Diamond electrode material deposition apparatus, diamond electrode material, and method of manufacturing the same

Abstract

This invention belongs to the field of conductive diamond electrode material preparation technology, specifically relating to diamond electrode material deposition equipment, diamond electrode materials, and their preparation methods. The deposition equipment includes a drum and a heating element. The drum has openings at both ends, and the heating element is located inside the drum and extends from the openings. The heating element is positioned between the central axis of the drum and the inner wall of the drum. One end of the drum has a first mounting base with a first through hole, the center of which is located on the central axis of the drum. A tubular or rod-shaped electrode substrate is fixed inside the drum cavity through the first through hole, and a particle electrode substrate is laid on the inner wall of the drum, thereby achieving simultaneous deposition of BDD films on both the tubular or rod-shaped electrode substrate and the particle electrode substrate. As the drum rotates, the BDD film deposition on the surfaces of both the tubular or rod-shaped electrode substrate and the particle electrode substrate becomes uniform.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of preparation of conductive diamond electrode material, and particularly relates to a diamond electrode material deposition device, a diamond electrode material and a preparation method thereof. BACKGROUND

[0002] Since the conductive diamond electrode (generally realized by doping boron in diamond, also known as BDD electrode) material generates effective components of ozone and hydroxyl radicals in water through direct current electrolysis, both of which have strong oxidizing properties and can oxidize and decompose organic pollutants in wastewater, the conductive diamond electrode material is often used for treatment of toxic and harmful organic wastewater generated in chemical, dyeing, pharmaceutical, livestock and other industries, as well as organic wastewater with complex components such as landfill leachate and membrane concentrate. In addition to the advantages of high oxygen evolution potential and high electrocatalytic activity, the BDD electrode also has excellent chemical stability and can resist electrode loss caused by electrochemical corrosion in long-term electrolysis application. Compared with noble metal electrode materials, the BDD electrode has the advantage of not being limited by the stock of mineral resources.

[0003] The existing organic wastewater treatment technology often uses plate-shaped BDD electrodes, but since the effective specific surface area of the plate-shaped BDD electrodes is low, the contact area with organic pollutants is small, resulting in extremely low water treatment efficiency. In addition, regarding the preparation of BDD electrodes, the existing technology mostly adopts a flat wire type hot wire CVD deposition process, but this deposition process can only realize planar deposition, and when the BDD particle electrode substrate or the columnar electrode substrate surface is deposited, multiple implementations are needed to ensure that a uniform film layer is deposited on the entire surface, which has the disadvantages of high deposition cost and low efficiency. SUMMARY

[0004] In view of the above problems, the present application designs a diamond electrode material deposition device, which comprises a roller and a heating body,

[0005] Both ends of the roller are provided with openings, and the heating body is located inside the roller and extends out of the openings; the openings can be small holes in the end walls of the roller or open ends at both ends of the roller;

[0006] The heating body is located between the central axis of the roller and the inner wall of the roller;

[0007] One end of the roller is provided with a first mounting seat, and the first mounting seat is provided with a first through hole, and the center of the first through hole is located on the central axis of the roller.

[0008] Compared with the prior art, the beneficial effects of the present application are that the columnar electrode base can be fixed in the inner cavity of the roller through the first through hole, and the particle electrode base can be laid on the inner wall of the roller, so that the BDD film layer is simultaneously deposited on the columnar electrode base and the particle electrode base, and as the roller rotates, the BDD film layer on the surface of the columnar electrode base and the particle electrode base can be uniformly deposited, which is beneficial to improve the deposition efficiency and reduce the cost. By using the deposition equipment of the present application, the columnar electrode material and the particle electrode material required by a water treatment unit can be obtained through one-time deposition, which greatly improves the deposition efficiency.

[0009] Preferably, the heating body comprises a plurality of heating wires, which are uniformly arranged along the circumferential direction of the central axis of the roller. More preferably, the heating wires are tantalum wires and / or tungsten wires.

[0010] The beneficial effects of the present preferred embodiment are that the heating wires are uniformly arranged along the circumferential direction of the central axis of the roller, which can make the columnar electrode base and the particle electrode base in the roller be uniformly heated, thereby facilitating the deposition of a uniform film layer on the surface of the base.

[0011] Preferably, the rotating speed of the roller is 0.5-6 r / h.

[0012] The beneficial effects of the present preferred embodiment are that the roller rotates at a fixed speed and time, which can make the particle electrode base roll, turn over or flow with the roller, thereby facilitating the deposition of a uniform film layer on the surface of the particle electrode base, while taking into account the efficiency and not causing the electrode base particles to move in a parabolic motion at a high place and fall to damage the heating wires.

[0013] Preferably, a plurality of separation ribs are arranged in the roller,

[0014] The separation ribs are uniformly arranged on the inner wall of the roller along the circumferential direction of the central axis of the roller.

