Titanium-doped nickel ferrite ceramic body for improving interface wettability as well as preparation method and application of titanium-doped nickel ferrite ceramic body

Abstract

The invention belongs to the technical field of metal-ceramic interface wetting, and relates to a titanium-doped nickel ferrite ceramic body for improving interface wettability and a preparation method and application of the titanium-doped nickel ferrite ceramic body. Preparation raw materials of the titanium-doped nickel ferrite ceramic body comprise nickel ferrite powder and titanium powder; when the total mass percentage of the nickel ferrite powder and the titanium powder is 100 wt%, the mass percentage of the nickel ferrite powder is 90 wt% or above, and the mass percentage of the titanium powder is 10 wt% or below; the particle size D50 of the nickel ferrite powder is 50 [mu] m or less; the titanium powder has a particle size D50 of 30 [mu] m or less. According to the titanium-doped nickel ferrite ceramic body, the wettability between the nickel ferrite ceramic body and Cu is improved, the interface connecting position between the nickel ferrite ceramic body and metal copper is close, no obvious hole or crack exists, and the three-dimensional meshing quality of the metal copper and the nickel ferrite ceramic body is improved.

Description

Technical Field

[0001] The invention belongs to the technical field of metal-ceramic interface wetting, and relates to a method for improving the wettability of the interface between metal copper and nickel ferrite ceramics, and in particular to a titanium-doped nickel ferrite ceramic body with improved interface wettability, and a preparation method and application thereof. Background Art

[0002] Aluminum has many excellent properties and is widely used, and its output is huge. At present, electrolysis is the main way to produce aluminum. Among them, carbon electrodes are widely used as anodes in the aluminum electrolysis industry due to their good conductivity, low cost, and easy processing. However, during the electrolysis process, carbon electrodes will be consumed in large quantities and produce a large amount of toxic and harmful gases such as CO2, CO and fluoride. Inert anode materials have the advantages of making up for losses or minor losses and only producing oxygen during the electrolysis process, and are regarded as ideal substitutes for carbon electrodes.

[0003] At present, inert anode materials are mainly composed of metal-based inert anodes, ceramic-based inert anodes and metal-ceramic inert anodes. Metal-based inert anodes and ceramic-based inert anodes have the disadvantages of poor corrosion resistance to molten salts and poor electrical conductivity, respectively. Metal-ceramic inert anodes have the advantages of high electrical conductivity and high corrosion resistance to molten salts, and are widely studied and used. As for metal-ceramic inert anodes, the oxide ceramic phase with a spinel structure has the advantages of a solid structure and good chemical stability, and has strong resistance to corrosion by various melts at high temperatures. Among them, nickel ferrite has a lower solubility than other spinel oxides, so it is widely used. The metal phase must have strong electrical conductivity, be cheap and easy to obtain, and be easy to form a composite material with the ceramic phase. It is also necessary to consider the reaction thermodynamics of metal oxidation, the reaction thermodynamics of metal oxides and electrolyte melts, and the corrosion behavior of metals during electrolysis. Therefore, Cu and its alloys are often used as the more common metal phases in nickel ferrite-based cermets.

[0004] Three-dimensional intermeshing metal ceramics are a new structural form of metal-ceramic composites developed in recent years, characterized by continuous interconnection of reinforcements and matrix in three-dimensional space, and interweaving of reinforcements and the matrix in three-dimensional space. For three-dimensional intermeshing metal ceramic materials with Cu as reinforcement and nickel ferrite ceramic as matrix, the three-dimensional penetration of Cu can give excellent conductive properties. However, due to the poor wettability of the interface between metal Cu and nickel ferrite ceramic, the preparation of composite materials of Cu reinforcement and nickel ferrite matrix is ​​affected, so it is crucial to improve the wettability at the interface between the two. Summary of the invention

[0005] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a titanium-doped nickel ferrite ceramic body with improved interface wettability, and a preparation method and application thereof, wherein the titanium-doped nickel ferrite ceramic body improves the wettability between the nickel ferrite ceramic body and Cu only by doping with titanium, so that the interface connection between the nickel ferrite ceramic body and metallic copper is tight without obvious holes and cracks, thereby improving the three-dimensional intermeshing quality of metallic copper and the nickel ferrite ceramic.

