A conductive ceramic carbon fiber roller, preparation method and application

Abstract

The present invention relates to the field of material technology, and particularly relates to a conductive ceramic carbon fiber roll, a preparation method and an application thereof. The conductive ceramic carbon fiber roll includes a carbon fiber prepreg roll core and a ceramic layer formed on the outer surface of the carbon fiber prepreg roll core. The ceramic layer is a coating formed by titanium suboxide, and the general formula of titanium suboxide is: Ti n O 2n‑1 (4 ≤ n ≤ 10). In the present invention, a ceramic layer composed of titanium suboxide is formed on the surface of the carbon fiber prepreg roll core, endowing the roll surface with excellent conductive performance.

Description

Technical Field

[0001] The present invention relates to the technical field of materials, and particularly relates to a conductive ceramic carbon fiber roll, a preparation method and an application thereof. Background Art

[0002] At present, the roller shafts commonly used in production lines generally have a main body made of metal, which has good static conductive effect, but the cost is relatively high, the quality of the roller shaft is relatively large, and the rotational energy required for operation is also large, which is not conducive to rapid start and stop. It is easy to be corroded after long-term use, and it is also easy to cause the main body of the roller shaft to bend and deform when placed horizontally for a long time, affecting the accuracy of the roller body.

[0003] Carbon fiber has many excellent properties such as high strength, high modulus, high temperature resistance, wear resistance, corrosion resistance, fatigue resistance, creep resistance, electrical conductivity, thermal conductivity and far-infrared radiation. Carbon fiber tubes can be used in textile machinery, aluminum foil machinery, plastic film machinery, paper machinery, printing / dyeing machinery to solve the problems of high cost of roller shafts made of metal, easy corrosion after long-term use, and easy bending and deformation of the main body of the roller shaft, which affect the accuracy of the roller body.

[0004] Therefore, when using carbon fiber as a roller shaft, the carbon fiber will be modified by adding a resin material to the carbon fiber raw yarn. And a ceramic coating is coated on the surface of the carbon fiber material. For example, a process of spraying ceramic on the surface of an epoxy resin carbon fiber composite product disclosed in CN101016614A includes the steps: A. roughening the surface of the epoxy resin-based carbon fiber composite product; B. spraying a metal bottom layer on the roughened surface; C. spraying ceramic powder on the surface of the metal bottom layer to form a ceramic coating. However, this will bring new problems. The carbon fiber raw yarn itself has good electrical conductivity, but its conductivity is weaker than that of metal, and the resin material itself is not conductive. After the resin material fully infiltrates the carbon fiber raw yarn, if it can evenly wrap the latter, the conductivity of the made carbon fiber roll will be greatly reduced or even completely lost. And after coating the ceramic coating on the surface, most of the ceramic coatings are not conductive, and it cannot meet the requirements when used in places that require anti-static, such as the film manufacturing in the lithium battery industry and the chip manufacturing industry. Summary of the Invention

[0005] The purpose of the present invention is to solve the defect of insufficient antistatic ability of the above-mentioned carbon fiber materials when used in places that require anti-static, and to provide a conductive ceramic carbon fiber roll, a preparation method and an application thereof, which have obvious advantages especially in industries such as lithium battery film manufacturing and chip manufacturing.

[0006] In the first aspect of the present invention, a conductive ceramic carbon fiber roll is provided, and the following technical solution is adopted:

[0007] A conductive ceramic carbon fiber roller, comprising a carbon fiber prepreg roll core and a ceramic layer formed on the outer surface of the carbon fiber prepreg roll core, wherein the ceramic layer is a coating formed by titanium suboxide, and the general formula of titanium suboxide is: Ti n O 2n-1 (4 ≤ n ≤ 10).

[0008] In the above solution, a conductive ceramic layer formed by coating a layer of titanium suboxide on the surface of the roll core formed by carbon fiber prepreg endows the carbon fiber roller with antistatic performance. After testing, the surface resistivity of the roller after spraying the conductive ceramic can reach 30 Ω·cm or less.

