio of 1:1, then put the selected raw materials into the planetary ball mill and mix uniformly, then put the mixed raw materials into the mold and pre-press into a cylinder under 3Mpa, then put it into the high-pressure assembly, wherein the outermost layer of the high-pressure assembly is wrapped by talc block, the peripheral center is a steel cap, then copper sheet and graphite sheet, then the sintered cylindrical liner pipe composed of magnesium oxide and aluminum oxide, the inner layer is a layer of graphite close to the inner wall, the liner pipe is closed at both ends by the plug sintered by magnesium oxide and aluminum oxide, and the inside is the sample, and the periphery of the sample is protected by molybdenum and insulating ring.

[0033] (2)Put the assembled high-pressure assembly into the synthesis cavity of the six-surface press, heat for 60min at a pressure of 4Gpa and a temperature of 1150℃, then cool and decompress, and the boron phosphide polycrystalline ceramic sintered body can be obtained.

[0034] Example two, a boron phosphide polycrystalline block, the synthesis method comprising the following steps:

[0035] (1)Take the purity of 99% amorphous boron powder (amorphous boron powder) and the purity of 98.5% of the initial raw material of non-crystalline red phosphorus with a mole ratio of 1:1, then put the selected raw materials into the planetary ball mill and mix uniformly, then put the mixed raw materials into the mold and pre-press into a cylinder under 3Mpa, then put it into the high-pressure assembly, wherein the outermost layer of the high-pressure assembly is wrapped by talc block, the peripheral center is a steel cap, then copper sheet and graphite sheet, then the sintered cylindrical liner pipe composed of magnesium oxide and aluminum oxide, the inner layer is a layer of graphite close to the inner wall, the liner pipe is closed at both ends by the plug sintered by magnesium oxide and aluminum oxide, and the inside is the sample, and the periphery of the sample is protected by molybdenum and insulating ring.

[0036] (2)Put the assembled high-pressure assembly into the synthesis cavity of the six-surface press, heat for 60min at a pressure of 4Gpa and a temperature of 1150℃, then cool and decompress, and the boron phosphide polycrystalline ceramic sintered body can be obtained.

[0037] Example three, a boron phosphide polycrystalline block, the synthesis method comprising the following steps:

[0038] (1)Take the purity of 99% amorphous boron powder (amorphous boron powder) and the purity of 98.5% of the initial raw material of non-crystalline red phosphorus with a mole ratio of 1:1, then put the selected raw materials into the planetary ball mill and mix uniformly, then put the mixed raw materials into the mold and pre-press into a cylinder under 3Mpa, then put it into the high-pressure assembly, wherein the outermost layer of the high-pressure assembly is wrapped by talc block, the peripheral center is a steel cap, then copper sheet and graphite sheet, then the sintered cylindrical liner pipe composed of magnesium oxide and aluminum oxide, the inner layer is a layer of graphite close to the inner wall, the liner pipe is closed at both ends by the plug sintered by magnesium oxide and aluminum oxide, and the inside is the sample, and the periphery of the sample is protected by molybdenum and insulating ring.

[0039] (2)Put the assembled high-pressure assembly into the synthesis cavity of the six-surface press, heat for 60min at a pressure of 4Gpa and a temperature of 950℃, then cool and decompress, and the boron phosphide polycrystalline ceramic sintered body can be obtained.

[0040] Example four, a boron phosphide polycrystalline block, the synthesis method comprising the following steps:

[0041] (1)Take the purity of 99% amorphous boron powder (amorphous boron powder) and the purity of 98.5% of the initial raw material of non-crystalline red phosphorus with a mole ratio of 1:1, then put the selected raw materials into the planetary ball mill and mix uniformly, then put the mixed raw materials into the mold and pre-press into a cylinder under 3Mpa, then put it into the high-pressure assembly, wherein the outermost layer of the high-pressure assembly is wrapped by talc block, the peripheral center is a steel cap, then copper sheet and graphite sheet, then the sintered cylindrical liner pipe composed of magnesium oxide and aluminum oxide, the inner layer is a layer of graphite close to the inner wall, the liner pipe is closed at both ends by the plug sintered by magnesium oxide and aluminum oxide, and the inside is the sample, and the periphery of the sample is protected by molybdenum and insulating ring.

[0042] (2)Put the assembled high-pressure assembly into the synthesis cavity of the six-surface press, heat for 60min at a pressure of 4Gpa and a temperature of 1250℃, then cool and decompress, and the boron phosphide polycrystalline ceramic sintered body can be obtained.