[0006] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a titanium-doped nickel ferrite ceramic body with improved interface wettability. The raw materials for preparing the titanium-doped nickel ferrite ceramic body include nickel ferrite powder and titanium powder.

[0008] Taking the total mass percentage of nickel ferrite powder and titanium powder as 100wt%, the mass percentage of the nickel ferrite powder is more than 90wt%, and the mass percentage of the titanium powder is less than 10wt%.

[0009] The particle size D50 of the nickel ferrite powder is less than 50 μm.

[0010] The particle size D50 of the titanium powder is less than 30 μm.

[0011] The titanium-doped nickel ferrite ceramic body with improved interfacial wettability provided by the present invention can improve the wettability between the nickel ferrite ceramic body and metal Cu. In the prior art, active metals are generally added to metal copper to form an alloy to improve the wettability between metal Cu and the nickel ferrite ceramic phase, which requires three stages of alloy fusion, ceramic body calcination and metal infiltration, has high requirements on equipment, is complex to operate and requires a large amount of material and financial resources. The titanium-doped nickel ferrite ceramic body with improved interfacial wettability provided by the present invention only requires titanium doping, without the use of other additives, thereby reducing the cost of raw materials, and, by controlling the amount of titanium powder, the particle size of the nickel ferrite powder and the particle size of the titanium powder, the wettability between the nickel ferrite ceramic body and the metal Cu is improved.

[0012] In the titanium-doped nickel ferrite ceramic provided by the present invention, taking the total mass percentage of nickel ferrite powder and titanium powder as 100wt%, the mass percentage of the nickel ferrite powder is greater than 90wt%, for example, it can be 90wt%, 91wt%, 93wt%, 95wt%, 96wt%, 98wt% or 99wt%, but is not limited to the listed values, and the remaining values ​​not listed within the numerical range are also applicable.

[0013] In the titanium-doped nickel ferrite ceramic provided by the present invention, the mass percentage of the titanium powder is less than 10wt%, for example, it can be 1wt%, 3wt%, 4wt%, 5wt%, 6wt%, 8wt% or 10wt%, taking the total mass percentage of the nickel ferrite powder and the titanium powder as 100wt%, but it is not limited to the listed values, and the remaining values ​​not listed in the numerical range are also applicable. When the mass percentage of the titanium powder exceeds 10wt%, the wettability between the nickel ferrite ceramic and Cu will be deteriorated, and it is not conducive to maintaining the stability of the titanium-doped nickel ferrite ceramic during the infiltration process.

[0014] Too large a particle size of nickel ferrite powder affects the wettability between nickel ferrite ceramics and Cu. In the raw materials for preparing the titanium-doped nickel ferrite ceramics described in the present invention, the particle size D50 of the nickel ferrite powder is less than 50 μm, for example, it can be 5 μm, 10 μm, 20 μm, 30 μm, 40 μm or 50 μm, but is not limited to the listed values. The remaining unlisted values ​​within the numerical range are also applicable. However, too small a particle size leads to increased costs and easily causes titanium powder agglomeration. Therefore, the particle size D50 of the nickel ferrite powder is preferably 10 μm-50 μm.

[0015] Too large a particle size of titanium powder affects the wettability between nickel ferrite ceramics and Cu. In the raw materials for preparing the titanium-doped nickel ferrite ceramics described in the present invention, the particle size D50 of the titanium powder is less than 30 μm, for example, it can be 5 μm, 10 μm, 15 μm, 20 μm, 25 μm or 30 μm, but is not limited to the listed values. The remaining unlisted values ​​within the numerical range are also applicable. However, too small a particle size leads to increased costs and easily causes titanium powder agglomeration. Therefore, the particle size D50 of the titanium powder is preferably 10 μm-30 μm.