[0009] As recorded in CN101016614A mentioned in the background art, in order to solve the problem of easy deformation of epoxy resin-based carbon fiber composites and expand their scope of use, a ceramic layer is sprayed on the surface, and with the characteristics of high temperature resistance, wear resistance, heat insulation, etc. of the ceramic, it plays a protective role for epoxy resin-based carbon fiber composites and their products. In the technology of this patent application, the antistatic performance of the material is not considered. Most ceramics are non-conductive and cannot endow the product with conductive performance.

[0010] Of course, in the prior art, there are also some conductive ceramics, such as cermets. In the initial stage of the inventor's research and development, some common types were selected from these conductive cermets, including carbide-based cermets, oxide-based cermets, and nitride-based cermets. However, through experiments, it was found that the conductive performance of some ceramics could not reach the expected effect, and it could not meet the requirements for industries with high antistatic performance requirements, such as lithium batteries and chips. For some ceramics, such as WC-12Co cermet, although the conductive performance can meet the requirements, it was found that the stability was poor, especially after being used for a period of time, the fluctuation of the resistivity was obvious.

[0011] Therefore, the inventor expanded the scope of conductive ceramics and found that by using titanium suboxide ceramics (Ti n O 2n-1 (4 ≤ n ≤ 10)) on the surface of the carbon fiber prepreg roll core, the carbon fiber roller can be endowed with excellent conductive performance and stable performance.

[0012] Preferably, a metal transition layer formed by metal powder is further formed between the carbon fiber prepreg roll core and the ceramic layer. Spraying ceramic powder directly on the surface of the carbon fiber prepreg to form a ceramic layer, due to the difference in the thermal barrier performance between the carbon fiber material and the ceramic material, thermal stress is generated during temperature change, affecting the interfacial bonding strength, and further causing the coating to crack or peel off: a poor interfacial bonding may be formed between the carbon fiber and the ceramic, affecting the overall performance of the surface ceramic coating. Adding a metal transition layer between the two is beneficial to overcoming the above problems to a certain extent.

[0013] Preferably, a sand layer is further formed between the carbon fiber prepreg roll core and the metal transition layer. By providing the sand layer, the specific surface area of the surface of the carbon fiber prepreg roll core is increased, which is beneficial to the stable formation of the subsequent coating.

[0014] Preferably, the sand layer is formed by spraying white fused alumina with a mesh size of 30 to 50.

[0015] Preferably, inorganic particles and organic resin are doped in the metal powder used for the metal transition layer. After adding a metal transition layer formed by pure metal powder between the carbon fiber prepreg roll core and the ceramic layer, although the problem of interface bonding can be solved to a certain extent, when forming the ceramic layer, there is a relatively large difference in conductivity between different rolls of the same batch and between rolls of different batches, and the stability between batches is poor. The inventor speculates that this may be due to the uneven distribution of ceramic powder during the spraying process of the surface ceramic layer. Attempts have been made to adjust the spraying process parameters, but the results have not been significantly improved. Therefore, it is considered whether it is the influence brought by the bottom metal transition layer. After a series of experiments, it is determined that the addition of the metal transition layer leads to a large difference in conductivity between different rolls of the same batch and between rolls of different batches. During the experiment, it is found that doping a small amount of inorganic particles and organic resin in the metal powder is beneficial to greatly improve the problem of large conductivity difference.

[0016] Preferably, the particle size of the inorganic particles is 50 nm to 150 nm.

[0017] Preferably, in the metal transition layer, the weight ratio of metal powder, inorganic particles and organic resin is 1: (0.1 - 0.15): (0.1 - 0.2).

[0018] Preferably, the inorganic particles are any one or a mixture of several of silicon dioxide, titanium dioxide, aluminum oxide, calcium carbonate, etc.

[0019] Preferably, the organic resin is epoxy resin.

[0020] In the second aspect of the present invention, a method for preparing the above-mentioned conductive ceramic carbon fiber roll is provided, including the following steps:

[0021] (1) Provide a roll core made of carbon fiber prepreg;

[0022] (2) Clean the surface of the roll core and form a sand layer by sandblasting;

[0023] (3) Spray metal powder on the roll surface formed with the sand layer to form a metal powder layer;

[0024] (4) Spray ceramic powder on the roll surface formed with the metal powder layer to form a ceramic layer.