[0015] The beneficial effects of the present preferred embodiment are that the separation ribs help to ensure that the particle electrode base rolls, turns over or flows, and further ensure that a uniform film layer is deposited on the surface of the particle electrode base.

[0016] Preferably, the length of the separation rib is the same as the length of the roller.

[0017] The beneficial effects of the present preferred embodiment are that the length of the separation rib is the same as the length of the roller, which can ensure that the particle electrode base laid on the inner wall of the roller can roll, turn over or flow under the auxiliary action of the separation rib.

[0018] Preferably, the vertical cross-sectional shape of the separation rib is any one of a rectangle, a triangle and an arc. More preferably, the vertical cross-sectional shape of the separation rib is a triangle and / or an arc.

[0019] The beneficial effect of the preferred embodiment is that the vertical cross-sectional shape of the partitioning ribs is triangular and arc-shaped, which can ensure that the particle electrode substrate is turned over under the action of the partitioning ribs and will not be stuck on the partitioning ribs, and is conducive to ensuring that the surface of the particle electrode substrate can deposit a uniform film layer.

[0020] Preferably, the height of the partitioning ribs is 0.1-1 mm. Further preferably, the height of the partitioning ribs is 0.15-0.5 mm.

[0021] The beneficial effect of the preferred embodiment is that by limiting the height of the partitioning ribs, the particle electrode substrate can be turned over under the action of the partitioning ribs, and the particle electrode substrate can be prevented from being stuck on the partitioning ribs due to the partitioning ribs being too high, and from colliding with the heating body due to the turning force being too large when turning down from a high position, which can cause damage to the heating body, and is conducive to ensuring the safety and deposition efficiency of the deposition equipment.

[0022] Preferably, the heating body comprises a plurality of heating wires, and the heating wires are arranged along the circumference of the central axis of the roller,

[0023] The number of the partitioning ribs is the same as the number of the heating wires.

[0024] Preferably, any of the heating wires is located between two adjacent partitioning ribs, and the distance between the heating wire and the two partitioning ribs is the same.

[0025] The beneficial effect of the preferred embodiment is that the particle electrode substrate is fully laid between adjacent partitioning ribs, and the heating wire is arranged directly above the middle line between the two partitioning ribs, which is conducive to making the distance between the particle electrode substrate and the heating wire consistent, ensuring uniform heating and consistent BDD film layer deposition thickness.

[0026] Preferably, the two ends of the roller are respectively provided with a first mounting seat and a second mounting seat, and the two ends of the heating body are respectively connected with the first mounting seat and the second mounting seat,

[0027] The first mounting seat and / or the second mounting seat is connected with a tensioning device, and the tensioning device is located on the outer side of the roller.

[0028] The beneficial effect of the preferred embodiment is that the heating wire is easily expanded and elongated at high temperature, and the first mounting seat and / or the second mounting seat is pulled tight by the tensioning device, so that the heating wire can be kept in a straight state, which can prevent the heating wire from sagging due to lengthening, and can prevent the surface of the columnar electrode substrate and the particle electrode substrate from being unevenly heated.

[0029] Preferably, the tensioning device comprises several high-temperature-resistant springs, and a third mounting base, two ends of the high-temperature-resistant springs are connected with the first mounting base and the third mounting base or connected with the second mounting base and the third mounting base. Preferably, the tension of the high-temperature-resistant spring is 0.4-7 N, and the relationship between the tension increment of the high-temperature-resistant spring and the length increment of the heat-generating body is 0.0015-0.007 N / mm.

[0030] The beneficial effect of the preferred embodiment is that the third mounting base is fixedly connected with the external device, used for controlling the tension of the high-temperature-resistant spring, so that the heating wire connected with the first mounting base and the second mounting base is kept in a flat state, which is beneficial to ensure that the columnar electrode base and the particle electrode base are uniformly heated.

[0031] Preferably, the second mounting base is provided with a second through hole, and the center of the second through hole is located on the central axis of the drum.

[0032] The beneficial effect of the preferred embodiment is that the heating wire is mounted on the first mounting base and the second mounting base, the columnar electrode base is fixed in the inner cavity of the drum through the first through hole and the second through hole, which can ensure that the heating wire is arranged along the circumference of the columnar electrode base, and is beneficial to uniformly heat the surface of the columnar electrode base and deposit a uniform film layer, thereby improving the deposition efficiency.

[0033] Preferably, the deposition device further comprises a reaction cavity, the drum and the first mounting base are located in the reaction cavity, the heat-generating body is mounted in the reaction cavity through the first mounting base and the second mounting base,

[0034] The drum is rotationally connected with the reaction cavity through a driving device.

