（一）技术领域(1) Technical field
本发明涉及一种新型PVD三元涂层，用来改善刀具、模具表面硬度、表面热稳定性和耐冲击磨损性能，大幅提高刀具、模具的使用寿命；改善模具表面的脱模性能，提高塑料件产品成型精度，即一种含有NiCrN三元复合涂层的制品及制备方法。The invention relates to a new type of PVD ternary coating, which is used to improve the surface hardness, surface thermal stability and impact wear resistance of tools and molds, greatly increase the service life of tools and molds; improve the mold release performance of mold surfaces, and improve plastic The forming accuracy of the product is a product containing NiCrN ternary composite coating and its preparation method.
（二）背景技术(2) Background technology
随着汽车工业的迅速发展，汽车配套零件的需求量大幅度增加。其中，工件的质量、产量和生产成本往往取决于模具的质量及有效使用寿命。然而在极其恶劣的工况条件下，模具钢经常发生早期表面失效。为防止模具发生早期失效，延长模具的使用寿命，最经济最有效的方式就是对模具进行表面处理。PVD磁控溅射涂层能有效改善基体的硬度、抗磨减摩等表面性能。其中，CrTiN三元复合涂层以其优异的机械性能得到了国内外科研工作者的广泛关注。CrTiN三元复合涂层比目前应用最广泛的TiN和CrN有更好的硬度、膜/基结合强度。CrTiN涂层在钻头、车刀等工具上的应用已经得到广泛认可，但对于模具，该涂层的应用却受到了限制。这主要是因为刀具和模具钢的工作环境极其恶劣，而CrTiN涂层自身性能也存在较大的缺陷，例如其韧性较差，在冲击载荷下易于开裂、剥落。为进一步优化涂层综合性能和提高膜基结合强度，本发明在CrTiN涂层的基础上引入Ni元素，旨在开发一种新型NiCrN三元涂层。With the rapid development of the automobile industry, the demand for automobile accessories has increased significantly. Among them, the quality, output and production cost of the workpiece often depend on the quality and effective service life of the mold. However, under extremely harsh working conditions, early surface failures often occur in die steel. In order to prevent early failure of the mold and prolong the service life of the mold, the most economical and effective way is to carry out surface treatment on the mold. PVD magnetron sputtering coating can effectively improve the surface properties of the substrate such as hardness, anti-wear and anti-friction. Among them, CrTiN ternary composite coating has attracted extensive attention of domestic and foreign researchers for its excellent mechanical properties. The CrTiN ternary composite coating has better hardness and film/substrate bonding strength than the most widely used TiN and CrN at present. The application of CrTiN coating on tools such as drill bits and turning tools has been widely recognized, but for molds, the application of this coating is limited. This is mainly because the working environment of tool and die steel is extremely harsh, and the CrTiN coating itself has relatively large defects, such as its poor toughness, and it is easy to crack and peel off under impact load. In order to further optimize the comprehensive performance of the coating and improve the bonding strength of the film base, the present invention introduces Ni element on the basis of the CrTiN coating, aiming to develop a new NiCrN ternary coating.
（三）发明内容(3) Contents of the invention
本发明目的是提供一种含有NiCrN三元涂层的制品及制备方法，进一步提高NiCrN复合涂层的膜基结合强度，控制每一层组织晶粒的大小在纳米尺度范围内且均匀；每一层的层厚度也在纳米尺度范围内；涂层组织空隙率低，组织致密，使涂层具有最佳的硬度/韧性组合，优化涂层的耐冲击磨损性能、减摩性能和表面热稳定性，提高模具的脱模性能。The object of the present invention is to provide a kind of product containing NiCrN ternary coating and preparation method, further improve the film-base bonding strength of NiCrN composite coating, control the size of each layer of structure crystal grain in the range of nanoscale and uniform; The layer thickness of the layer is also in the nanoscale range; the coating structure has low porosity and dense structure, so that the coating has the best hardness/toughness combination, and optimizes the impact and wear resistance, anti-friction performance and surface thermal stability of the coating , Improve the release performance of the mold.