[0016] In a second aspect, the present invention provides a method for preparing a titanium-doped nickel ferrite ceramic body with improved interface wettability, the preparation method comprising the following steps:

[0017] (1) mixing nickel ferrite powder and titanium powder according to a formula amount, and wet ball milling to obtain a mixed slurry;

[0018] (2) The mixed slurry in step (1) is subjected to solid-liquid separation, and the obtained solid material is dried to obtain a mixed powder;

[0019] (3) The mixed powder is formed and calcined to obtain the titanium-doped nickel ferrite ceramic body as claimed in claim 1.

[0020] The preparation method provided by the present invention is simple to operate and has low requirements on equipment, and can reduce the preparation cost of titanium-doped nickel ferrite ceramics. The obtained titanium-doped nickel ferrite ceramics improve the wettability between the nickel ferrite ceramics and Cu, so that the interface connection between the nickel ferrite ceramics and metallic copper is tight without obvious holes and cracks, thereby improving the three-dimensional intermeshing quality of metallic copper and nickel ferrite ceramics.

[0021] Preferably, the wet ball milling in step (1) comprises: mixing nickel ferrite powder and titanium powder according to the formula amount, mixing deionized water and grinding balls, and then ball milling.

[0022] Preferably, the deionized water is used in a water-to-material ratio of 2:1-4:1, for example, 2:1, 2.5:1, 3:1, 3.5:1 or 4:1, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0023] The water-to-material ratio in the present invention refers to the ratio of the mass of deionized water to the total mass of nickel ferrite powder and titanium powder.

[0024] Preferably, the grinding balls are used in a ball-to-material ratio of 4:1-6:1, for example, 4:1, 4.5:1, 5:1, 5.5:1 or 6:1, but are not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0025] The ball-to-material ratio in the present invention refers to the ratio of the mass of the grinding balls to the total mass of the nickel ferrite powder and the titanium powder.

[0026] Preferably, the rotation speed of the ball mill is 100 rpm-300 rpm, for example, it can be 100 rpm, 150 rpm, 200 rpm, 250 rpm or 300 rpm, but it is not limited to the listed values, and other values ​​not listed in the numerical range are also applicable.

[0027] Preferably, the ball milling time is 24h-48h, for example, it can be 24h, 25h, 28h, 30h, 32h, 35h, 38h, 40h, 42h, 45h or 48h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0028] Preferably, the solid-liquid separation method in step (2) comprises suction filtration.

[0029] Preferably, the drying method in step (2) comprises vacuum drying.

[0030] Preferably, the vacuum drying temperature is 120°C-150°C, for example, it can be 120°C, 125°C, 130°C, 135°C, 140°C, 145°C or 150°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0031] Preferably, the molding in step (3) comprises: mixing a binder with a mixed powder, and then pressing and molding.

[0032] Preferably, the amount of the binder is 4%-6% of the mass of the mixed powder, for example, 4%, 4.5%, 5%, 5.5% or 6%, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0033] Optionally, the adhesive includes PVA glue.

[0034] Preferably, the pressing pressure is 200 MPa-300 MPa, for example, 200 MPa, 220 MPa, 240 MPa, 250 MPa, 270 MPa, 280 MPa or 300 MPa, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0035] Preferably, the holding time for the compression molding is 20 min-35 min, for example, it can be 20 min, 24 min, 25 min, 27 min, 28 min, 30 min, 32 min or 35 min, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0036] Preferably, the calcination in step (3) comprises a first calcination and a second calcination performed sequentially.

[0037] Preferably, the calcining atmosphere includes any one of argon, nitrogen, helium or air, or a combination of at least two of them. Typical but non-limiting combinations include a combination of helium and nitrogen, a combination of argon and nitrogen, a combination of argon and helium, or a combination of argon, nitrogen, helium and air.