[0035] The beneficial effect of the preferred embodiment is that the reaction cavity is a vacuum environment, the heat-generating body is fixed through the first mounting base and the second mounting base, and the drum rotates in the reaction cavity, which is beneficial to uniformly heat the surfaces of the columnar electrode base and the particle electrode base and deposit a uniform film layer.

[0036] The application designs a preparation method of diamond electrode material, which is prepared by using the above-mentioned deposition device, and comprises the following steps:

[0037] The rod-shaped or tubular electrode base is fixed in the inner cavity of the drum through the first through hole and / or the second through hole;

[0038] The particle electrode base is arranged between the partition ribs below the heat-generating body;

[0039] The deposition device is placed in a vacuum device, and borane, hydrogen and methane are introduced into the vacuum device, wherein the molar ratio B / C of boron to carbon is 0.2%-1.5%, and the volume ratio CH4 / H2 of methane to hydrogen is 1.5%-5%.

[0040] The electrode base is deposited to obtain a diamond electrode material.

[0041] Compared with the prior art, the present application has the advantages that the present application can simultaneously deposit rod-shaped or tubular electrode bases and particle electrode bases, and can make the surface film layer of the base uniformly deposited, so that the columnar electrode material and the particle electrode material required by a water treatment unit can be obtained only once, which is beneficial to improve the deposition efficiency and reduce the cost.

[0042] Preferably, the diameter of the rod-shaped electrode base is 3-50 mm, and the thickness of the BDD film layer deposited on the surface of the rod-shaped electrode base is 1-30 um, and is further preferably 8-20 mm.

[0043] The diameter of the tubular electrode base is 5-200 mm, the wall thickness is 1-15 mm, and the thickness of the BDD film layer deposited on the surface of the tubular electrode base is 1-30 um, and is further preferably 10-15 mm.

[0044] The present preferred embodiment has the advantages that if the deposited film layer is too thin, the coverage is poor, resulting in poor water treatment effect; and if the deposited film layer is too thick, it is easy to be affected by stress, causing the BDD film layer to separate from the base, thereby reducing the water treatment capacity. Therefore, by limiting the thickness of the BDD film layer, the present preferred embodiment can ensure that the diamond electrode material has good water treatment capacity.

[0045] Preferably, the particle electrode base is in the shape of a cylinder and / or a sphere, wherein the diameter of the cylindrical particle electrode base is 0.5-3 mm, and the ratio of the diameter to the height is 0.3-2; and the diameter of the spherical particle electrode base is 0.5-3 mm.

[0046] Preferably, the material of the rod-shaped electrode base, the tubular electrode base, and the particle electrode base is any one or more of niobium, tantalum, monocrystalline silicon, silicon carbide, silicon nitride, titanium, copper / nickel composite, and graphite / titanium composite.

[0047] Preferably, the distance L1 from the heating wire to the surface of the rod-shaped or tubular electrode base is 5-35 mm, and is further preferably 15-35 mm.

[0048] The distance L2 from the heating wire to the surface of the particle electrode base is 7-35 mm, and is further preferably 17-35 mm; and more preferably, the difference between the distance L1 and the distance L2 is not greater than 5 mm.

[0049] The present preferred embodiment has the advantages that by limiting the distance L1 and the distance L2, the distance from the rod-shaped or tubular electrode base and the particle electrode base to the heating wire can be as same as possible, and the deposition completion time of the rod-shaped or tubular electrode base and the particle electrode base can be the same or close, which is beneficial to improve the deposition efficiency.

[0050] Preferably, the temperature of the heating element is 1700–2200°C, and the temperature of the surface of the rod-shaped or tubular electrode substrate or particle electrode substrate subjected to radiation is 650–1050°C.

[0051] Preferably, the deposition of the electrode substrate includes,

[0052] First, increase the power from 0 kW at a rate of 0.2–5 kW / min.

[0053] Rise to maximum power P max During this period, the deposition time is maintained at 2–100 hours.

[0054] After deposition, at a rate not exceeding 0.05 kW / min, from the maximum power P max Reduced to 2 / 3P max Maintain for 1-2 hours; then at a rate not exceeding 0.05 kW / min, from 2 / 3 P max Reduced to 1 / 3P max After maintaining the temperature for 1-2 hours, reduce the power to 0 kW and wait until the temperature drops below 60℃ before removing the electrode substrate to obtain the diamond electrode material.

[0055] The advantages of this preferred embodiment are as follows: By controlling the temperature of the heating element through power control, this invention can prevent voltage control instability caused by changes in the resistance of the heating element, thus improving the accuracy and stability of the deposition process control. The power reduction mechanism can prevent the separation of the BDD film from the substrate due to thermal stress, thereby improving the bonding strength.

[0056] The present invention also designs a diamond electrode material, which is prepared by the above-described preparation method.

