技术领域technical field
本发明涉及材料技术研究领域，具体的涉及一种等离子涂层的制备方法。 The invention relates to the field of material technology research, in particular to a method for preparing a plasma coating. the
背景技术Background technique
TiN涂层具有低的摩擦系数和高的硬度，以及良好的耐腐蚀性被广泛应用为装饰涂层、耐磨涂层、耐腐蚀涂层。目前，许多研究者通过反应热喷涂、化学气相沉积(CVD)、物理气相沉积(PVD)、电孤镀、等技术制备了TiN涂层，并对涂层的沉积过程，显微结构和性能进行了研究。采用CVD、PVD等技术制备的TiN涂层厚度较薄，降低涂层的机械性能；而利用热喷涂反应技术可以制备较厚的TiN涂层，但涂层内含有较多的孔隙，脆性较大，涂层质量不易控制。采用等离子喷技术直接喷涂TiN粉末可以在短时间内制备较厚的涂层，同时在喷涂过程TiN发生氧化，产生Ti的氧化物相，可以提高涂层的韧性。 TiN coating has low coefficient of friction, high hardness, and good corrosion resistance, and is widely used as decorative coating, wear-resistant coating, and corrosion-resistant coating. At present, many researchers have prepared TiN coatings by reactive thermal spraying, chemical vapor deposition (CVD), physical vapor deposition (PVD), arc plating, etc. studied. The thickness of the TiN coating prepared by CVD, PVD and other technologies is thin, which reduces the mechanical properties of the coating; while the thermal spraying reaction technology can be used to prepare a thicker TiN coating, but the coating contains more pores and is more brittle. , The coating quality is not easy to control. The direct spraying of TiN powder by plasma spraying technology can prepare a thicker coating in a short time. At the same time, TiN is oxidized during the spraying process to produce Ti oxide phase, which can improve the toughness of the coating. the
等离子喷涂技术被广泛应用于制备金属、陶瓷和复合涂层以抵抗磨损、腐蚀和高温。在喷涂过程中，易产生氧化物和孔隙等微观缺陷，这是由于熔融颗粒在熔化和飞行以及与基体表面接触过程中与周围介质发生了化学反应，使得喷涂材料出现氧化，而且还由于熔融颗粒的陆续堆叠和部分颗粒的反弹散失，在颗粒之间不可避免的出现孔隙。涂层内氧化物含量和孔隙率等微观缺陷是评判涂层质量的重要标准，有学者对等离子喷涂过程中氧化物的控制和孔隙率对涂层性能的影响进行了研究，通过控制合适的工艺参数能够显著改善涂层的微观结构和性能。TiN高温下易分解氧化，的活性较大，在等离子喷涂过程中与其它介质反应生成Ti的氧化物，Ti的氧化物相相比TiN相硬度和强度较低，TiN涂层内氧化物含量直接影响了涂层性能。断裂韧性是材料抵抗断裂破坏的能力，采用压痕法对涂层断裂韧性的测量已得到广泛应用，涂层硬度和断裂韧性是涂层抵抗裂纹增殖和发生断裂的主要指标，直接影响了涂层的服役性能和 寿命。 Plasma spraying technology is widely used to prepare metal, ceramic and composite coatings to resist wear, corrosion and high temperature. During the spraying process, it is easy to produce microscopic defects such as oxides and pores. This is due to the chemical reaction of the molten particles with the surrounding medium during melting and flight and contact with the surface of the substrate, which makes the sprayed material oxidized, and also due to the molten particles. The continuous stacking and the rebound of some particles are lost, and pores inevitably appear between the particles. Microscopic defects such as oxide content and porosity in the coating are important criteria for judging the quality of the coating. Some scholars have studied the influence of oxide control and porosity on the performance of the coating during the plasma spraying process. By controlling the appropriate process parameter can significantly improve the microstructure and properties of the coating. TiN is easy to decompose and oxidize at high temperature, and has a high activity. It reacts with other media to form Ti oxides during