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一种烧结钕铁硼磁体表面功能膜层及其制备方法 【EN】Sintered neodymium-iron-boron magnet surface functional film layer and preparation method thereof

申请(专利)号:CN201911401802.2国省代码:辽宁 21
申请(专利权)人:【中文】沈阳中北通磁科技股份有限公司【EN】SHENYANG GENERAL MAGNETIC Co.,Ltd.
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摘要:
【中文】本发明公开一种烧结钕铁硼磁体表面功能膜层及其制备方法,包括磁体预处理工艺、磁体沉积前处理以及物理气相沉积法制备功能膜层。该功能膜层是以Al2O3层和TiN层为周期的多周期复合膜层,该功能膜层同时具有15GPa以上的硬度、良好的腐蚀防护性能和抗氧化性能。与此同时通过层和TiN层的交替沉积,避免形成贯穿单层薄膜的针孔、通孔和微裂纹等组织缺陷的出现,较好地解决了传统单层薄膜厚度难以控制的缺陷,并通过Al2O3的加入增强了磁体的耐高温氧化性。采用双层膜交替沉积,多周期组合的形式,减少了膜层内应力,增强了膜基结合力。通过在钕铁硼表面沉积功能膜层扩展了钕铁硼在高湿热及酸碱环境下的应用领域。 【EN】The invention discloses a functional film layer on the surface of a sintered neodymium-iron-boron magnet and a preparation method thereof. The functional film layer is Al2O3The layer and the TiN layer are periodic multi-period composite film layers, and the functional film layer has the hardness of more than 15GPa, good corrosion protection performance and oxidation resistance. Meanwhile, through the alternate deposition of the layer and the TiN layer, the occurrence of structural defects such as pinholes, through holes, microcracks and the like penetrating through the single-layer film is avoided, the defect that the thickness of the traditional single-layer film is difficult to control is well solved, and Al is used for preparing the thin film2O3The addition of (2) enhances the endurance of the magnetHigh-temperature oxidation. The double-layer film alternate deposition and multi-period combination are adopted, the internal stress of the film layer is reduced, and the film-substrate binding force is enhanced. The application field of the neodymium iron boron in high-humidity, high-heat and acid-base environments is expanded by depositing the functional film layer on the surface of the neodymium iron boron.

主权项:
【中文】1.一种烧结钕铁硼磁体表面功能膜层,其特征在于:该功能膜层是以AlO层和TiN层为周期的(AlO/TiN)结构多周期复合膜层,其中n为4~20;功能膜层采用磁控溅射沉积而成。 【EN】1. The utility model provides a sintered neodymium iron boron magnet surface function rete which characterized in that: the functional film layer is AlOThe layer and TiN layer being periodic (Al)O/TiN)The structure is a multi-period composite film layer, wherein n is 4-20; the functional film layer is formed by magnetron sputtering deposition.


说明书

【中文】

一种烧结钕铁硼磁体表面功能膜层及其制备方法

技术领域

本发明属于永磁器件表面防护领域,具体涉及一种烧结钕铁硼磁体表面功能膜层及其制备方法。

背景技术

钕铁硼磁体作为一种饱和磁化强度高、矫顽力强且性价比高的磁体,在新能源汽车制造、风能发电、新型电机等高科技行业应用非常广泛,但由于钕铁硼自身的特性易产生腐蚀现象。

目前工业中多采用电镀方式对钕铁硼表面形成保护膜,但容易出现二次腐蚀现象。现阶段采用物理相沉积方法在烧结钕铁硼磁体上沉积功能薄膜成为热点,而单一氮化钛薄膜一般均存在针孔、微裂纹等组织缺陷,当在合适的环境下就通过组织缺陷形成的路径侵害到烧结钕铁硼磁体,导致烧结钕铁硼磁体耐腐蚀性差,从而影响烧结钕铁硼磁体的应用范围。因此开发一种烧结钕铁硼磁体表面高耐蚀、绿色环保且涂覆均匀结合力强的复合膜层,具有重要的经济效益、社会效益和环保效益。