[0057] Compared with the prior art, the beneficial effects of the present invention are as follows: the diamond electrode material includes columnar and particle electrodes. Compared with the plate electrode, the particle electrode can prevent the problem of local BDD layer separation from the substrate and gradual large-area electrode failure after peeling, from small points to large areas, and ensure that the particle electrode will not fail due to the failure of other particle electrode surfaces. Attached Figure Description

[0058] Figure 1 This is a front view of the deposition apparatus of Embodiment 1 of the present invention.

[0059] Figure 2 This is a diagram showing the usage state of the deposition equipment in Embodiment 1 of the present invention.

[0060] Figure 3 This is a side view of the deposition apparatus of Embodiment 1 of the present invention.

[0061] Figure 4This is a diagram showing the usage state of the deposition equipment in Embodiment 2 of the present invention.

[0062] Figure 5 This is a side view of the deposition apparatus of Embodiment 2 of the present invention.

[0063] Figure 6 This is a side view of the deposition apparatus of Embodiment 3 of the present invention.

[0064] Figure 7 This is a side view of the deposition apparatus of Embodiment 5 of the present invention.

[0065] 1-Roller, 2-Heating wire, 3-Separating rib, 4-First mounting base, 41-First through hole, 5-Second mounting base, 51-Second through hole, 61-High temperature resistant spring, 62-Third mounting base, 7-Ring or tubular electrode substrate. Detailed Implementation

[0066] To make the objectives, technical solutions, and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention.

[0067] Example 1

[0068] This embodiment provides a deposition apparatus, such as... Figure 1 As shown, the device includes a drum 1 and a heating element. Both ends of the drum 1 have openings, and the heating element is located inside the drum 1 and extends out from the openings. Optionally, the openings can be holes in the end walls of the drum 1 or open openings at both ends of the drum 1; in this embodiment, an open opening is preferred. The drum 1 has a first mounting base 4 and a second mounting base 5 at its two ends, respectively. The heating element includes a plurality of heating wires 2, both ends of which are connected to the first mounting base 4 and the second mounting base 5, and are evenly arranged circumferentially along the central axis of the drum 1. Preferably, in this embodiment, the length of the heating wires 2 is 400 mm, and the diameter of the drum 1 is 80 mm. Optionally, the heating wires 2 are tantalum wires and / or tungsten wires. The first mounting base 4 has a first through hole 41, and the second mounting base 5 has a second through hole 51. The centers of the first through hole 41 and the second through hole 51 are located on the central axis of the drum 1. Using the deposition equipment of this embodiment, columnar electrode material and particle electrode material required for a water treatment unit can be obtained through a single deposition, greatly improving deposition efficiency.

[0069] The roller 1 rotates at a speed of 0.5 r / h. This constant rotation speed and timing allows the particle electrode substrate to roll, tumble, or flow with the roller, facilitating the deposition of a uniform film on its surface. Furthermore, the roller 1 contains several dividing ribs 3, which are evenly distributed along the circumference of the roller 1's central axis on its inner wall. The length of each dividing rib is the same as the length of the roller 1. These dividing ribs further ensure that the particle electrode substrate rolls, tumbles, or flows, thereby guaranteeing the deposition of a uniform film on its surface.

[0070] As an optional feature, the vertical cross-sectional shape of the partition rib 3 can be any one of rectangle, triangle, or arc. It should be explained that, in this embodiment, rectangle, triangle, and arc refer to the vertical cross-sectional shape of the portion of the partition rib 3 protruding outward from its connection with the inner wall of the roller 1, with the bottom of the partition rib 3 connected to the inner wall of the roller 1 in an arc shape. Preferably, in this embodiment, the vertical cross-sectional shape of the partition rib 3 is arc-shaped. Figure 3 As shown, this design ensures that the particle electrode substrate flips under the action of the separator 3 without getting stuck on it. The height of the separator 3 is 0.15 mm. By limiting the height of the separator 3, it is possible to ensure that the particle electrode substrate flips under the action of the separator 3, while preventing the particle electrode substrate from getting stuck on the separator 3 due to excessive height. This would prevent the particle electrode substrate from colliding with the heating element due to excessive flipping force when flipping down from a high position, thus damaging the heating element. This helps to ensure the safety and deposition efficiency of the deposition equipment.

[0071] like Figure 3 As shown, the number of separating ribs 3 and the number of heating wires 2 are both 12. Any heating wire 2 is located between two adjacent separating ribs 3, and the distance between the heating wire 2 and the two separating ribs 3 is the same. The particle electrode substrate is completely filled between adjacent separating ribs 3. Placing the heating wire 2 between two separating ribs 3 helps to ensure that the distance between the particle electrode substrate and the heating wire 2 is consistent, thus ensuring uniform heating and consistent BDD film deposition thickness.