[0038] The calcination of the present invention comprises a first calcination and a second calcination which are carried out in sequence, wherein the first calcination is for removing the binder and the second calcination is for sintering to form the final titanium-doped nickel ferrite ceramic body.

[0039] Preferably, the first calcination has a heating rate of 1°C / min-5°C / min, a temperature of 400°C-650°C, and a holding time of 2h-5h.

[0040] The heating rate of the first calcination is 1°C / min-5°C / min, for example, 1°C / min, 2°C / min, 3°C / min, 4°C / min or 5°C / min, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0041] The temperature of the first calcination is 400°C-650°C, for example, 400°C, 450°C, 500°C, 550°C, 600°C or 650°C, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0042] The holding time of the first calcination is 2 h-5 h, for example, 2 h, 3 h, 3.5 h, 4 h, 4.5 h or 5 h, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0043] Preferably, the second calcination has a heating rate of 1°C / min-4°C / min, a temperature of 1000°C-1550°C, and a holding time of 2h-16h.

[0044] The heating rate of the second calcination is 1°C / min-4°C / min, for example, it can be 1°C / min, 1.5°C / min, 2°C / min, 2.5°C / min, 3°C / min, 3.5°C / min or 4°C / min, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0045] The temperature of the second calcination is 1000°C-1550°C, for example, 1000°C, 1100°C, 1200°C, 1300°C, 1400°C or 1550°C, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0046] The holding time of the second calcination is 2h-16h, for example, 2h, 4h, 5h, 6h, 8h, 10h, 12h, 15h or 16h, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0047] In a third aspect, the present invention provides a three-dimensional intermeshing metal ceramic, wherein the ceramic phase in the three-dimensional intermeshing metal ceramic is the titanium-doped nickel ferrite ceramic body with improved interface wettability as described in the first aspect, or the titanium-doped nickel ferrite ceramic body with improved interface wettability prepared by the preparation method described in the second aspect.

[0048] The metal phase of the three-dimensional intermeshing cermet is copper.

[0049] The numerical range described in the present invention not only includes the point values ​​listed above, but also includes any point values ​​between the above numerical ranges that are not listed. Due to space limitations and for the sake of simplicity, the present invention no longer exhaustively lists the specific point values ​​included in the range.

[0050] Compared with the prior art, the present invention has the following beneficial effects:

[0051] (1) The titanium-doped nickel ferrite ceramic provided by the present invention only requires titanium doping, without the use of other additives, thereby reducing the cost of raw materials. In addition, the wettability between the nickel ferrite ceramic and metal Cu is improved by controlling the amount of titanium powder, the particle size of the nickel ferrite powder, and the particle size of the titanium powder.

[0052] (2) The preparation method provided by the present invention is simple to operate and has low requirements on equipment, which can reduce the preparation cost of titanium-doped nickel ferrite ceramics. The obtained titanium-doped nickel ferrite ceramics improve the wettability between the nickel ferrite ceramics and Cu, making the interface connection between the nickel ferrite ceramics and metallic copper tight without obvious holes and cracks, thereby improving the three-dimensional intermeshing quality of metallic copper and nickel ferrite ceramics. BRIEF DESCRIPTION OF THE DRAWINGS

[0053] Figure 1 This is a contact angle test result diagram of the titanium-doped nickel ferrite ceramic body obtained in Example 1.

[0054] Figure 2 This is a graph showing the contact angle test results of the titanium-doped nickel ferrite ceramic body obtained in Example 2.

[0055] Figure 3 This is a graph showing the contact angle test results of the titanium-doped nickel ferrite ceramic body obtained in Example 3.

[0056] Figure 4 This is a graph showing the contact angle test results of the titanium-doped nickel ferrite ceramic body obtained in Example 4.

[0057] Figure 5 This is a graph showing the contact angle test results of the titanium-doped nickel ferrite ceramic body obtained in Example 5.

[0058] Figure 6 This is a graph showing the contact angle test results of the titanium-doped nickel ferrite ceramic body obtained in Comparative Example 1.