发明内容

本发明针对烧结钕铁硼磁体表面单一TiN层存在耐蚀性能差的问题,提供一种烧结钕铁硼磁体表面高耐蚀复合膜层及其制备方法。

为了达到上述目的,本发明采用的主要技术方案包括:

一方面,本发明提供了一种具有复合膜层的烧结钕铁硼磁体,包括磁体本体,以及依次层叠设置于所述磁体本体表面的铝膜层 、氧化铝膜层和氮化钛膜层,形成以Al2O3层和TiN层为周期的(Al2O3/TiN)n 结构多周期复合膜层,其中n为4~20,该功能膜层采用磁控溅射沉积而成。

根据本发明,所述氧化铝膜层的厚度为0.03~0.15μm;所述氮化钛膜层的厚度为0.22~1.1μm;

所述复合膜层的总厚度为2~8μm。

另一方面,本发明还提供了一种具有复合膜层的烧结钕铁硼磁体的制备方法,包括以下步骤:

对所述磁体本体表面进行打磨、抛光以及清洗;

利用物理气相沉积法在所述磁体本体表面沉积氧化铝膜层和氮化钛膜层。

如上述方法,所述对磁体本体表面进行打磨、抛光以及清洗包括:

分别利用#400、#600、#1000、#1500、#2000砂纸依次打磨所述磁体本体的表面;

利用抛光机对经过打磨的磁体本体的表面进行抛光,直至其呈镜面状;

将抛光完成的磁体本体依次放置在无水乙醇和丙酮溶液中进行超声清洗5~15min,并反复清洗两次;

将处理后的磁体本体放入物理气相沉积涂覆设备的真空室中,将真空室真空度为设置为0.5~1Pa、氩气的流量设置为10~20sccm,采用循环氩离子轰击工艺对磁体本体轰击30min。

在利用物理气相沉积法在所述磁体本体表面依次沉积氧化铝膜层和氮化钛膜层的过程包括:

向真空室中充入氩气至气压为0.4~1.0Pa,打开射频电源,调节射频功率150W~300W,通过射频溅射在磁体本体上沉积氧化铝膜层;

将真空室内气体排出,按照氩气流量30sccm和氮气流量2sccm将氩气和氮气充入真空室直至真空室气压为0.3~1.0Pa,对钛靶通电,调节钛靶功率为100~150W,在磁体本体的氧化铝膜层上沉积氮化钛膜层,完成后关闭钛靶电源,此为完成一个周期,按照以上步骤重复完成4-20个周期。

如上述方法,在氧化铝膜层上沉积氮化钛膜层包括:

对靶材进行10min的预溅射,以去除靶材表面附着的污染物;

移开样品台挡板,在所述氧化铝膜层进行溅射沉积氮化钛膜层。

氮气的纯度大于99.9 wt %,氩气的纯度大于99.9 wt %。

本发明的有益效果在于:

本发明提供的在磁铁本体的表面多层复合膜层结构,从基体材料表面到复合膜层表面,复合膜层为以Al2O3/TiN为一个周期的,多周期(Al2O3/TiN)n功能膜层,n值为4-20。该功能具有良好硬度和耐腐蚀防护性能。通过在磁体本体表面交替沉积氧化铝膜层和氮化钛膜层,能够解决由单层膜引起的针孔和通孔缺陷。同时多层膜的结构解决了单层膜过薄起不到保护作用,过厚易产生裂纹的现状。此外,通过氧化铝膜层的设置,还提高了烧结铷铁硼磁体的耐高温抗氧化性。

具体实施方式

实施例1

向真空室充入氩气至气压为0.5Pa,射频功率为115W,通过射频溅射在磁体本体上沉积氧化铝膜层;最后,将真空室内的气体排出,按照氩气流量30sccm和氮气流量2sccm将氩气和氮气充入真空室直至真空室气压为0.35Pa,调节钛靶功率为115W,在磁体本体的氧化铝膜层上沉积氮化钛膜层,完成后关闭钛靶电源,氧化铝与氮化钛厚度比3:22,此时完成一个周期的沉积,按照以上步骤沉积4个周期,经检测,在该条件下得到的复合膜层的性能如下:

实施例2

向真空室充入氩气至气压为0.5Pa,射频功率为115W,通过射频溅射在磁体本体上沉积氧化铝膜层;最后,将真空室内气体排出,按照氩气流量30sccm和氮气流量2sccm将氩气和氮气充入真空室,直至真空室气压为0.35Pa,调节钛靶功率为115W,在磁体本体的氧化铝膜层上沉积氮化钛膜层,完成后关闭钛靶电源,氧化铝与氮化钛厚度比3:22,此时完成一个周期的沉积,按照以上步骤沉积20个周期。经检测,在该条件下得到的复合膜层的性能如下:

在一个可选的实施例中,具体包括以下步骤:

对靶材进行10min的预溅射,以去除靶材表面附着的污染物;

移开样品台挡板,在氧化铝膜层上沉积氮化钛膜层。

由于金属靶材往往会附着氧化物或者杂质等污染物,所以在溅射沉积之前,需要对靶材进行预溅射,预溅射可以起到清洁靶材表面的作用,防止靶材表面的污染物通过溅射沉积到烧结钕铁硼磁体表面,影响复合膜层的性能。

在预溅射时,可以在样品台设置挡板,防止预溅射时靶材表面的污染物沉积到烧结钕铁硼磁体表面,在预溅射完成后,移开样品台上的挡板,在烧结钕铁硼磁体氧化铝膜层上进行溅射沉积氮化钛膜层。

在一个可选的实施例中,氮气的纯度大于99.9wt%,氩气的纯度大于99.9wt %。氩气作为物理气相沉积过程的重要工作气体,其具有较高纯度可以使沉积过程更加稳定,使得每一个膜层的沉积更加牢固不容易脱落,保证了复合膜层的耐高温和耐腐蚀性,在沉积氮化钛膜层时,氮气是必要的反应气体,较高纯度的氮气能够保证溅射过程中钛与氮气的充分反应,保证了氮化钛膜层的纯度,从而保证了复合膜层的硬度和耐腐蚀程度。

在一个可选的实施例中,氧化铝的纯度大于99 wt %,氧化铝膜层可以提高铷铁硼磁体的耐高温抗氧化性,同时较高纯度的氧化铝可以作为氮化钛膜层与磁体之间的缓冲层,有利于提高功能膜层的膜基结合力。

在一个可选的实施例中,钛纯度可以大于99 wt %,钛作为氮化钛膜层的主要原料,其纯度越高,越能减小氮化钛膜层中的杂质,提高氮化钛膜层的硬度和膜层表面致密度,从而保证该复合膜层的硬度和耐腐蚀性能。

【EN】

Sintered neodymium-iron-boron magnet surface functional film layer and preparation method thereof

Technical Field

The invention belongs to the field of surface protection of permanent magnet devices, and particularly relates to a surface functional film layer of a sintered neodymium-iron-boron magnet and a preparation method thereof.

Background

The neodymium iron boron magnet is a magnet with high saturation magnetization, strong coercive force and high cost performance, is widely applied to high-tech industries such as new energy automobile manufacturing, wind power generation, novel motors and the like, but is easy to generate corrosion due to the characteristics of the neodymium iron boron magnet.

At present, the protection film is formed on the surface of the neodymium iron boron by adopting an electroplating mode in the industry, but the secondary corrosion phenomenon is easy to occur. At the present stage, a physical phase deposition method is adopted to deposit a functional film on the sintered neodymium iron boron magnet to form a hot spot, while a single titanium nitride film generally has structural defects such as pinholes, microcracks and the like, and when the single titanium nitride film infringes the sintered neodymium iron boron magnet through a path formed by the structural defects in a proper environment, the sintered neodymium iron boron magnet has poor corrosion resistance, so that the application range of the sintered neodymium iron boron magnet is influenced. Therefore, the composite film layer with high corrosion resistance, environmental protection and uniform coating and strong binding force on the surface of the sintered neodymium-iron-boron magnet is developed, and has important economic benefits, social benefits and environmental protection benefits.