本发明采用的技术方案是：The technical scheme adopted in the present invention is:
本发明提供一种含有NiCrN三元涂层的制品，所述制品以Cr层为底层，以NiCrN层为过渡层，在NiCrN过渡层上沉积若干层NiCrN-CrN复合涂层使复合涂层的厚度达到2~5μm。通常在NiCrN过渡层上沉积NiCrN-CrN复合涂层2~2.5h能使复合涂层的厚度达到2~5μm。The invention provides a kind of product that contains NiCrN ternary coating, and described product is bottom layer with Cr layer, is transition layer with NiCrN layer, deposits several layers of NiCrN-CrN composite coating on NiCrN transition layer so that the thickness of composite coating Reach 2~5μm. Usually, depositing NiCrN-CrN composite coating on the NiCrN transition layer for 2~2.5h can make the thickness of the composite coating reach 2~5μm.
本发明还提供一种所述含有NiCrN三元涂层制品的制备方法，所述方法为：（1）预处理：将制品基件在碱性溶液中超声清洗5~10min，再在丙酮中超声清洗6~9min，最后在无水乙醇中超声清洗4~8min，获得预处理后的制品基件；（2）采用非平衡磁控溅射法，将Cr层在Cr靶电流3~5A，基体偏压为-80~-120V条件下沉积到预处理后的制品基件上作为底层；（3）通氮气，在NiCr合金靶电流5~7A，基体偏压为-40~-80V的条件下，在底层上沉积NiCrN层作为过渡层；（4）最后制备NiCrN-CrN复合涂层，通氮气，在 Cr靶电流5-7A，基体偏压为-50~-80V，NiCr合金靶电流4~6A，基体偏压为-50~-80V条件下，将NiCrN-CrN复合涂层沉积到过渡层上使NiCrN-CrN复合涂层厚度为2~5μm，即获得含有NiCrN三元涂层的制品。The present invention also provides a method for preparing the product containing NiCrN ternary coating. The method is as follows: (1) Pretreatment: ultrasonically clean the base of the product in alkaline solution for 5-10 minutes, and then ultrasonically clean it in acetone Clean for 6-9 minutes, and finally ultrasonically clean in absolute ethanol for 4-8 minutes to obtain the pretreated product substrate; Deposit on the pretreated product substrate as the bottom layer under the condition of bias voltage of -80~-120V; (3) nitrogen gas, under the condition of NiCr alloy target current of 5~7A and substrate bias voltage of -40~-80V , deposit a NiCrN layer on the bottom layer as a transition layer; (4) Finally, prepare a NiCrN-CrN composite coating, pass nitrogen gas, and use a Cr target current of 5-7A, a substrate bias of -50~-80V, and a NiCr alloy target current of 4~ 6A, under the condition of substrate bias of -50~-80V, the NiCrN-CrN composite coating is deposited on the transition layer so that the thickness of the NiCrN-CrN composite coating is 2~5μm, and the product containing the NiCrN ternary coating is obtained.
进一步，步骤（1）所述方法为：将制品基件在碱性溶液中超声清洗8min，再在丙酮中超声清洗9min，最后在无水乙醇中超声清洗8min，获得预处理后的制品基件；所述碱性溶液为10g/L碱性水溶液，所述碱性水溶液中碱性物质为NaOH。Further, the method described in step (1) is: ultrasonically clean the product substrate in alkaline solution for 8 minutes, then ultrasonically clean it in acetone for 9 minutes, and finally ultrasonically clean it in absolute ethanol for 8 minutes to obtain the pretreated product substrate ; The alkaline solution is a 10g/L alkaline aqueous solution, and the alkaline substance in the alkaline aqueous solution is NaOH.
进一步，步骤（1）所述预处理过程还包括将制品基件在无水乙醇中超声清洗4~8min后，再进行渗氮处理或碳氮共渗处理。渗氮处理或碳氮共渗处理是本领域技术人员公知的方法，通常渗氮处理是指将模具钢在渗氮炉中570℃下渗氮处理8个小时；碳氮共渗处理是指向钢的表层同时渗入碳和氮的过程。Further, the pretreatment process in step (1) further includes ultrasonically cleaning the product substrate in absolute ethanol for 4-8 minutes, and then performing nitriding treatment or carbonitriding treatment. Nitriding treatment or carbonitriding treatment is a method well known to those skilled in the art. Usually, nitriding treatment refers to nitriding treatment of die steel at 570°C for 8 hours in a nitriding furnace; The process of simultaneously infiltrating the surface layer of carbon and nitrogen.