[0072] The first mounting seat 4 and / or the second mounting seat 5 is connected with a tensioning device, preferably only the second mounting seat 5 is connected with the tensioning device in the embodiment, and the tensioning device is located outside the roller 1. The heating wire 2 is easy to expand and elongate at high temperature, the first mounting seat 4 and / or the second mounting seat 5 is pulled tight by the tensioning device, so that the heating wire 2 is kept in a straight state, which can prevent the heating wire 2 from sagging due to lengthening, and cause the surface of the columnar electrode base and the particle electrode base to be unevenly heated. The tensioning device comprises several high-temperature-resistant springs 61 and a third mounting seat 62, and the two ends of the high-temperature-resistant spring 61 are connected with the first mounting seat 4 or the second mounting seat 5 and the third mounting seat 62 respectively. Preferably, the tension of the high-temperature-resistant spring 61 is 0.4-7 N, and the relationship between the tension increment of the high-temperature-resistant spring 61 and the length increment of the heating body is 0.0015-0.007 N / mm. The third mounting seat 62 is fixedly connected with an external device, and is used for controlling the tension of the high-temperature-resistant spring 61. For example, the initial tension of the high-temperature-resistant spring 61 is 2 N, and as the heating wire 2 lengthens, the high-temperature-resistant spring 61 retracts, and the tension may be reduced to 1.9 N, so that the heating wire 2 connected with the first mounting seat 4 and the second mounting seat 5 is kept in a straight state, which is conducive to ensuring that the surface of the columnar electrode base and the particle electrode base is evenly heated. Preferably, the first mounting seat 4, the second mounting seat 5 and the third mounting seat 62 are all plate-shaped.

[0073] The embodiment also provides a preparation method of the diamond electrode material, as shown in the figure, the deposition device of the embodiment is used for preparation, and the preparation method comprises the following steps. Figure 2

[0074] S1: The rod-shaped electrode base 7 is subjected to sand blasting treatment by using 300-mesh silicon carbide powder, and the particle electrode base is subjected to ultrasonic treatment by using W20 diamond powder.

[0075] The diameter of the rod-shaped electrode base 7 in the embodiment is 4 mm, the particle electrode base is in a cylindrical shape, the diameter of the cylindrical particle electrode base is 0.5 mm, and the ratio of the diameter to the height is 0.3. The material of the rod-shaped electrode base 7 and the particle electrode base is niobium.

[0076] S2: The rod-shaped electrode base 7 passes through the first through hole 41, the other end of the rod-shaped electrode base 7 is connected with the second mounting plate and is fixed in the inner cavity of the roller 1 and does not rotate with the roller 1.

[0077] S3: The particle electrode base is arranged between the partition ribs 3 below the heating body. There are 12 partition spaces in the roller 1, and the particle electrode base is fully arranged on the inner walls of 4-5 partition spaces in the lower half of the roller 1.

[0078] ​The distance L1 between the heating wire 2 and the surface of the rod electrode base 7 is 19 mm, and the distance L2 between the heating wire 2 and the surface of the particle electrode base is 18.6 mm.

[0079] S4: placing the deposition device in a vacuum device, and introducing borane, hydrogen, and methane into the vacuum device, wherein the molar ratio of boron to carbon B / C is 0.2%, and the volume ratio of methane to hydrogen CH4 / H2 is 1.5%.

[0080] S5: increasing the power from 0 kW to the maximum power P = 30 kW at a power increasing slope of 0.2 kw / min, and maintaining the deposition time for 5 h. The temperature of the heating wire 2 is 1900°C, and the temperature of the surface of the rod electrode base 7 and the particle electrode base subjected to radiation is 850°C. max

[0081] S6: after the deposition is completed, decreasing the power from 30 kW to 20 kW at a rate of 0.04 kw / min, maintaining for 1 h, then decreasing the power from 20 kW to 10 kW at a rate of 0.04 kw / min, maintaining for 1 h, and then directly decreasing the power to 0, and taking out the electrode base when the temperature decreases to 50°C, thereby obtaining the rod and particle diamond electrode materials.

[0082] Example 2

[0083] The deposition device of the present example is different from that of Example 1 in that:

[0084] (1) the length of the heating wire 2 of the deposition device is 200 mm, and the diameter of the roller 1 is 100 mm.

[0085] (2) the rotating speed of the roller 1 is 3 r / h.

[0086] (3) as shown in the figure, the vertical cross-sectional shape of the partition rib 3 is rectangular, and the height of the partition rib 3 is 0.3 mm. Figure 5 (4) the number of the partition rib 3 and the number of the heating wire 2 are both 8.

[0087] The present example also provides a preparation method of a diamond electrode material, as shown in the figure, which is prepared by using the deposition device of the present example, and comprises the following steps:

[0088] Figure 4 S1: performing sand blasting treatment on the tubular electrode base 7 by using 400 mesh silicon carbide powder, and performing ultrasonic treatment on the particle electrode base by using W30 diamond powder.