[0025] Preferably, in step (4), the ceramic layer is sprayed using a plasma spraying device, and the spraying conditions are as follows: spraying current 500 - 555 A, main gas flow rate 25 - 32 L / min, secondary gas flow rate 3 - 5.5 L / min, powder feeding rate 30 - 50 g / min.

[0026] In the third aspect of the present invention, there is provided an application of the above-mentioned conductive ceramic carbon fiber roll for manufacturing lithium battery films or chips.

[0027] By implementing the above technical solutions, compared with the prior art, the present invention has the following advantages:

[0028] 1. The present invention forms a ceramic layer composed of titanium suboxide on the surface of the carbon fiber prepreg roll core, endowing the roll surface with excellent electrical conductivity.

[0029] 2. By forming a sand layer and a metal powder layer on the surface of the roll core before forming the ceramic layer, the adhesion of the ceramic layer is improved, making the formation of the ceramic layer more stable.

[0030] 3. By specifically improving the composition of the metal powder layer, the stability of the electrical conductivity of the conductive ceramic carbon fiber roll is provided. Description of the Drawings

[0031] Figure 1 It is a schematic diagram of the hierarchical structure of the conductive ceramic carbon fiber roll shown in an embodiment of the present invention.

[0032] In the figure, 101 - roll core, 102 - metal powder layer, 103 - ceramic layer. Detailed Embodiments

[0033] The following specific embodiments illustrate the implementation manners of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification. The present invention can also be implemented or applied through other different specific implementation manners. Various details in this specification can also be modified or changed based on different viewpoints and applications without departing from the spirit of the present invention. It should be noted that, without conflict, the following embodiments and the features in the embodiments can be combined with each other. Unless otherwise specified, the methods used in the embodiments of the present invention are all conventional methods.

[0034] Example 1

[0035] This embodiment provides a conductive ceramic carbon fiber roll, which includes a carbon fiber prepreg roll core and a ceramic layer formed on the outer surface of the carbon fiber prepreg roll core. The ceramic layer is a coating formed by spraying titanium suboxide Ti4O7 using a plasma spraying device. The spraying current is 550 A, the main gas flow rate is 30 L / min, the secondary gas flow rate is 4 L / min, the feeding amount is 35 g / min, and the coating thickness is 0.5 mm.

[0036] Example 2

[0037] This embodiment provides a conductive ceramic carbon fiber roll, which is different from that of Example 1 in that a 0.07-mm-thick aluminum alloy coating is first sprayed on the carbon fiber prepreg roll core, and then a ceramic layer is formed on the aluminum alloy coating. The aluminum alloy coating is formed by arc spraying under the spraying conditions of a current of 100 A, a voltage of 25 V, and a spraying distance of 100 mm. The ceramic layer is a coating formed by spraying titanium suboxide Ti4O7. The spraying current is 550 A, the main gas flow rate is 30 L / min, the secondary gas flow rate is 4 L / min, the feeding amount is 35 g / min, and the coating thickness is 0.5 mm.

[0038] Example 3

[0039] This embodiment provides a conductive ceramic carbon fiber roll, which is different from that of Example 2 in that 30-50 mesh white fused alumina is first sandblasted and sprayed (the sandblasting pressure is 0.5 MPa and the sandblasting amount is 300 g) on the carbon fiber prepreg roll core, then a 0.07-mm-thick aluminum coating is sprayed, and then a ceramic layer is formed on the aluminum coating. The aluminum alloy coating is formed by arc spraying under the spraying conditions of a current of 100 A, a voltage of 25 V, and a spraying distance of 100 mm. The ceramic layer is a coating formed by spraying titanium suboxide Ti4O7. The spraying current is 550 A, the main gas flow rate is 30 L / min, the secondary gas flow rate is 4 L / min, the feeding amount is 35 g / min, and the coating thickness is 0.5 mm.