[0043] Example five, a boron phosphide polycrystalline block, the synthesis method comprising the following steps:

[0044] (1)Take the purity of 99% amorphous boron powder (amorphous boron powder) and the purity of 98.5% of the initial raw material of non-crystalline red phosphorus with a mole ratio of 1:1, then put the selected raw materials into the planetary ball mill and mix uniformly, then put the mixed raw materials into the mold and pre-press into a cylinder under 3Mpa, then put it into the high-pressure assembly, wherein the outermost layer of the high-pressure assembly is wrapped by talc block, the peripheral center is a steel cap, then copper sheet and graphite sheet, then the sintered cylindrical liner pipe composed of magnesium oxide and aluminum oxide, the inner layer is a layer of graphite close to the inner wall, the liner pipe is closed at both ends by the plug sintered by magnesium oxide and aluminum oxide, and the inside is the sample, and the periphery of the sample is protected by molybdenum and insulating ring.

[0045] (2)Put the assembled high-pressure assembly into the synthesis cavity of the six-surface press, heat for 60min at a pressure of 3Gpa and a temperature of 1150℃, then cool and decompress, and the boron phosphide polycrystalline ceramic sintered body can be obtained.

[0046] Example six, a boron phosphide polycrystalline block, the synthesis method comprising the following steps:

[0047] (1)Take the purity of 99% amorphous boron powder (amorphous boron powder) and the purity of 98.5% of the initial raw material of non-crystalline red phosphorus with a mole ratio of 1:1, then put the selected raw materials into the planetary ball mill and mix uniformly, then put the mixed raw materials into the mold and pre-press into a cylinder under 3Mpa, then put it into the high-pressure assembly, wherein the outermost layer of the high-pressure assembly is wrapped by talc block, the peripheral center is a steel cap, then copper sheet and graphite sheet, then the sintered cylindrical liner pipe composed of magnesium oxide and aluminum oxide, the inner layer is a layer of graphite close to the inner wall, the liner pipe is closed at both ends by the plug sintered by magnesium oxide and aluminum oxide, and the inside is the sample, and the periphery of the sample is protected by molybdenum and insulating ring;

[0048] (2)Put the assembled high-pressure assembly into the synthesis cavity of the six-surface press, heat for 60min at a pressure of 2Gpa and a temperature of 1150℃, then cool and decompress, and the boron phosphide polycrystalline ceramic sintered body can be obtained.

[0049] Example seven, a boron phosphide polycrystalline block, the synthesis method comprising the following steps:

[0050] (1)Take the purity of 99% amorphous boron powder (amorphous boron powder) and the purity of 98.5% of the initial raw material of non-crystalline red phosphorus with a mole ratio of 1:1, then put the selected raw material into the planetary ball mill and mix uniformly, then put the mixed raw material into the mold and pre-press into a cylinder under 3Mpa, then put it into the high-pressure assembly, wherein the outermost layer of the high-pressure assembly is wrapped by talc block, the peripheral center is a steel cap, then copper sheet and graphite sheet, then the sintered cylindrical liner pipe composed of magnesium oxide and aluminum oxide, the inner layer is a layer of graphite close to the inner wall, the liner pipe is closed at both ends by the plug sintered by magnesium oxide and aluminum oxide, and the inside is the sample, and the periphery of the sample is protected by molybdenum and insulating ring.

[0051] (2)Put the assembled high-pressure assembly into the synthesis cavity of the six-surface press, heat for 60min at a pressure of 5Gpa and a temperature of 1150℃, then cool and decompress, and the boron phosphide polycrystalline ceramic sintered body can be obtained.

[0052] Example eight, a boron phosphide polycrystalline block, the synthesis method comprising the following steps:

[0053] (1)Take the purity of 99% amorphous boron powder (amorphous boron powder) and the purity of 98.5% of the initial raw material of non-crystalline red phosphorus with a mole ratio of 1:1, then put the selected raw material into the planetary ball mill and mix uniformly, then put the mixed raw material into the mold and pre-press into a cylinder under 3Mpa, then put it into the high-pressure assembly, wherein the outermost layer of the high-pressure assembly is wrapped by talc block, the peripheral center is a steel cap, then copper sheet and graphite sheet, then the sintered cylindrical liner pipe composed of magnesium oxide and aluminum oxide, the inner layer is a layer of graphite close to the inner wall, the liner pipe is closed at both ends by the plug sintered by magnesium oxide and aluminum oxide, and the inside is the sample, and the periphery of the sample is protected by molybdenum and insulating ring.

[0054] (2)Put the assembled high-pressure assembly into the synthesis cavity of the six-surface press, heat for 60min at a pressure of 5Gpa and a temperature of 1150℃, then cool and decompress, and the boron phosphide polycrystalline ceramic sintered body can be obtained.