[0059] Figure 7 This is a cross-sectional SEM image of the titanium-doped nickel ferrite ceramic body obtained in Example 4, which is a three-dimensional intermeshing metal ceramic obtained after copper pressureless infiltration. DETAILED DESCRIPTION

[0060] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0061] Example 1

[0062] The present embodiment provides a titanium-doped nickel ferrite ceramic body with improved interface wettability, and the raw materials for preparing the ceramic body include nickel ferrite powder and titanium powder.

[0063] The method for preparing a titanium-doped nickel ferrite ceramic body with improved interface wettability provided in this embodiment comprises the following steps:

[0064] (1) mixing nickel ferrite powder, titanium powder, deionized water and grinding balls, and performing ball milling to obtain a mixed slurry;

[0065] Taking the total mass percentage of nickel ferrite powder and titanium powder as 100wt%, the mass percentage of the nickel ferrite powder is 99wt%, and the mass percentage of the titanium powder is 1wt%; the particle size D50 of the nickel ferrite powder is 20μm, and the particle size D50 of the titanium powder is 20μm.

[0066] The deionized water was used at a water-to-material ratio of 2:1, and the grinding balls were used at a ball-to-material ratio of 4:1; the ball milling speed was 200 rpm, and the ball milling time was 24 h.

[0067] (2) The mixed slurry in step (1) is filtered, and the obtained solid material is placed in a vacuum oven at 120° C. and dried for 12 h to obtain a mixed powder.

[0068] (3) The mixed powder described in step (2) is evenly mixed with PVA glue (PVA2488), and the mixture is kept under a pressure of 200 MPa for 20 minutes; then, a first calcination and a second calcination are performed in sequence in an argon atmosphere to obtain a titanium-doped nickel ferrite ceramic body with improved interface wettability.

[0069] The dosage of PVA glue is 5% of the mass of the mixed powder.

[0070] The first calcination is: heating to 500°C at a heating rate of 5°C / min and keeping at this temperature for 2h;

[0071] The second calcination is as follows: at the end temperature of the first calcination, the temperature is increased to 1200°C at a heating rate of 4°C / min and kept at this temperature for 8h.

[0072] Example 2

[0073] This embodiment provides a titanium-doped nickel ferrite ceramic body with improved interface wettability, which is the same as Example 1 except that the mass percentage of nickel ferrite powder is 97wt% and the mass percentage of titanium powder is 3wt% when the total mass percentage of nickel ferrite powder and titanium powder is 100wt%.

[0074] Example 3

[0075] This embodiment provides a titanium-doped nickel ferrite ceramic body with improved interface wettability, which is the same as Example 1 except that the mass percentage of nickel ferrite powder is 95wt% and the mass percentage of titanium powder is 5wt% when the total mass percentage of nickel ferrite powder and titanium powder is 100wt%.

[0076] Example 4

[0077] This embodiment provides a titanium-doped nickel ferrite ceramic body with improved interface wettability, which is the same as the embodiment 3 except that the end temperature of the second calcination is 1300°C.

[0078] Example 5

[0079] This embodiment provides a titanium-doped nickel ferrite ceramic body with improved interface wettability, which is the same as the embodiment 3 except that the end temperature of the second calcination is 1400°C.

[0080] Example 6

[0081] This embodiment provides a titanium-doped nickel ferrite ceramic body with improved interface wettability, which is the same as the embodiment 3 except that the end temperature of the second calcination is 1550°C.

[0082] Example 7

[0083] This embodiment provides a titanium-doped nickel ferrite ceramic body with improved interface wettability, which is the same as the embodiment 3 except that the end temperature of the second calcination is 1000°C.

[0084] Example 8

[0085] The present embodiment provides a titanium-doped nickel ferrite ceramic body with improved interface wettability, and the raw materials for preparing the ceramic body include nickel ferrite powder and titanium powder.