the plasma spraying process. The Ti oxide phase has lower hardness and strength than the TiN phase, and the oxide content in the TiN coating is directly affect the coating performance. Fracture toughness is the ability of materials to resist fracture damage. The measurement of coating fracture toughness by indentation method has been widely used. Coating hardness and fracture toughness are the main indicators of coating resistance to crack proliferation and fracture, which directly affect the coating. service performance and lifespan. the
目前，许多研究者通过反应热喷涂、化学气相沉积(CVD)、物理气相沉积(PVD)、电弧镀、等技术制备了TiN涂层，并对涂层的沉积过程，显微结构和性能进行了研究。采用CVD、PVD等技术制备的TiN涂层厚度较薄，降低涂层的机械性能；而利用热喷涂反应技术可以制备较厚的TiN涂层，但涂层内含有较多的孔隙，脆性较大，涂层质量不易控制。而采用等离子直接喷涂TiN粉末，即可以保证涂层的厚度，同时，TiN涂层内Ti的氧化物相可以提高涂层的韧性，从而得到韧性和硬度都较好的TiN涂层。 At present, many researchers have prepared TiN coatings by reactive thermal spraying, chemical vapor deposition (CVD), physical vapor deposition (PVD), arc plating, etc. Research. The thickness of the TiN coating prepared by CVD, PVD and other technologies is thin, which reduces the mechanical properties of the coating; while the thermal spraying reaction technology can be used to prepare a thicker TiN coating, but the coating contains more pores and is more brittle. , The coating quality is not easy to control. The direct spraying of TiN powder by plasma can ensure the thickness of the coating. At the same time, the oxide phase of Ti in the TiN coating can improve the toughness of the coating, thus obtaining a TiN coating with better toughness and hardness. the
发明内容Contents of the invention
为了解决上述问题，本发明的目的是提供一种TiN涂层的制备方法。 In order to solve the above problems, the object of the present invention is to provide a preparation method of TiN coating. the
为了实现本发明的目的，本发明提供了一种制备TiN涂层的方法，其包括如下步骤： In order to realize the purpose of the present invention, the present invention provides a kind of method for preparing TiN coating, it comprises the steps:
(1)制备TiN团聚粉末：该粉末包括原子分数为Ti-72％和N-28％，其团聚后形成粒径为40～80μm球状团聚体； (1) Preparation of TiN agglomerated powder: the powder includes atomic fractions of Ti-72% and N-28%, which form spherical aggregates with a particle size of 40-80 μm after agglomeration;
(2)模具表面预处理； (2) Mold surface pretreatment;
(3)喷涂：利用等离子喷枪进行喷涂，喷涂参数为，喷涂主气为氩气，气体流量为38L·min-1-42L·min-1；次气为氢气气体流量为12L·min-1-16L·min-1；送粉气为氩气，喷涂距离为100-140mm；送粉量为40g·min-1，喷涂电压为41KW-50KW；喷涂电流为500A-600A； (3) Spraying: Utilize a plasma spray gun for spraying, the spraying parameters are, the main gas for spraying is argon, the gas flow rate is 38L·min−1 -42L·min−1 ; the secondary gas is hydrogen, and the gas flow rate is 12L·min−1 −1 16L·min-1 ; the powder feeding gas is argon, the spraying distance is 100-140mm; the powder feeding amount is 40g·min-1 , the spraying voltage is 41KW-50KW; the spraying current is 500A-600A;
(4)制得TiN涂层：该涂层三强峰相为TiN相，还存在部分TiO、TiO2和Ti3O氧化物相。 (4) Preparation of TiN coating: the three-peak phase of the coating is TiN phase, and part of TiO, TiO2 and Ti3 O oxide phases also exist.