进一步，步骤（2）采用非平衡磁控溅射法将Cr层沉积到预处理后的制品基件上作为底层，沉积条件为：Cr靶电流3~5A，基体偏压为-100V。Further, in step (2), the unbalanced magnetron sputtering method is used to deposit the Cr layer on the pretreated product substrate as the bottom layer, and the deposition conditions are: Cr target current 3-5A, substrate bias voltage -100V.
进一步，步骤（3）采用磁控溅射法将NiCrN层沉积到Cr底层上作为过渡层，沉积条件为：通氮气，NiCr合金靶电流6A，基体偏压为-65V。Further, in step (3), magnetron sputtering is used to deposit a NiCrN layer on the Cr underlayer as a transition layer, the deposition conditions are: nitrogen gas flow, NiCr alloy target current 6A, substrate bias voltage -65V.
进一步，步骤（4）采用非平衡磁控溅射法将NiCrN-CrN复合涂层沉积到NiCrN过渡层上制成含有（NiCrN-CrN）复合三元涂层的制品，沉积条件为：在 Cr靶电流6A，基体偏压为-65V，NiCr合金靶电流5A，基体偏压为-65V。其中（NiCrN-CrN）复合涂层沉积以过渡层的沉积基础。Further, in step (4), the NiCrN-CrN composite coating is deposited onto the NiCrN transition layer by unbalanced magnetron sputtering to make a product containing (NiCrN-CrN) composite ternary coating, and the deposition conditions are: on a Cr target The current is 6A, the substrate bias is -65V, the NiCr alloy target current is 5A, and the substrate bias is -65V. Among them, the (NiCrN-CrN) composite coating is deposited based on the deposition of the transition layer.
本发明设计制备多层纳米梯度涂层，以提高涂层的膜基结合强度，在CrTiN复合涂层的基础上用Ni元素替代Ti，Ni元素能在很大程度上改善涂层韧性和热稳定性，并能减小模具与液态塑料的润湿程度；在镀膜前增加渗氮工艺或进行碳氮共渗处理。工件在炉内运行状态为两轴转动，即围绕主轴公转，同时也完成自转。The invention designs and prepares multi-layer nano-gradient coatings to improve the film-base bonding strength of the coating, and replaces Ti with Ni element on the basis of the CrTiN composite coating, and the Ni element can greatly improve the toughness and thermal stability of the coating Sex, and can reduce the degree of wetting between the mold and liquid plastic; add nitriding process or carbonitriding treatment before coating. The running state of the workpiece in the furnace is two-axis rotation, that is, it revolves around the main axis and completes the rotation at the same time.
本发明所述Cr靶，NiCr合金靶均为高纯金属，推荐购自英国梯尔镀层公司。The Cr target and the NiCr alloy target described in the present invention are all high-purity metals, and are recommended to be purchased from British Thiel Coating Company.
与现有技术相比，本发明的有益效果主要体现在：Compared with the prior art, the beneficial effects of the present invention are mainly reflected in:
（1）本发明采用多层梯度设计和镀膜前的渗氮工艺大大提高了涂层的膜基结合强度，本发明制备的梯度涂层在划痕试验中的临界载荷高达75N（一般膜基结合强度在45N左右），远高于其它方法和工艺制备的相关镀层；(1) The present invention adopts the multi-layer gradient design and the nitriding process before coating to greatly improve the film-base bonding strength of the coating. The critical load of the gradient coating prepared by the present invention in the scratch test is as high as 75N (general film-base bonding The strength is about 45N), which is much higher than the related coatings prepared by other methods and processes;
（2）由于弥散富Ni区的存在，涂层中弥散强化和应力强化作用增强通过调节NiCr合金靶的电流，使含NiCrN三元涂层制品的硬度可达到2780HV；(2) Due to the existence of the dispersed Ni-rich region, the dispersion strengthening and stress strengthening effects in the coating are enhanced. By adjusting the current of the NiCr alloy target, the hardness of the NiCrN-containing ternary coating product can reach 2780HV;
（3）Ni元素在很大程度上改善了涂层的韧性，通过控制制备工艺可以获得最优的硬度/韧性组合，Ni的存在使涂层晶粒细化，孔隙率降低，致密性变好；(3) The Ni element improves the toughness of the coating to a large extent, and the optimal hardness/toughness combination can be obtained by controlling the preparation process. The presence of Ni makes the grain of the coating refine, the porosity decreases, and the compactness becomes better. ;
（4）NiCrN三元涂层大幅提高了模具和刀具表面的抗冲击耐磨减摩性能和热稳定性，摩擦系数和磨损失重率都大幅降低；(4) The NiCrN ternary coating greatly improves the impact resistance, wear resistance and friction reduction performance and thermal stability of the surface of the mold and tool, and the friction coefficient and wear weight loss rate are greatly reduced;
（5）NiCrN三元涂层大大提高了模具钢对有机溶剂的润湿角，表明该涂层可大幅改善模具的脱模性能。(5) The NiCrN ternary coating greatly improves the wetting angle of the mold steel to organic solvents, indicating that the coating can greatly improve the release performance of the mold.