[0089] S1: performing sand blasting treatment on the tubular electrode base 7 by using 400 mesh silicon carbide powder, and performing ultrasonic treatment on the particle electrode base by using W30 diamond powder.

[0090] ​​In this embodiment, the tubular electrode substrate 7 has a diameter of 5 mm and a wall thickness of 1 mm, and the particle electrode substrate is spherical with a diameter of 1 mm. Both the rod-shaped electrode substrate 7 and the particle electrode substrate are made of tantalum.

[0091] S2: The tubular electrode substrate 7 is passed through the first through hole 41 and the second through hole 51 and fixed in the inner cavity of the roller 1. Both ends of the tubular electrode substrate 7 extend out of the first through hole 41 and the second through hole 51 and do not rotate with the roller 1.

[0092] S3: Place the particle electrode substrate between the partition ribs 3 below the heating element. In this embodiment, the roller 1 has 8 partition spaces, and the inner walls of 2 to 3 partition spaces in the lower half of the roller 1 are covered with particle electrode substrate.

[0093] In this embodiment, the distance L1 from the heating wire 2 to the surface of the rod-shaped electrode substrate 7 is 23 mm, and the distance L2 from the heating wire 2 to the surface of the particle electrode substrate is 24 mm.

[0094] S4: Place the deposition equipment in a vacuum device, and introduce borane, hydrogen, and methane into the vacuum device, wherein the molar ratio of boron to carbon (B / C) is 1%, and the volume ratio of methane to hydrogen (CH4 / H2) is 3%.

[0095] S5: With a power increase slope of 3 kW / min, the power increases from 0 kW to the maximum power P over 3 minutes. max =9kW, maintaining a deposition time of 10h. The temperature of the heating wire 2 is 2000℃, and the surface of the rod-shaped electrode substrate 7 and the particle electrode substrate is irradiated to a temperature of 950℃.

[0096] S6: After deposition, the power is reduced from 9 kW to 6 kW at a rate of 0.03 kW / min and held for 2 hours. Then, the power is reduced from 6 kW to 3 kW at a rate of 0.05 kW / min and held for 1 hour. The power is then reduced to 0. The electrode substrate is removed when the temperature drops to 40°C to obtain tubular and particle diamond electrode materials.

[0097] Example 3

[0098] The deposition apparatus in this embodiment differs from those in embodiments 1 and 2 in that:

[0099] (1) The length of the heating wire 2 of the deposition equipment is 300mm and the diameter of the drum 1 is 70mm.

[0100] (2) The rotational speed of the roller 1 is 6 r / h.

[0101] (3) Figure 6 As shown, the vertical cross-sectional shape of the partition rib 3 is triangular, and the height of the partition rib 3 is 0.5mm.

[0102] (4) The number of the partitioning ribs 3 and the number of the heating wires 2 are both 10.

[0103] The present embodiment also provides a preparation method of diamond electrode material, which is prepared by using the deposition device of the present embodiment, and comprises the following steps:

[0104] S1: The rod-shaped electrode substrate 7 is sandblasted with 500-mesh silicon carbide powder, and the particle electrode substrate is ultrasonically treated with W10 diamond powder.

[0105] The diameter of the rod-shaped electrode substrate 7 in the present embodiment is 40 mm, and the particle electrode substrate is in the shape of a cylinder with a diameter of 3 mm and a diameter-to-height ratio of 2. The rod-shaped electrode substrate 7 and the particle electrode substrate are both made of silicon carbide.

[0106] S2: The rod-shaped electrode substrate 7 is passed through the first through hole 41 and connected to the second mounting plate at the other end, and fixed in the inner cavity of the roller 1 and does not rotate with the roller 1.

[0107] S3: The particle electrode substrate is placed between the partitioning ribs 3 below the heating body. The roller 1 in the present embodiment is provided with 10 partitioning spaces, and the particle electrode substrate is fully laid on the inner walls of 3-4 partitioning spaces in the lower half of the roller 1.

[0108] The distance L1 from the heating wire 2 to the surface of the rod-shaped electrode substrate 7 in the present embodiment is 6.7 mm, and the distance L2 from the heating wire 2 to the surface of the particle electrode substrate is 6.8 mm.

[0109] S4: The deposition device is placed in a vacuum device, and borane, hydrogen and methane are introduced into the vacuum device, wherein the molar ratio of boron to carbon B / C is 1.5%, and the volume ratio of methane to hydrogen CH4 / H2 is 5%.