优选地，制备TiN涂层的方法中步骤(1)具体为： Preferably, step (1) in the method for preparing TiN coating is specifically:
(1-1)TiN粉末原料进行雾化，粉末粒径为1-5μm； (1-1) The TiN powder raw material is atomized, and the particle size of the powder is 1-5 μm;
(1-2)对雾化后的TiN粉末和粘结剂进行混料加入到团聚设备内进行团聚，并对团聚后的粉末进行干燥，造粒成形； (1-2) Mix the atomized TiN powder and binder into the agglomeration equipment for agglomeration, dry the agglomerated powder, and granulate it;
(1-3)将团聚后的粉末通过-200目～400目粉末筛，得到的TiN团聚粉末粒径为40-80微米球状团聚体。 (1-3) Pass the agglomerated powder through a powder sieve of -200 mesh to 400 mesh, and the obtained TiN agglomerated powder has a particle size of 40-80 micron spherical agglomerates. the
更优选地，采用聚乙烯醇(PVA)作为粘结剂，粘结剂加入一般不超过1％(质量比)，其可以用来调节粉末自由流动性。 More preferably, polyvinyl alcohol (PVA) is used as the binder, and the addition of the binder generally does not exceed 1% (mass ratio), which can be used to adjust the free flow of the powder. the
优选地，步骤(2)具模具表面预处理包括模具的磨削、清洗和喷砂。 Preferably, the surface pretreatment of the mold in step (2) includes grinding, cleaning and sandblasting of the mold. the
更优选地，步骤(2)具体步骤为： More preferably, the specific steps of step (2) are:
(2-1)对模具表面首先进行磨削处理，使模具表面的粗糙度达到Ra＝0.8μm； (2-1) Grinding the mold surface first, so that the roughness of the mold surface reaches Ra=0.8μm;
(2-2)然后对模具表面进行酒精或丙酮清洗，去除模具表面的油污； (2-2) Carry out alcohol or acetone cleaning to mold surface then, remove the oil stain on mold surface;
(2-3)对模具表面进行喷砂处理，喷砂材料选用粒径小于700μm的棕刚玉，喷砂气压为0.7MPa，喷砂角度为45°，喷枪离模具表面距离为0.15m。 (2-3) Perform sandblasting on the surface of the mold. The sandblasting material is brown corundum with a particle size of less than 700 μm. The sandblasting air pressure is 0.7MPa, the sandblasting angle is 45°, and the distance between the spray gun and the mold surface is 0.15m. the
优选地，步骤(3)具体步骤为： Preferably, the specific steps of step (3) are:
(3-1)在喷涂参数下，利用超音速等离子喷枪对工件表面进行喷涂，扫描过程采用“井”字扫描，扫描速度为1.25m/min； (3-1) Under the spraying parameters, use a supersonic plasma spray gun to spray the surface of the workpiece. The scanning process uses "well" character scanning, and the scanning speed is 1.25m/min;
(3-2)根据沉积速度对工件表面进行4～6次“井”字扫描，得到厚度约为200μm厚度的涂层。 (3-2) Scan the surface of the workpiece 4 to 6 times according to the deposition rate to obtain a coating with a thickness of about 200 μm. the
更优选地，步骤(3)中喷涂参数为，喷涂主气为氩气，气体流量为38L·min-1；次气为氢气气体流量为16L·min-1；送粉气为氩气，喷涂距离为125mm；送粉量为40g·min-1，喷涂电压为46KW；喷涂电流为540A。 More preferably, the spraying parameters in step (3) are: the primary gas for spraying is argon, and the gas flow rate is 38L·min-1 ; the secondary gas is hydrogen, and the gas flow rate is 16L·min-1 ; the powder feeding gas is argon, and the spraying The distance is 125mm; the powder feeding amount is 40g·min-1 , the spraying voltage is 46KW; the spraying current is 540A.
优选地，制备TiN涂层的方法中步骤(4)具体为： Preferably, step (4) in the method for preparing TiN coating is specifically:
(4-1)TiN粉末熔点约为2950℃，喷涂粉末TiN团聚粉末在等离子束的高温下熔化，超音速等离子喷涂设备可以使熔化粉末具有高的飞行速度，可以形成较致密的涂层； (4-1) The melting point of TiN powder is about 2950°C. Spray powder TiN agglomerated powder is melted at the high temperature of the plasma beam. The supersonic plasma spraying equipment can make the molten powder have a high flying speed and form a denser coating;
(4-2)喷涂粉末由于沉积到基体上，熔化颗粒在飞行过程中，与周围的空气发生了反应，产生了氧化，生成了TiO，Ti3O，TiO2氧化物，Ti的氧化物相比TiN相强度和硬度较低，可以提高涂层的韧性。 (4-2) Due to the deposition of the spray powder on the substrate, the molten particles reacted with the surrounding air during the flight, resulting in oxidation, and formed TiO, Ti3 O, TiO2 oxides, Ti oxide phases It has lower strength and hardness than TiN phase, which can improve the toughness of the coating.