Disclosure of Invention

The invention provides a high-corrosion-resistance composite film layer on the surface of a sintered neodymium-iron-boron magnet and a preparation method thereof, aiming at the problem that a single TiN layer on the surface of the sintered neodymium-iron-boron magnet is poor in corrosion resistance.

In order to achieve the purpose, the invention adopts the main technical scheme that:

on one hand, the invention provides a sintered neodymium-iron-boron magnet with a composite film layer, which comprises a magnet body, and an aluminum film layer, an aluminum oxide film layer and a titanium nitride film layer which are sequentially stacked on the surface of the magnet body to form Al2O3The layer and TiN layer being periodic (Al)2O3/TiN)nThe structural multi-period composite film layer is characterized in that n is 4-20, and the functional film layer is formed by magnetron sputtering deposition.

According to the invention, the thickness of the alumina film layer is 0.03-0.15 μm; the thickness of the titanium nitride film layer is 0.22-1.1 mu m;

the total thickness of the composite film layer is 2-8 mu m.

On the other hand, the invention also provides a preparation method of the sintered neodymium-iron-boron magnet with the composite film layer, which comprises the following steps:

grinding, polishing and cleaning the surface of the magnet body;

and depositing an aluminum oxide film layer and a titanium nitride film layer on the surface of the magnet body by using a physical vapor deposition method.

As in the above method, the grinding, polishing and cleaning of the surface of the magnet body includes:

sequentially polishing the surface of the magnet body by using #400, #600, #1000, #1500 and #2000 sandpaper respectively;

polishing the surface of the polished magnet body by using a polishing machine until the surface is in a mirror surface shape;

placing the polished magnet body in absolute ethyl alcohol and acetone solution in sequence, carrying out ultrasonic cleaning for 5-15 min, and repeatedly cleaning twice;

and (3) putting the processed magnet body into a vacuum chamber of physical vapor deposition coating equipment, setting the vacuum degree of the vacuum chamber to be 0.5-1 Pa, setting the flow of argon to be 10-20 sccm, and bombarding the magnet body for 30min by adopting a circulating argon ion bombardment process.

The process of sequentially depositing an alumina film layer and a titanium nitride film layer on the surface of the magnet body by using a physical vapor deposition method comprises the following steps:

filling argon into the vacuum chamber until the air pressure is 0.4-1.0 Pa, turning on a radio frequency power supply, adjusting the radio frequency power to 150-300W, and depositing an alumina film on the magnet body by radio frequency sputtering;

discharging gas in the vacuum chamber, filling argon and nitrogen into the vacuum chamber according to the flow rate of the argon being 30sccm and the flow rate of the nitrogen being 2sccm until the air pressure of the vacuum chamber is 0.3-1.0 Pa, electrifying the titanium target, adjusting the power of the titanium target to be 100-150W, depositing a titanium nitride film layer on the alumina film layer of the magnet body, turning off the power supply of the titanium target after the titanium target is completed, and repeating the steps for 4-20 periods.

As described above, depositing a titanium nitride film on an alumina film includes:

pre-sputtering the target for 10min to remove pollutants attached to the surface of the target;

and moving away the sample stage baffle, and performing sputtering deposition on the aluminum oxide film layer to obtain a titanium nitride film layer.

The purity of nitrogen is more than 99.9wt%, and the purity of argon is more than 99.9 wt%.

The invention has the beneficial effects that:

the invention provides a multilayer composite film structure on the surface of a magnet body, which is characterized in that from the surface of a base material to the surface of a composite film, the composite film is made of Al2O3One-cycle, multicycle with/TiN (Al)2O3/TiN)nThe functional film layer has n value of 4-20. The function has good hardness and corrosion resistance and protection performance. The aluminum oxide film layer and the titanium nitride film layer are alternately deposited on the surface of the magnet body, so that the defects of pinholes and through holes caused by a single-layer film can be overcome. Meanwhile, the structure of the multilayer film solves the problems that a single-layer film is too thin and cannot play a role in protection, and cracks are easily generated due to too thick single-layer film. In addition, the high-temperature resistance and the oxidation resistance of the sintered rubidium-iron-boron magnet are also improved through the arrangement of the alumina film layer.