[0110] S5: The power is increased from 0 kw to the maximum power P = 22 kw at a power increasing slope of 0.6 kw / min for 36.6 min, and the deposition time is kept for 80 h. The temperature of the heating wire 2 is 2200℃, and the temperature of the surface of the rod-shaped electrode substrate 7 and the particle electrode substrate subjected to radiation is 1050℃. max

[0111] S6: After the deposition is completed, the power is decreased from 22 kw to 14.5 kw at a rate of 0.02 kw / min, kept for 1 h, then decreased from 14.5 kw to 7.3 kw at a rate of 0.03 kw / min, kept for 1 h, and then directly decreased to 0, and the temperature is decreased to 30℃, and the electrode substrate is taken out, thereby obtaining the rod-shaped and particle diamond electrode material.

[0112] Example 4​

[0113] The deposition device of the present embodiment is different from that of Embodiment 1 in that:

[0114] (1) The length of the heating wire 2 of the deposition device is 100 mm, and the diameter of the roller 1 is 60 mm.

[0115] (2) The rotating speed of the roller 1 is 5 r / h.

[0116] (3) The vertical cross-sectional shape of the partition rib 3 is rectangular, and the height of the partition rib 3 is 0.4 mm.

[0117] (4) The number of the partition rib 3 and the number of the heating wire 2 are both 8.

[0118] The present embodiment also provides a preparation method of a diamond electrode material, which is prepared by using the deposition device of the present embodiment, and comprises the following steps:

[0119] S1: The tubular electrode base 7 is sandblasted by using 500-mesh silicon carbide powder, and the particle electrode base is ultrasonically treated by using W30 diamond powder.

[0120] The diameter of the tubular electrode base 7 of the present embodiment is 10 mm, and the wall thickness is 2 mm. The shape of the particle electrode base is spherical, and the diameter of the spherical particle electrode base is 2 mm. The material of the tubular electrode base 7 and the particle electrode base is titanium.

[0121] S2: The tubular electrode base 7 is passed through the first through hole 41, and the other end is connected with the second mounting plate and fixed in the inner cavity of the roller 1, so as not to rotate with the roller 1.

[0122] S3: The particle electrode base is placed between the partition ribs 3 below the heating body. The roller 1 of the present embodiment is provided with 8 partition spaces, and the particle electrode bases are fully laid on the inner walls of 2-3 partition spaces in the lower half of the roller 1.

[0123] The distance L1 from the heating wire 2 to the surface of the tubular electrode base 7 is 12 mm, and the distance L2 from the heating wire 2 to the surface of the particle electrode base is 12 mm.

[0124] S4: The deposition device is placed in a vacuum device, and borane, hydrogen and methane are introduced into the vacuum device, wherein the molar ratio B / C of boron to carbon is 0.7%, and the volume ratio CH4 / H2 of methane to hydrogen is 2%.

[0125] S5: The power is increased from 0 kw to the maximum power P with a power increasing slope of 1 kw / min. max=9kW, maintaining a deposition time of 15h. The temperature of the heating wire 2 is 1800℃, and the surface of the rod-shaped electrode substrate 7 and the particle electrode substrate is irradiated to a temperature of 700℃.

[0126] S6: After deposition, the power is reduced from 9 kW to 6 kW at a rate of 0.05 kW / min and held for 2 hours. Then, the power is reduced from 6 kW to 3 kW at a rate of 0.03 kW / min and held for 1 hour. The power is then reduced to 0. The electrode substrate is removed when the temperature drops to 40°C to obtain tubular and particle diamond electrode materials.

[0127] Example 5

[0128] The difference between the deposition apparatus in this embodiment and that in Embodiment 1 is:

[0129] (1) The length of the heating wire 2 of the deposition equipment is 80mm and the diameter of the drum 1 is 100mm.

[0130] (2) The rotational speed of the roller 1 is 4 r / h.

[0131] (3) Figure 7 As shown, the vertical cross-sectional shape of the partition rib 3 is triangular, and the height of the partition rib 3 is 0.3mm.

[0132] (4) The number of the dividing ribs 3 and the number of the heating wires 2 are both 16.

[0133] This embodiment also provides a method for preparing diamond electrode material, which is prepared using the deposition equipment of this embodiment, and includes the following steps:

[0134] S1: The rod-shaped electrode substrate 7 is sandblasted with 400-mesh silicon carbide powder, and the particle electrode substrate is ultrasonically treated with W20 diamond powder.

[0135] In this embodiment, the diameter of the rod-shaped electrode substrate 7 is 50 mm, and the shape of the particle electrode substrate is spherical with a diameter of 3 mm. Both the rod-shaped electrode substrate 7 and the particle electrode substrate are made of graphite / titanium composite.

[0136] S2: The rod-shaped electrode substrate 7 passes through the first through hole 41, and the other end is connected to the second mounting plate and fixed in the inner cavity of the roller 1, and does not rotate with the roller 1.