[0040] Example 4

[0041] This embodiment provides a conductive ceramic carbon fiber roll, which includes a carbon fiber prepreg roll core, a metal powder layer formed on the outer surface of the carbon fiber prepreg roll core, and a ceramic layer formed on the outer surface of the metal powder layer. The ceramic layer is a coating formed by spraying titanium suboxide Ti4O7. The spraying current is 550 A, the main gas flow rate is 30 L / min, the secondary gas flow rate is 4 L / min, the feeding amount is 35 g / min, and the coating thickness is 0.5 mm. The thickness of the metal powder layer is 0.07 mm. The raw materials of the metal powder layer are: 1 part by weight of aluminum powder, 0.1 part by weight of silicon dioxide particles, and 0.1 part by weight of epoxy resin powder. The particle size of the silicon dioxide particles is between 100 and 150 nm. The metal powder coating is formed by arc spraying under the spraying conditions of a current of 100 A, a voltage of 25 V, and a spraying distance of 100 mm.

[0042] The difference from Example 2 lies in that the coating material for forming the metal powder is different.

[0043] Example 5

[0044] This example provides a conductive ceramic carbon fiber roll, which includes a carbon fiber prepreg roll core, a metal powder layer formed on the outer surface of the carbon fiber prepreg roll core, and a ceramic layer formed on the outer surface of the metal powder layer. The ceramic layer is a coating formed by spraying titanium suboxide Ti4O7, with a spraying current of 550 A, a main gas flow rate of 30 L / min, a secondary gas flow rate of 4 L / min, a feeding amount of 35 g / min, and a coating thickness of 0.5 mm. The thickness of the metal powder layer is 0.07 mm. The raw materials of the metal powder layer are: 1 part by weight of aluminum powder, 0.15 part by weight of silicon dioxide particles, and 0.1 part by weight of epoxy resin powder. The particle size of the silicon dioxide particles is between 100 - 150 nm. The metal powder coating is formed by arc spraying, and the spraying conditions are a current of 100 A, a voltage of 25 V, and a spraying distance of 100 mm.

[0045] Example 6

[0046] This example provides a conductive ceramic carbon fiber roll, which includes a carbon fiber prepreg roll core, a metal powder layer formed on the outer surface of the carbon fiber prepreg roll core, and a ceramic layer formed on the outer surface of the metal powder layer. The ceramic layer is a coating formed by spraying titanium suboxide Ti4O7, with a spraying current of 550 A, a main gas flow rate of 30 L / min, a secondary gas flow rate of 4 L / min, a feeding amount of 35 g / min, and a coating thickness of 0.5 mm. The thickness of the metal powder layer is 0.07 mm. The raw materials of the metal powder layer are: 1 part by weight of aluminum powder, 0.15 part by weight of silicon dioxide particles, and 0.2 part by weight of epoxy resin powder. The particle size of the silicon dioxide particles is between 100 - 150 nm. The metal powder coating is formed by arc spraying, and the spraying conditions are a current of 100 A, a voltage of 25 V, and a spraying distance of 100 mm.

[0047] Example 7

[0048] This embodiment provides a conductive ceramic carbon fiber roll, which includes a carbon fiber prepreg roll core, a metal powder layer formed on the outer surface of the carbon fiber prepreg roll core, and a ceramic layer formed on the outer surface of the metal powder layer. The ceramic layer is a coating formed by spraying titanium suboxide Ti4O7. The spraying current is 550 A, the main gas flow rate is 30 L / min, the secondary gas flow rate is 4 L / min, the feeding amount is 35 g / min, and the coating thickness is 0.5 mm. The thickness of the metal powder layer is 0.07 mm. The raw materials of the metal powder layer are: 1 part by weight of aluminum powder, 0.13 part by weight of silicon dioxide particles, and 0.15 part by weight of epoxy resin powder. The particle size of the silicon dioxide particles is between 100 - 150 nm. The metal powder coating is formed by arc spraying, and the spraying conditions are a current of 100 A, a voltage of 25 V, and a spraying distance of 100 mm.