[0086] The method for preparing a titanium-doped nickel ferrite ceramic body with improved interface wettability provided in this embodiment comprises the following steps:

[0087] (1) mixing nickel ferrite powder, titanium powder, deionized water and grinding balls, and performing ball milling to obtain a mixed slurry;

[0088] Taking the total mass percentage of nickel ferrite powder and titanium powder as 100wt%, the mass percentage of the nickel ferrite powder is 95wt%, and the mass percentage of the titanium powder is 5wt%; the particle size D50 of the nickel ferrite powder is 10μm, and the particle size D50 of the titanium powder is 10μm.

[0089] The deionized water was used at a water-to-material ratio of 3:1, and the grinding balls were used at a ball-to-material ratio of 5:1; the ball milling speed was 100 rpm, and the ball milling time was 48 h.

[0090] (2) The mixed slurry in step (1) was filtered, and the obtained solid material was placed in a vacuum oven at 130° C. and dried for 12 h to obtain a mixed powder.

[0091] (3) The mixed powder described in step (2) is evenly mixed with PVA glue (PVA2488), and the mixture is kept under a pressure of 250 MPa for 30 minutes; then, a first calcination and a second calcination are performed in sequence in an argon atmosphere to obtain a titanium-doped nickel ferrite ceramic body.

[0092] The first calcination was as follows: heating to 650°C at a heating rate of 3°C / min and keeping the temperature for 3h;

[0093] The second calcination is as follows: at the end temperature of the first calcination, the temperature is increased to 1000°C at a heating rate of 2°C / min and kept at this temperature for 16 hours.

[0094] Example 9

[0095] The present embodiment provides a titanium-doped nickel ferrite ceramic body with improved interface wettability, and the raw materials for preparing the ceramic body include nickel ferrite powder and titanium powder.

[0096] The method for preparing a titanium-doped nickel ferrite ceramic body with improved interface wettability provided in this embodiment comprises the following steps:

[0097] (1) mixing nickel ferrite powder, titanium powder, deionized water and grinding balls, and performing ball milling to obtain a mixed slurry;

[0098] Taking the total mass percentage of nickel ferrite powder and titanium powder as 100wt%, the mass percentage of the nickel ferrite powder is 95wt%, and the mass percentage of the titanium powder is 5wt%; the particle size D50 of the nickel ferrite powder is 50μm, and the particle size D50 of the titanium powder is 30μm.

[0099] The deionized water was used at a water-to-material ratio of 4:1, and the grinding balls were used at a ball-to-material ratio of 6:1; the ball milling speed was 300 rpm, and the ball milling time was 24 h.

[0100] (2) The mixed slurry in step (1) is filtered, and the obtained solid material is placed in a vacuum oven at 150° C. and dried for 12 h to obtain a mixed powder.

[0101] (3) The mixed powder described in step (2) is evenly mixed with PVA glue (PVA2488), and the mixture is kept under a pressure of 300 MPa for 35 minutes; then, a first calcination and a second calcination are performed in sequence in an argon atmosphere to obtain a titanium-doped nickel ferrite ceramic body.

[0102] The first calcination was as follows: heating to 400°C at a heating rate of 1°C / min and keeping at that temperature for 5h;

[0103] The second calcination is as follows: at the end temperature of the first calcination, the temperature is increased to 1550°C at a heating rate of 1°C / min and kept at this temperature for 2h.

[0104] Example 10

[0105] This embodiment provides a titanium-doped nickel ferrite ceramic body with improved interface wettability, which is the same as Example 1 except that the mass percentage of nickel ferrite powder is 90wt% and the mass percentage of titanium powder is 10wt% when the total mass percentage of nickel ferrite powder and titanium powder is 100wt%.

[0106] Comparative Example 1

[0107] This comparative example provides a nickel ferrite ceramic body, and the raw materials for preparing the nickel ferrite ceramic body include nickel ferrite powder.