（四）附图说明(4) Description of drawings
图1本发明制备的涂层结构示意图。Fig. 1 is a schematic diagram of the coating structure prepared by the present invention.
图2 靶材分布与样品架放置示意图。Figure 2 Schematic diagram of target distribution and sample holder placement.
图3 Teer-UDP850/4型磁控溅射仪照片。Figure 3 Photo of Teer-UDP850/4 magnetron sputtering apparatus.
图4 含NiCrN三元涂层制品表面的扫描电镜图。Fig. 4 SEM image of the surface of the product containing NiCrN ternary coating.
图5 含NiCrN三元涂层制品有机溶剂的润湿角。Fig. 5 Wetting angle of organic solvent for NiCrN ternary coating products.
图6 无涂层制品表面有机溶剂的润湿角。Fig. 6 Wetting angle of organic solvent on the surface of uncoated article.
（五）具体实施方式(5) Specific implementation methods
下面结合具体实施例对本发明进行进一步描述，但本发明的保护范围并不仅限于此：The present invention is further described below in conjunction with specific embodiment, but protection scope of the present invention is not limited thereto:
选用英国梯尔镀层公司制造的Teer-UDP850/4型闭合场非平衡磁控溅射离子镀设备（Teer-UDP850/4 closed-filed unbalanced magnetron sputtering ion plating coater）来制备本发明所述含CrNiN三元涂层的制品，该设备由真空系统、电源系统、控制系统、冷却系统四部分组成，照片见图3所示。The Teer-UDP850/4 closed-field unbalanced magnetron sputtering ion plating equipment (Teer-UDP850/4 closed-filed unbalanced magnetron sputtering ion plating coater) manufactured by British Till Coating Company was selected to prepare the CrNiN-containing three The product of meta-coating, the equipment is composed of four parts: vacuum system, power supply system, control system and cooling system. The photo is shown in Figure 3.
真空系统为两级真空，前级采用机械泵粗抽，后级采用扩散泵精抽。如图2所示，真空壁上安装有四块靶材（2个Cr靶、2个NiCr合金靶，均购自英国梯尔镀层公司）。The vacuum system is a two-stage vacuum, the first stage uses a mechanical pump for rough pumping, and the latter stage uses a diffusion pump for fine pumping. As shown in Figure 2, four targets are installed on the vacuum wall (2 Cr targets and 2 NiCr alloy targets, all purchased from British Thiel Coating Company).
实施例1Example 1
（1）基件预处理：以和H13模具钢为制品基件，将制品基件在10 g/L氢氧化钠水溶液中超声清洗8min，再在丙酮中超声清洗9min，最后在无水乙醇中超声清洗8min，获得预处理后的制品基件。(1) Substrate pretreatment: take H13 mold steel as the product substrate, ultrasonically clean the product substrate in 10 g/L sodium hydroxide aqueous solution for 8 minutes, then ultrasonically clean it in acetone for 9 minutes, and finally clean it in absolute ethanol Ultrasonic cleaning for 8 minutes to obtain the pretreated product substrate.