[0049] Example 8

[0050] This embodiment provides a conductive ceramic carbon fiber roll, which includes a carbon fiber prepreg roll core, a metal powder layer formed on the outer surface of the carbon fiber prepreg roll core, and a ceramic layer formed on the outer surface of the metal powder layer. The ceramic layer is a coating formed by spraying titanium suboxide Ti4O7. The spraying current is 550 A, the main gas flow rate is 30 L / min, the secondary gas flow rate is 4 L / min, the feeding amount is 35 g / min, and the coating thickness is 0.5 mm. The thickness of the metal powder layer is 0.07 mm. The raw materials of the metal powder layer are: 1 part by weight of aluminum-magnesium alloy powder, 0.15 part by weight of titanium dioxide particles, and 0.2 part by weight of epoxy resin powder. The particle size of the silicon dioxide particles is between 50 - 100 nm. The metal powder coating is formed by arc spraying, and the spraying conditions are a current of 100 A, a voltage of 25 V, and a spraying distance of 100 mm.

[0051] Example 9

[0052] This embodiment provides a conductive ceramic carbon fiber roll, which includes a carbon fiber prepreg roll core, a sand layer sprayed on the surface of the roll core, a metal powder layer formed on the surface of the sand layer, and a ceramic layer formed on the outer surface of the metal powder layer. The sand layer is formed by spraying 30 - 50 mesh white corundum. The ceramic layer is a coating formed by spraying titanium suboxide Ti4O7. The spraying current is 550 A, the main gas flow rate is 30 L / min, the secondary gas flow rate is 4 L / min, the feeding amount is 35 g / min, and the coating thickness is 0.5 mm. The thickness of the metal powder layer is 0.07 mm. The raw materials of the metal powder layer are: 1 part by weight of aluminum-magnesium alloy powder, 0.15 part by weight of titanium dioxide particles, and 0.2 part by weight of epoxy resin powder. The particle size of the silicon dioxide particles is between 50 - 100 nm. The metal powder coating is formed by arc spraying, and the spraying conditions are a current of 100 A, a voltage of 25 V, and a spraying distance of 100 mm.

[0053] The average resistivity of the surface of the ceramic carbon fiber rollers obtained in the above embodiments (when just leaving the factory and after 3 months of use) was detected using a resistivity tester, and the test results are shown in Table 1 below (the resistivity in Table 1 is the average value obtained by selecting 5 ceramic carbon fiber rollers).

[0054] Table 1 Resistivity of the surface of the carbon fiber rollers obtained in each embodiment

[0055]

[0056] As can be seen from the results shown in Table 1, the resistivity of the surface of the ceramic carbon fiber rollers obtained in the above embodiments is below 30 Ω·cm at the initial stage of leaving the factory, which can meet the use in places with high anti-static requirements. Especially for Embodiments 4 to 9, after adopting a specific metal powder layer, it is below 20 Ω·cm at the initial stage of leaving the factory, showing a significant improvement, and the anti-static performance is more excellent. Among them, in Embodiment 7, the composition ratio of the metal powder layer was optimized, and the obtained ceramic carbon fiber roller has the best anti-static performance. From the resistivity after three months of use, for the ceramic carbon fiber rollers (Embodiments 1 and 2) corresponding to the metal powder layer formed by conventional metal powder, the resistivity increases after three months, and the anti-static performance decreases. In the scheme of adding a sand layer (Embodiment 3), it is alleviated to a certain extent, but the anti-static performance still decreases. While for the ceramic carbon fiber rollers (Embodiments 4 - 9) corresponding to the specific metal powder layer of the present invention, the resistivity changes insignificantly after three months, and the ceramic carbon fiber rollers still have a relatively good anti-static effect. Compared with Embodiment 8, although a sand layer is added in Embodiment 9, it has no positive effect on the final result. It shows that by adopting the specific metal powder layer of the present invention, the sand layer can be omitted, which is more conducive to the simplification of the process and the control of production costs.

