A titanium-doped nickel ferrite ceramic body with improved interfacial wettability, and a preparation method and application thereof

Abstract

The application belongs to the technical field of metal-ceramic interface wetting, and relates to a titanium-doped nickel ferrite ceramic body for improving interface wetting, a preparation method and application thereof. The preparation raw material of the titanium-doped nickel ferrite ceramic body comprises nickel ferrite powder and titanium powder. The mass percentage of the nickel ferrite powder is more than 90wt% and the mass percentage of the titanium powder is less than 10wt% based on 100wt% of the total mass percentage of the nickel ferrite powder and the titanium powder. The particle size D50 of the nickel ferrite powder is less than 50um. The particle size D50 of the titanium powder is less than 30um. The titanium-doped nickel ferrite ceramic body improves the wetting between the nickel ferrite ceramic body and Cu, makes the interface connection between the nickel ferrite ceramic body and the metal copper compact, free of obvious holes and cracks, and improves the three-dimensional interlocking quality of the metal copper and the nickel ferrite ceramic.

Description

Technical Field

[0001] The present 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 is widely used due to its numerous excellent properties and is produced in large quantities. Currently, electrolysis is the primary method for aluminum production. Carbon electrodes are widely used as anodes in the aluminum electrolysis industry due to their excellent conductivity, low cost, and ease of processing. However, during the electrolysis process, carbon electrodes are consumed in large quantities and produce large amounts of toxic and hazardous gases such as CO2, CO, and fluorides. Inert anode materials offer the advantages of replenishing or minimizing losses during electrolysis and producing only oxygen, making them an ideal alternative to carbon electrodes.

[0003] Current inert anode materials primarily consist of metal-based, ceramic-based, and cermet-based. Metal-based and ceramic-based inert anodes suffer from poor molten salt corrosion resistance and electrical conductivity, respectively. Cermet-based inert anodes, however, combine high electrical conductivity and high molten salt corrosion resistance and are widely studied and used. Among cermet-based inert anodes, spinel-type oxide ceramic phases offer structural robustness and excellent chemical stability, making them highly resistant to corrosion by various melts at high temperatures. Nickel ferrite, among these oxides, is widely used due to its lower solubility compared to other spinel oxides. The metallic phase must be highly conductive, inexpensive, readily available, and easily composited with the ceramic phase. Furthermore, the reaction thermodynamics of the metal oxidation, the reaction thermodynamics of the metal oxide with the electrolyte melt, and the corrosion behavior of the metal during electrolysis must also be considered. Therefore, Cu and its alloys are commonly used as the metallic phase in nickel ferrite-based cermets.

[0004] Three-dimensional intermeshing cermets are a new structural form of metal-ceramic composites developed in recent years. These materials exhibit continuous interconnection of the reinforcements and matrix in three dimensions, with the reinforcements and matrix interwoven in three dimensions. For three-dimensional intermeshing cermets composed of copper (Cu) as the reinforcement and nickel ferrite (NiFe) ceramic as the matrix, the three-dimensional interconnection of Cu imparts excellent electrical conductivity. However, the poor wettability of the interface between Cu and NiFe ceramics hinders the preparation of Cu reinforcement / NiFe matrix composites. Therefore, improving the wettability at the interface is crucial. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the present invention aims to provide a titanium-doped nickel ferrite ceramic body with improved interfacial wettability, as well as a preparation method and application thereof. The titanium-doped nickel ferrite ceramic body improves the wettability between the nickel ferrite ceramic body and Cu only by titanium doping, 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 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 having 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 greater 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. The prior art generally adds active metals to metal copper to form an alloy to improve the wettability between metal Cu and the nickel ferrite ceramic phase, which requires three stages: alloy fusion, ceramic body calcination, and metal infiltration. It 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. Moreover, the wettability between the nickel ferrite ceramic body 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.

[0012] In the titanium-doped nickel ferrite ceramic provided by the present invention, the mass percentage of the nickel ferrite powder is greater than 90wt%, based on the total mass percentage of the nickel ferrite powder and the titanium powder as 100wt%, 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 10 wt% or less, based on the total mass percentage of the nickel ferrite powder and the titanium powder being 100 wt%. For example, it can be 1 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 8 wt%, or 10 wt%, but the mass percentage is not limited to the values ​​listed above, and other values ​​not listed within the numerical range are also applicable. If the mass percentage of the titanium powder exceeds 10 wt%, the wettability between the nickel ferrite ceramic and Cu will deteriorate, which 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 interfacial wettability, the preparation method comprising the following steps:

[0017] (1) mixing nickel ferrite powder and titanium powder according to the formula, 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 according to claim 1.

[0020] The preparation method provided by the present invention is simple to operate, has low requirements on equipment, can reduce the preparation cost of titanium-doped nickel ferrite ceramics, and 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 amount of the grinding balls is such that the ball-to-material ratio is 4:1-6:1, for example, 4:1, 4.5:1, 5:1, 5.5:1 or 6:1, but is 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 ball milling speed is 100 rpm-300 rpm, for example, 100 rpm, 150 rpm, 200 rpm, 250 rpm or 300 rpm, but is not limited to the listed values, and other values ​​not listed within 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 values ​​not listed within the numerical range are also applicable.