（2）采用Teer-UDP850/4型闭合场非平衡磁控溅射离子镀设备制备NiCrN三元涂层（涂层结构示意图见图1所示）的主要步骤如下：(2) The main steps of preparing NiCrN ternary coating (see Figure 1 for the schematic diagram of the coating structure) are as follows:
1）开机预热，通冷却水，打开机械泵抽真空至4.0×10-4Pa，并将真空室加热至100℃；1) Turn on the machine for preheating, pass cooling water, turn on the mechanical pump to evacuate to 4.0×10-4 Pa, and heat the vacuum chamber to 100°C;
2）通入氩气，调节气瓶阀门和流量计，调整真空室内气压使靶材起辉；2) Introduce argon gas, adjust the gas cylinder valve and flow meter, and adjust the air pressure in the vacuum chamber to make the target glow;
3）离子清洗：使基体旋转，调节基体偏压至400V，用Ar+清洗基体表面20min，去除表面杂质，为正式镀膜做准备；3) Ion cleaning: rotate the substrate, adjust the bias voltage of the substrate to 400V, clean the surface of the substrate with Ar+ for 20 minutes, remove surface impurities, and prepare for the formal coating;
4）沉积金属Cr打底：开启Cr靶，靶电流为4A，调整基体偏压为-100V，沉积一层Cr，作为底层，以提高涂层与基体的结合强度；4) Deposit metal Cr as a primer: turn on the Cr target, set the target current to 4A, adjust the substrate bias to -100V, and deposit a layer of Cr as the bottom layer to improve the bonding strength between the coating and the substrate;
5）沉积NiCrN过渡层：将NiCr合金靶电流增至6 A，基体偏压-65V，打开氮气阀门，沉积一层NiCrN，作为过渡层，以进一步增强涂层与基体的结合强度；5) Deposit NiCrN transition layer: increase the NiCr alloy target current to 6 A, substrate bias -65V, open the nitrogen valve, and deposit a layer of NiCrN as a transition layer to further enhance the bonding strength between the coating and the substrate;
6）沉积（NiCrN-CrN）复合涂层：四靶（2个Cr靶、2个NiCr合金靶）按图2所示排列，全部开启，通氮气，Cr靶电流均为6A，基体偏压-65V，NiCr合金靶电流均为5A，基体偏压-65V。6) Deposition (NiCrN-CrN) composite coating: Four targets (2 Cr targets, 2 NiCr alloy targets) are arranged as shown in Figure 2, all are turned on, nitrogen gas is passed, the Cr target current is 6A, and the substrate bias is - 65V, the NiCr alloy target current is 5A, and the substrate bias is -65V.
7）镀膜完毕：冷却30分钟后，充氩气，开炉，取样，制品中NiCrN-CrN复合涂层厚度为3μm，即获得含有NiCrN三元涂层的制品，并将含有NiCrN三元涂层的制品作为试样进行性能测试。具体的工艺参数见表1所示。7) Coating completed: After cooling for 30 minutes, fill with argon, turn on the furnace, and take samples. The thickness of the NiCrN-CrN composite coating in the product is 3 μm, that is, the product containing NiCrN ternary coating will be obtained, and will contain NiCrN ternary coating The products are used as samples for performance testing. The specific process parameters are shown in Table 1.
表1 CrNiN三元涂层的制备工艺参数Table 1 Preparation process parameters of CrNiN ternary coating
采用HMV-1T型显微硬度计，测定10g载荷下的显微硬度值，保载时间为10s。为了减小误差每个试样测量显微硬度值五次，取五次的算术平均值作为该试样的硬度值。含NiCrN三元涂层的显微硬度值可达到2580HV。The HMV-1T microhardness tester was used to measure the microhardness value under a load of 10g, and the holding time was 10s. In order to reduce the error, measure the microhardness value of each sample five times, and take the arithmetic mean value of the five times as the hardness value of the sample. The microhardness value of the NiCrN ternary coating can reach 2580HV.
采用CQY-18型球痕仪测量计算含NiCrN三元涂层制品中涂层的厚度为3μm；采用WS-2004型涂层附着力划痕仪表征涂层的膜基结合强度，划痕试验中的临界载荷为60N。The thickness of the coating in the NiCrN-containing ternary coating product is 3 μm measured and calculated by the CQY-18 ball trace meter; the film-base bonding strength of the coating is characterized by the WS-2004 coating adhesion scratch meter, and the scratch test The critical load is 60N.