[0108] The preparation method of the nickel ferrite ceramic body provided in this comparative example comprises the following steps:

[0109] (1) mixing nickel ferrite powder, deionized water and grinding balls, and performing ball milling to obtain a mixed slurry;

[0110] The particle size D50 of the nickel ferrite powder is 20 μm.

[0111] The deionized water was used at a water-to-material ratio of 2:1, and the grinding balls were used at a ball-to-material ratio of 4:1; the ball milling speed was 200 rpm, and the ball milling time was 24 h.

[0112] (2) The mixed slurry in step (1) is filtered, and the obtained solid material is placed in a vacuum oven at 120° C. and dried for 12 h to obtain a mixed powder.

[0113] (3) The mixed powder described in step (2) is evenly mixed with PVA glue (PVA2488), and the mixture is kept under a pressure of 200 MPa for 20 minutes; then, a first calcination and a second calcination are performed in sequence in an argon atmosphere to obtain a nickel ferrite ceramic body.

[0114] The first calcination is: heating to 500°C at a heating rate of 5°C / min and keeping at this temperature for 2h;

[0115] The second calcination is as follows: at the end temperature of the first calcination, the temperature is increased to 1200°C at a heating rate of 4°C / min and kept at this temperature for 8h.

[0116] Comparative Example 2

[0117] This comparative example provides a titanium-doped nickel ferrite ceramic body, which is the same as Example 1 except that when the total mass percentage of nickel ferrite powder and titanium powder is 100wt%, the mass percentage of nickel ferrite powder is 88wt% and the mass percentage of titanium powder is 12wt%.

[0118] Comparative Example 3

[0119] This comparative example provides a titanium-doped nickel ferrite ceramic body, which is the same as Example 1 except that the particle size D50 of the nickel ferrite powder is 55 μm.

[0120] Comparative Example 4

[0121] This comparative example provides a titanium-doped nickel ferrite ceramic body, which is the same as Example 1 except that the particle size D50 of the titanium powder is 35 μm.

[0122] Performance Testing

[0123] The high temperature contact angle between the ceramic body and the metal copper provided in the above embodiments and comparative examples was tested. The testing method was as follows: the surfaces of the Cu metal block and the ceramic body were polished; then the Cu metal block was placed above the ceramic body and horizontally placed in a high temperature contact angle testing furnace; the furnace was evacuated, and when the vacuum degree reached 10 -5 Pa, argon was introduced to 1atm, and then the temperature was raised to 1200℃ at a heating rate of 5℃ / min and kept at this temperature for 30min. A USB 3.0 high-speed camera was used to monitor and record the droplet spreading process in real time, and the contact angle analysis software SCA20 was used to analyze the droplet profile to obtain the high-temperature contact angles at the two interfaces. The results are shown in Table 1. The larger the contact angle, the worse the wettability.

[0124] The contact angle test results of the titanium-doped nickel ferrite ceramic body obtained in Example 1 are shown in FIG. Figure 1 As shown, the contact angle is 90.08°; the contact angle test results of the titanium-doped nickel ferrite ceramic body obtained in Example 2 are shown in FIG. Figure 2 As shown, the contact angle is 77.58°; the contact angle test results of the titanium-doped nickel ferrite ceramic body obtained in Example 3 are shown in FIG. Figure 3 As shown, the contact angle is 56.44°; the contact angle test results of the titanium-doped nickel ferrite ceramic body obtained in Example 4 are shown in FIG. Figure 4As shown, the contact angle is 13.37°; the contact angle test results of the titanium-doped nickel ferrite ceramic body obtained in Example 5 are shown in FIG. Figure 5 As shown, the contact angle is 88.57°; the contact angle test results of the titanium-doped nickel ferrite ceramic body obtained in Comparative Example 1 are shown in FIG. Figure 6 As shown, the contact angle is 111.86°; the cross-sectional SEM image of the titanium-doped nickel ferrite ceramic body obtained in Example 4 after copper pressureless infiltration to obtain a three-dimensional intermeshing metal ceramic is shown in Figure 7 shown.