Detailed Description

Example 1

Argon is filled into the vacuum chamber until the air pressure is 0.5Pa and the radio frequency power is 115W, and an alumina film layer is deposited on the magnet body through radio frequency sputtering; and finally, discharging gas in the vacuum chamber, filling argon and nitrogen into the vacuum chamber according to the argon flow of 30sccm and the nitrogen flow of 2sccm until the air pressure of the vacuum chamber is 0.35Pa, adjusting the power of the titanium target to be 115W, depositing a titanium nitride film layer on the aluminum oxide film layer of the magnet body, closing a power supply of the titanium target after the deposition is finished, wherein the thickness ratio of the aluminum oxide to the titanium nitride is 3:22, the deposition of one period is finished, the deposition is carried out for 4 periods according to the steps, and the performance of the composite film layer obtained under the conditions is detected as follows:

example 2

Argon is filled into the vacuum chamber until the air pressure is 0.5Pa and the radio frequency power is 115W, and an alumina film layer is deposited on the magnet body through radio frequency sputtering; and finally, discharging gas in the vacuum chamber, filling argon and nitrogen into the vacuum chamber according to the argon flow rate of 30sccm and the nitrogen flow rate of 2sccm until the air pressure of the vacuum chamber is 0.35Pa, adjusting the power of the titanium target to be 115W, depositing a titanium nitride film layer on the aluminum oxide film layer of the magnet body, closing a power supply of the titanium target after the deposition is finished, wherein the thickness ratio of aluminum oxide to titanium nitride is 3:22, and at the moment, completing the deposition of one period, and depositing for 20 periods according to the steps. Through detection, the performance of the composite film layer obtained under the condition is as follows:

in an optional embodiment, the method specifically includes the following steps:

pre-sputtering the target for 10min to remove pollutants attached to the surface of the target;

and (4) moving away the sample table baffle, and depositing a titanium nitride film layer on the alumina film layer.

Because the metal target material is always attached with pollutants such as oxides or impurities, the target material needs to be pre-sputtered before sputtering deposition, the pre-sputtering can play a role in cleaning the surface of the target material, and the pollutants on the surface of the target material are prevented from being deposited on the surface of the sintered neodymium iron boron magnet through sputtering, so that the performance of the composite film layer is not affected.

When the pre-sputtering is performed, a baffle can be arranged on the sample table to prevent pollutants on the surface of the target from being deposited on the surface of the sintered neodymium iron boron magnet during the pre-sputtering, after the pre-sputtering is completed, the baffle on the sample table is removed, and a titanium nitride film layer is sputtered and deposited on the alumina film layer of the sintered neodymium iron boron magnet.

In an alternative embodiment, the purity of nitrogen is greater than 99.9wt% and the purity of argon is greater than 99.9 wt%. The argon gas is used as an important working gas in the physical vapor deposition process, the argon gas has higher purity, so that the deposition process is more stable, the deposition of each film layer is firmer and is not easy to fall off, the high temperature resistance and the corrosion resistance of the composite film layer are ensured, when the titanium nitride film layer is deposited, the nitrogen gas is necessary reaction gas, the nitrogen gas with higher purity can ensure the full reaction of titanium and the nitrogen gas in the sputtering process, the purity of the titanium nitride film layer is ensured, and the hardness and the corrosion resistance of the composite film layer are ensured.

In an optional embodiment, the purity of the alumina is greater than 99 wt%, the alumina film layer can improve the high-temperature oxidation resistance of the rubidium-iron-boron magnet, and meanwhile, the alumina with higher purity can be used as a buffer layer between the titanium nitride film layer and the magnet, which is beneficial to improving the film-substrate binding force of the functional film layer.

In an optional embodiment, the purity of titanium can be more than 99 wt%, and the higher the purity of titanium is as a main raw material of the titanium nitride film layer, the more impurities in the titanium nitride film layer can be reduced, and the hardness of the titanium nitride film layer and the surface compactness of the film layer are improved, so that the hardness and the corrosion resistance of the composite film layer are ensured.

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