本发明制备的NiCrN三元涂层具有合理的成分梯度结构，涂层的结构设计如图1所示：由于Cr和钢基体有着公认良好的附着力，所以首先用Cr打底，然后其上用NiCrN过渡，最后沉积具有纳米多层结构的NiCrN-CrN复合层薄膜。这种连续平滑过渡的膜层成分可以使膜层的物理、化学性能和组织结构逐渐连续过渡，缓解界面处的应力状况，从而能很大程度上提高薄膜的综合性能。The NiCrN ternary coating prepared by the present invention has a reasonable compositional gradient structure, and the structural design of the coating is as shown in Figure 1: because Cr and the steel substrate have recognized good adhesion, so at first make a primer with Cr, then use NiCrN transition, and finally deposit a NiCrN-CrN composite layer film with a nano-multilayer structure. This continuous and smooth transition film composition can gradually and continuously transition the physical and chemical properties and organizational structure of the film layer, relieve the stress condition at the interface, and thus greatly improve the comprehensive performance of the film.
实施例2Example 2
将预处理后的H13模具钢在渗氮炉中570℃下渗氮处理8个小时，然后采用Teer-UDP850/4型闭合场非平衡磁控溅射离子镀设备制备NiCrN三元涂层。其他操作及方法同实施例1，制品中NiCrN-CrN复合涂层厚度为3μm，即获得含有NiCrN三元涂层的制品，并将含有NiCrN三元涂层的制品作为试样进行性能测试。The pretreated H13 die steel was nitriding at 570°C for 8 hours in a nitriding furnace, and then a NiCrN ternary coating was prepared using Teer-UDP850/4 closed-field unbalanced magnetron sputtering ion plating equipment. Other operations and methods are the same as in Example 1. The thickness of the NiCrN-CrN composite coating in the product is 3 μm, that is, the product containing the NiCrN ternary coating is obtained, and the product containing the NiCrN ternary coating is used as a sample for performance testing.
采用捷克TESCAN公司生产的VEGA-3-S型扫描电子显微镜对试样表面形貌进行观察，结果见图4所示。图4显示了NiCrN三元涂层表面纳米晶形貌。The VEGA-3-S scanning electron microscope produced by the Czech TESCAN company was used to observe the surface morphology of the sample, and the results are shown in Figure 4. Figure 4 shows the nanocrystalline morphology of the NiCrN ternary coating surface.
采用HMV-1T型显微硬度计，测定10g载荷下的显微硬度值，保载时间为10s。为了减小误差每个试样测量显微硬度值五次，取五次的算术平均值作为该试样的硬度值。涂层的显微硬度值可达到2780HV。The HMV-1T microhardness tester was used to measure the microhardness value under a load of 10g, and the holding time was 10s. In order to reduce the error, measure the microhardness value of each sample five times, and take the arithmetic mean value of the five times as the hardness value of the sample. The microhardness value of the coating can reach 2780HV.
采用CQY-18型球痕仪测量计算涂层的厚度为3μm；采用WS-2004型涂层附着力划痕仪表征涂层的膜基结合强度，划痕试验中的临界载荷为75N。The thickness of the coating was measured and calculated by the CQY-18 ball trace tester to be 3 μm; the film-substrate bonding strength of the coating was characterized by the WS-2004 coating adhesion scratch tester, and the critical load in the scratch test was 75N.
采用德国德菲QCA35型接触角测量仪测量了模具钢表面NiCrN三元涂层有机溶剂润湿角为101.9度（图5），而无涂层模具表面有机溶剂的润湿角78.3度（图6），表明该涂层可大幅改善模具的脱模性能。The organic solvent wetting angle of the NiCrN ternary coating on the surface of the mold steel was measured by the German Defei QCA35 contact angle measuring instrument as 101.9 degrees (Figure 5), while the wetting angle of the organic solvent on the uncoated mold surface was 78.3 degrees (Figure 6 ), indicating that the coating can greatly improve the release performance of the mold.
| Application Number | Priority Date | Filing Date | Title |
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| CN201210528707.0ACN103029366B (en) | 2012-12-06 | 2012-12-06 | Product containing NiCrN ternary coating and preparation method thereof |
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210528707.0ACN103029366B (en) | 2012-12-06 | 2012-12-06 | Product containing NiCrN ternary coating and preparation method thereof |
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| CN103029366A CN103029366A (en) | 2013-04-10 |
| CN103029366Btrue CN103029366B (en) | 2015-05-27 |
| Application Number | Title | Priority Date | Filing Date |
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| CN201210528707.0AActiveCN103029366B (en) | 2012-12-06 | 2012-12-06 | Product containing NiCrN ternary coating and preparation method thereof |
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