[0137] S3: Place the particle electrode substrate between the partition ribs 3 below the heating element. In this embodiment, the roller 1 has 16 partition spaces, and the inner walls of 7 to 8 partition spaces in the lower half of the roller 1 are covered with particle electrode substrate.

[0138] The distance L1 between the heating wire 2 and the surface of the rod electrode base 7 is 12 mm, and the distance L2 between the heating wire 2 and the surface of the particle electrode base is 11.5 mm.

[0139] S4: placing the deposition device in a vacuum device, and introducing borane, hydrogen and methane into the vacuum device, wherein the molar ratio of boron to carbon B / C is 1.5%, and the volume ratio of methane to hydrogen CH4 / H2 is 5%.

[0140] S5: increasing the power from 0 kw to the maximum power P = 7.4 kw at a power increasing slope of 0.6 kw / min, and maintaining the deposition time for 20 h. During the process, the temperature of the heating wire 2 is 1700 ℃, and the temperature of the surface of the rod electrode base 7 and the particle electrode base subjected to radiation is 650 ℃. max

[0141] S6: after the deposition is completed, decreasing the power from 7.4 kw to 4.88 kw at a rate of 0.04 kw / min, maintaining for 1 h, then decreasing the power from 4.88 kw to 2.44 kw at a rate of 0.02 kw / min, maintaining for 1 h, and then directly decreasing the power to 0. After the temperature is decreased to 20 ℃, the electrode base is taken out, and the rod and particle diamond electrode materials are obtained.

[0142] The above embodiments are only used to illustrate the technical solutions of the present application, but not limit the present application; based on the embodiments of the present application, all other embodiments obtained by those skilled in the art without creative work fall within the protection scope of the present application. Although the present application is described in detail with reference to the foregoing embodiments, those skilled in the art should understand that they can modify the technical solutions recorded in the foregoing embodiments, or make equivalent replacement to some technical features; and the modifications or replacement do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.​

Claims

1. A diamond electrode material deposition apparatus, characterized by, The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material.

2. The deposition apparatus of claim 1, wherein The application relates to a deposition device for preparing a diamond electrode material.

3. The deposition apparatus of claim 1, wherein The application relates to a deposition device for preparing a diamond electrode material.

4. The deposition apparatus of claim 3, wherein The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material.

5. The deposition apparatus of claim 1, wherein The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material.

6. The deposition apparatus of claim 5, wherein, The application relates to a deposition device for preparing a diamond electrode material.

7. The deposition apparatus of claim 6, wherein The application relates to a deposition device for preparing a diamond electrode material.

8. The deposition apparatus of claim 5, wherein, The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material.

9. A method of producing a diamond electrode material, characterized by, The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material.

10. The method of claim 9, wherein, The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to a deposition device for preparing a diamond electrode material. The application relates to The tubular electrode base has a diameter of 5-200 mm, a wall thickness of 1-15 mm, and a BDD film layer thickness of 1-30 μm deposited on the surface of the tubular electrode base; and / or The particle electrode base has a cylindrical shape and / or a spherical shape, wherein the cylindrical particle electrode base has a diameter of 0.5-3 mm and a diameter-to-height ratio of 0.3-2, and the spherical particle electrode base has a diameter of 0.5-3 mm; and / or The rod-shaped electrode base, the tubular electrode base, and the particle electrode base are made of any one or more of niobium, tantalum, monocrystalline silicon, silicon carbide, silicon nitride, titanium, copper / nickel composite, and graphite / titanium composite.

11. The preparation method according to claim 9, characterized in that, The distance L1 between the heating body and the surface of the rod-shaped or tubular electrode base is 5-35 mm, The distance L2 between the heating body and the surface of the particle electrode base is 7-35 mm.

12. The method of claim 11, wherein, The difference between the distance L1 and the distance L2 is not more than 5 mm.

13. The preparation method according to claim 11, characterized in that, During the deposition process, the temperature of the heating body is controlled at 1700-2200 ℃, and the temperature of the surface of the rod-shaped or tubular electrode base or the particle electrode base subjected to radiation is 650-1050 ℃.

14. The preparation method according to claim 9, characterized in that, The deposition on the electrode base comprises, First, the power is increased from 0 kW to the maximum power P at a rate of 0.2 to 5 kW / min max for a deposition time of 2 to 100 h, After the deposition, the power is decreased from the maximum power P max to 2 / 3 P max at a rate not greater than 0.05 kw / min, and maintained for 1-2 h; then the power is decreased from 2 / 3 P max to 1 / 3 P max at a rate not greater than 0.05 kw / min, and maintained for 1-2 h; then the power is decreased to 0 kw, and the electrode substrate is removed when the temperature drops to below 60°C, to obtain the diamond electrode material.

15. A diamond electrode material, characterized in that, The diamond electrode material is prepared by the preparation method of any one of claims 9-14.

Images