[0057] In order to study the stability of the anti-static performance of the ceramic carbon fiber rollers among batches, the resistivity of the ceramic carbon fiber rollers obtained in the above embodiments at the time of leaving the factory was also detected and analyzed for the same production batch and different production batches (the production conditions are the same among different production batches), and the results are shown in Table 2 (the resistivity of the same production batch, the resistivity corresponding to 5 selected ceramic carbon fiber rollers) and Table 3 (the resistivity among different production batches, the average value obtained by selecting 5 ceramic carbon fiber rollers for each of the three batches). Among them, the uniformity calculation formula is as follows: Uniformity = [(maximum film thickness - minimum film thickness) / (2 * average film thickness)] * 100%. The smaller the uniformity, the more stable the resistivity; conversely, the larger the uniformity, the more unstable the resistivity.

[0058] Table 2 Resistivity of ceramic carbon fiber rollers in the same production batch

[0059]

[0060] Table 3 Resistivity of Ceramic Carbon Fiber Rolls in Different Production Batches

[0061]

[0062] Comparative Example 1

[0063] This comparative example provides a conductive ceramic carbon fiber roll, which is different from Example 2 in that the ceramic layer is formed by spraying with WC-12Co powder material.

[0064] Comparative Example 2

[0065] This comparative example provides a conductive ceramic carbon fiber roll, which is different from Example 2 in that the ceramic layer is formed by spraying with WC-12Ni powder material.

[0066] Comparative Example 3

[0067] This comparative example provides a conductive ceramic carbon fiber roll, which is different from Example 2 in that the ceramic layer is formed by spraying with Cr3C2-NiCr (75% (Cr3C2)-25% (NiCr)) powder material.

[0068] Comparative Examples 1-3 are several commonly used conductive cermet powders purchased by the inventors from the market. A ceramic layer is formed on the metal powder coating on the surface of the carbon fiber prepreg roll core. The average resistivity of the surfaces of the ceramic carbon fiber rolls obtained in Example 2 and each comparative example is detected, and the detection results are shown in Table 4 below (the resistivity in Table 4 is the average value obtained by selecting 5 ceramic carbon fiber rolls).

[0069] Table 4 Average Resistivity of the Surfaces of the Ceramic Carbon Fiber Rolls Obtained in Example 2 and Each Comparative Example

[0070]

[0071] As can be seen from Table 4, when the ceramic powder of the comparative example is used to form the ceramic layer, the resistivity of the corresponding ceramic carbon fiber roll increases significantly, failing to meet the requirements for high antistatic performance.

Claims

1. A conductive ceramic carbon fiber roller, comprising a carbon fiber prepreg roller core and a ceramic layer formed on the outer surface of the carbon fiber prepreg roller core, characterized in that: The ceramic layer is a coating formed by titanium oxide, and the general formula of titanium oxide is: Ti n O 2n-1 (4≤n≤10); a metal transition layer formed of metal powder is also formed between the carbon fiber prepreg roller core and the ceramic layer, the metal powder used in the metal transition layer is doped with inorganic particles and organic resin, and the weight ratio of the metal powder, the inorganic particles and the organic resin is 1: (0.1-0.15): (0.1-0.2), wherein the inorganic particles are any one of silicon dioxide, titanium dioxide, aluminum oxide, and calcium carbonate or a mixture of several thereof, and the organic resin is epoxy resin.

2. A conductive ceramic carbon fiber roller according to claim 1, characterized in that: A sand layer is also formed between the carbon fiber prepreg roll core and the metal transition layer.

3. A conductive ceramic carbon fiber roller according to claim 2, characterized in that: The sand layer is formed by spraying white corundum with a mesh size of 30 to 50.

4. A conductive ceramic carbon fiber roller according to claim 1, characterized in that: The particle size of the inorganic particles is 50 nm to 150 nm.

5. A method for preparing a conductive ceramic carbon fiber roller according to any one of claims 1 to 4, characterized in that: The steps include: S1. Providing a roller core made of carbon fiber prepreg; S2. Clean the surface of the roller core and blast it to form a sand layer; S3. Spraying metal powder on the roller surface forming a sand layer to form a metal transition layer; S4. Spraying ceramic powder on the roller surface having the metal transition layer formed thereon to form a ceramic layer.

6. The use of a conductive ceramic carbon fiber roller according to any one of claims 1 to 4, characterized in that: Used in lithium battery thin film manufacturing or chip manufacturing.

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