[0125] Table 1

[0126]

[0127]

[0128] In summary, the titanium-doped nickel ferrite ceramic provided by the present invention only requires titanium doping, and does not require the use of other additives, thereby reducing the cost of raw materials. Moreover, the wettability between the nickel ferrite ceramic and metal Cu is improved by controlling the amount of titanium powder, the particle size of the nickel ferrite powder and the particle size of the titanium powder. The preparation method provided by the present invention is simple to operate, has low requirements on equipment, can reduce the preparation cost of the titanium-doped nickel ferrite ceramic, and the obtained titanium-doped nickel ferrite ceramic improves the wettability between the nickel ferrite ceramic and Cu, makes the interface connection between the nickel ferrite ceramic and the metal copper tight, without obvious holes and cracks, and improves the three-dimensional intermeshing quality of the metal copper and the nickel ferrite ceramic.

[0129] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A titanium-doped nickel ferrite ceramic body with improved interface wettability, characterized in that: The raw materials for preparing the titanium-doped nickel ferrite ceramic body include nickel ferrite powder and titanium powder; Taking the total mass percentage of nickel ferrite powder and titanium powder as 100wt%, the mass percentage of the nickel ferrite powder is greater than 90wt%, and the mass percentage of the titanium powder is less than 10wt%; The particle size D50 of the nickel ferrite powder is less than 50 μm; The particle size D50 of the titanium powder is less than 30 μm.

2. A method for preparing a titanium-doped nickel ferrite ceramic body with improved interface wettability, characterized in that: The preparation method comprises the following steps: (1) mixing nickel ferrite powder and titanium powder according to a formula amount, and wet ball milling to obtain a mixed slurry; (2) The mixed slurry in step (1) is subjected to solid-liquid separation, and the obtained solid material is dried to obtain a mixed powder; (3) The mixed powder is formed and calcined to obtain the titanium-doped nickel ferrite ceramic body with improved interface wettability as claimed in claim 1.

3. The preparation method according to claim 2, characterized in that: The wet ball milling in step (1) comprises: mixing nickel ferrite powder and titanium powder according to the formula amount, mixing deionized water and grinding balls, and then ball milling.

4. The preparation method according to claim 3, characterized in that: The deionized water is used in an amount of 2:1-4:1 water-to-material ratio; Preferably, the grinding balls are used in a ratio of balls to materials of 4:1-6:1; Preferably, the rotation speed of the ball mill is 100rpm-300rpm; Preferably, the ball milling time is 24h-48h.

5. The preparation method according to claim 2, characterized in that: The solid-liquid separation method in step (2) comprises suction filtration; Preferably, the drying method in step (2) comprises vacuum drying; Preferably, the vacuum drying temperature is 120°C-150°C.

6. The preparation method according to claim 2, characterized in that: The molding in step (3) includes: mixing the binder and the mixed powder, and then pressing and molding.

7. The preparation method according to claim 6, characterized in that: The compression molding pressure is 200MPa-300MPa; Preferably, the holding time of the compression molding is 20 min-35 min.

8. The preparation method according to any one of claims 2 to 7, characterized in that: The calcination in step (3) includes a first calcination and a second calcination performed sequentially; Preferably, the calcination atmosphere includes any one of argon, nitrogen, helium or air, or a combination of at least two of them.

9. The preparation method according to claim 8, characterized in that: The first calcination has a heating rate of 1°C / min-5°C / min, a temperature of 400°C-650°C, and a holding time of 2h-5h; Preferably, the second calcination has a heating rate of 1°C / min-4°C / min, a temperature of 1000°C-1550°C, and a holding time of 2h-16h.

10. A three-dimensional intermeshing metal ceramic, characterized in that: The ceramic phase in the three-dimensional intermeshing metal ceramic is the titanium-doped nickel ferrite ceramic body with improved interface wettability as described in claim 1, or the titanium-doped nickel ferrite ceramic body with improved interface wettability prepared by the preparation method described in any one of claims 2-9.

Images