[0055] Example nine, a boron phosphide polycrystalline block, the synthesis method comprising the following steps:

[0056] (1) Take the initial raw material of amorphous boron powder (amorphous boron powder) with a purity of 90% and amorphous red phosphorus with a purity of 98.5% in a molar ratio of 1:1, then put the selected raw material into a planetary ball mill for mixing, then put the mixed raw material into a mold for pre-pressing into a cylinder under 3Mpa, then put it into a high-pressure assembly, wherein the outermost layer of the high-pressure assembly is wrapped with a block of pyrophyllite, the peripheral center is a steel cap, then copper and graphite sheets, then a sintered cylindrical liner pipe composed of magnesium oxide and aluminum oxide, the inner layer of which is a layer of graphite close to the inner wall, the two ends of the liner pipe are closed by plugs sintered from magnesium oxide and aluminum oxide, and the inside is the sample, which is protected by molybdenum and an insulating ring;

[0057] (2) Put the assembled high-pressure assembly into the synthesis cavity of the six-surface press, heat for 60min at a pressure of 5Gpa and a temperature of 1150℃, then cool and decompress to obtain a boron phosphide polycrystalline ceramic sintered body.

[0058] Example Ten, a boron phosphide polycrystalline block, the synthesis method comprising the following steps:

[0059] (1) Take the initial raw material of amorphous boron powder (amorphous boron powder) with a purity of 90% and amorphous red phosphorus with a purity of 98.5% in a molar ratio of 1:1, then put the selected raw material into a planetary ball mill for mixing, then put the mixed raw material into a mold for pre-pressing into a cylinder under 3Mpa, then put it into a high-pressure assembly, wherein the outermost layer of the high-pressure assembly is wrapped with a block of pyrophyllite, the peripheral center is a steel cap, then copper and graphite sheets, then a sintered cylindrical liner pipe composed of magnesium oxide and aluminum oxide, the inner layer of which is a layer of graphite close to the inner wall, the two ends of the liner pipe are closed by plugs sintered from magnesium oxide and aluminum oxide, and the inside is the sample, which is protected by molybdenum and an insulating ring;

[0060] (2) Put the assembled high-pressure assembly into the synthesis cavity of the six-surface press, heat for 60min at a pressure of 2Gpa and a temperature of 1150℃, then cool and decompress to obtain a boron phosphide polycrystalline ceramic sintered body.

[0061] Performance test:

[0062] The sample prepared in Example 1 was analyzed, and the actual photo is as shown in Figure 1 The sample is a small disc with a diameter of 10mm and a height of 4mm, the sintering density is 2.85g / cm 3 , the compactness is close to 98.3%, the electrical conductivity is 4S / m, and the structure is zinc blende structure. Figure 2 The sample prepared in Example 7 was analyzed, and the scanning electron microscope picture is as shown in Under the electron microscope, the grain size is micron level.

[0063] The X-ray diffraction pattern of the sample prepared in Example 8 is shown in Figure 3 The X-ray diffraction pattern of the sample prepared in Example 1 is shown in Figure 4 The X-ray diffraction pattern of the sample prepared in Example 1 is shown in

[0064] The above description is only the preferred embodiment of the application, not to limit the application, any modification, equivalent replacement and improvement within the spirit and principle of the application should be included in the protection scope of the application.

Claims

1. A method for synthesizing boron phosphide polycrystalline bulk in one step from an amorphous boron source and a phosphorus source, characterized in that, The method comprises the following steps: (1) mixing amorphous boron powder and amorphous phosphorus powder by ball milling, wherein the molar ratio of the amorphous boron powder to the amorphous phosphorus powder is 1:1; (2) pressing the raw materials into a cylinder under the condition of 3Mpa; (3) placing the cylinder into a high-pressure assembly, and then placing the high-pressure assembly into a cavity of a cubic press, and heating under the condition of a pressure of 2GPa and a temperature of 950-1350℃ for 60min.

2. The method of claim 1, wherein the method of synthesizing boron phosphide polycrystalline bulk with amorphous boron source and phosphorus source in one step is characterized by, In step (1), the purity of the amorphous boron powder is 90%.

3. The method of claim 1, wherein the method of synthesizing boron phosphide polycrystalline bulk with amorphous boron source and phosphorus source in one step is characterized by, In step (1), the purity of the amorphous boron powder is 99%.

4. The method of claim 1, wherein the method of synthesizing boron phosphide polycrystalline bulk with amorphous boron source and phosphorus source in one step is characterized by, In step (1), the purity of the amorphous phosphorus powder is 98.5%.

5. The method of claim 1, wherein the method of synthesizing boron phosphide polycrystalline bulk with amorphous boron source and phosphorus source in one step is characterized by, In step (2), the diameter of the cylinder is 10mm, and the height is 4mm.

6. A poly crystalline boron phosphide bulk body, characterized by, The boron phosphide polycrystal block is synthesized by the method according to any one of claims 1-5.

7. Use of the boron phosphide polycrystal block according to claim 6 in the preparation of a high-heat-dissipation device.

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