[0028] Preferably, the solid-liquid separation method in step (2) includes 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) includes: mixing the binder and the 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, it can be 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 values ​​not listed 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) includes 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 includes a first calcination and a second calcination performed in sequence, wherein the first calcination is for removing the binder and the second calcination is a sintering process 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 hours to 5 hours, for example, 2 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours or 5 hours, 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 values ​​not listed 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 2 hours to 16 hours, for example, 2 hours, 4 hours, 5 hours, 6 hours, 8 hours, 10 hours, 12 hours, 15 hours or 16 hours, 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 includes not only the point values ​​listed above, but also 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. 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.

[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 diagram showing the contact angle test results of the titanium-doped nickel ferrite ceramic body obtained in Example 2.

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

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

[0057] Figure 5 This is a diagram 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 way of specific embodiments. It should be understood by those skilled in the art that the embodiments are merely to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0061] Example 1

[0062] This 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 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) was filtered, and the obtained solid material was 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 sequentially performed in an argon atmosphere to obtain a titanium-doped nickel ferrite ceramic body with improved interface wettability.

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

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

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

[0072] Example 2

[0073] This embodiment provides a titanium-doped nickel ferrite ceramic body with improved interfacial wettability. 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%, the rest is the same as Example 1.

[0074] Example 3

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

[0076] Example 4

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

[0078] Example 5

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

[0080] Example 6

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

[0082] Example 7

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

[0084] Example 8

[0085] This 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 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 pressure is maintained at 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 holding for 3 h;

[0093] The second calcination was as follows: at the end temperature of the first calcination, the temperature was raised to 1000° C. at a heating rate of 2° C. / min and kept at that temperature for 16 h.

[0094] Example 9

[0095] This 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 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) was filtered, and the obtained solid material was 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 pressure is maintained at 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 holding for 5 h;

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

[0104] Example 10

[0105] This embodiment provides a titanium-doped nickel ferrite ceramic body with improved interfacial wettability. 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%, all other aspects are the same as Example 1.

[0106] Comparative Example 1

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

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

[0109] (1) mixing nickel ferrite powder, deionized water, and grinding balls, and 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) was filtered, and the obtained solid material was 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 sequentially performed in an argon atmosphere to obtain a nickel ferrite ceramic body.

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

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

[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 the mass percentage of nickel ferrite powder is 88wt% and the mass percentage of titanium powder is 12wt%, with the total mass percentage of nickel ferrite powder and titanium powder being 100wt%.

[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 copper metal provided in the above embodiments and comparative examples was tested. The test 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 placed horizontally in a high temperature contact angle test furnace; the furnace was vacuumed, and when the vacuum reached 10 -5 Pa, argon was introduced to 1 atm, and the temperature was then raised to 1200°C at a rate of 5°C / min and held for 30 minutes. A USB 3.0 high-speed camera was used to monitor and record the droplet spreading process in real time. The droplet profile was analyzed using contact angle analysis software SCA20 to obtain the high-temperature contact angles at the two interfaces. The results are shown in Table 1. A larger contact angle indicates poorer 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, the three-dimensional intermeshing metal ceramic is as shown 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 and has low requirements for equipment, which can reduce the preparation cost of the titanium-doped nickel ferrite ceramic. The obtained titanium-doped nickel ferrite ceramic improves the wettability between the nickel ferrite ceramic and Cu, so that the interface connection between the nickel ferrite ceramic and metal copper is tight and free of obvious holes and cracks, thereby improving the three-dimensional intermeshing quality of metal copper and the nickel ferrite ceramic.

[0129] The applicant declares that the above is only a specific embodiment of the present invention, but the scope of protection 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 fall within the scope of protection and disclosure 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; Based on the total mass percentage of the nickel ferrite powder and the titanium powder being 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 interfacial wettability as claimed in claim 1, characterized in that: The preparation method comprises the following steps: (1) Mixing nickel ferrite powder and titanium powder according to the formula, 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, 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 such that the water-to-material ratio is 2:1-4:

1.

5. The preparation method according to claim 3, characterized in that The amount of the grinding balls used is such that the ball-to-material ratio is 4:1-6:

1.

6. The preparation method according to claim 2, characterized in that The rotation speed of the wet ball mill is 100 rpm-300 rpm.

7. The preparation method according to claim 2, characterized in that The wet ball milling time is 24h-48h.

8. The preparation method according to claim 2, characterized in that The solid-liquid separation method in step (2) includes suction filtration.

9. The preparation method according to claim 2, characterized in that The drying method in step (2) includes vacuum drying.

10. The preparation method according to claim 9, characterized in that The vacuum drying temperature is 120°C-150°C.

11. 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.

12. The preparation method according to claim 11, characterized in that The compression molding pressure is 200MPa-300MPa.

13. The preparation method according to claim 11, characterized in that The holding time of the compression molding is 20 minutes to 35 minutes.

14. The preparation method according to claim 2, characterized in that The calcination in step (3) includes a first calcination and a second calcination performed sequentially.

15. The preparation method according to claim 2, characterized in that The calcination atmosphere includes any one of argon, nitrogen, helium or air, or a combination of at least two of them.

16. The preparation method according to claim 14, 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.

17. The preparation method according to claim 14, characterized in that 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.

18. 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 according to any one of claims 2 to 17.

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