本发明的有益效果如下： The beneficial effects of the present invention are as follows:
本发明直接对TiN粉末进行喷涂，可以再零件表面直接制备耐磨陶瓷涂层，涂层中Ti氧化物的出现，提高了涂层的韧性。直接喷涂TiN涂层可以避免传统的采用反应喷涂TiN层较大的脆性和工艺复杂，需要较多的人力和物力资源。 The invention directly sprays the TiN powder, and can directly prepare a wear-resistant ceramic coating on the surface of the part, and the appearance of Ti oxide in the coating improves the toughness of the coating. Direct spraying of TiN coating can avoid the greater brittleness and complicated process of traditional reaction spraying TiN layer, which requires more manpower and material resources. the
本发明采用超音速喷涂TiN涂层，涂层较致密，有少量空隙，与基体结合良好，厚度约200μm，采用压痕法测量涂层断裂韧性为The present invention adopts supersonic spraying TiN coating, the coating is denser, has a small amount of voids, is well combined with the substrate, and has a thickness of about 200 μm. The fracture toughness of the coating is measured by indentation method as
本发明采用等离子喷涂TiN粉末制备的TiN涂层，该方法可以采用粉末直接喷涂，操作方便，易于推广，大大的节约了成本。 The invention adopts the TiN coating prepared by plasma spraying TiN powder, and the method can be directly sprayed by powder, which is convenient to operate, easy to popularize, and greatly saves cost. the
本发明采用超音速等离子喷涂TiN涂层，硬度较高，可以达到1210HV0.1，高的硬度可以提高涂层的耐磨性，涂层的断裂韧性较大，可以提高涂层内断裂力学性能，延长涂层的疲劳寿命。 The invention adopts supersonic plasma spraying TiN coating, the hardness is high, can reach 1210HV0.1 , the high hardness can improve the wear resistance of the coating, the fracture toughness of the coating is large, can improve the fracture mechanical properties of the coating, prolong the Coating fatigue life.
附图说明Description of drawings
图1本发明实施例1制得的TiN涂层； The TiN coating that Fig. 1 embodiment of the present invention 1 makes;
图2喷涂功率对孔隙率的影响趋势图； Fig. 2 influence trend diagram of spraying power on porosity;
图3喷涂距离对氧化物含量的影响； The influence of Fig. 3 spraying distance on oxide content;
图4涂层的XRD测试结果； The XRD test result of Fig. 4 coating;
图5涂层的SEM扫描形貌； The SEM scanning morphology of the coating in Fig. 5;
图6涂层硬度测试结果； Fig. 6 coating hardness test result;
图7断裂韧性测试压痕形貌； Figure 7 Fracture toughness test indentation morphology;
图8不同孔隙率对涂层硬度的影响； The influence of Fig. 8 different porosity on coating hardness;
图9不同氧化物含量对涂层断裂韧性的影响。 Figure 9 Effect of different oxide contents on the fracture toughness of the coating. the
具体实施方式Detailed ways
下面结合附图及其具体实施方式详细介绍本发明。但本发明的保护范围并不局限于以下实例，应包含权利要求书中的全部内容。 The present invention will be described in detail below in conjunction with the accompanying drawings and specific embodiments thereof. But the scope of protection of the present invention is not limited to the following examples, and should include all content in the claims. the
以下实施例中所使用的常规仪器，所用的发酵罐型号为BIOSTAR Bplus，Germany。 The conventional instrument used in the following examples, the fermenter model used is BIOSTAR Bplus, Germany. the
实施例1涂层的制备 The preparation of embodiment 1 coating
涂层的制备过程分为制备TiN团聚粉末，模具表面预处理，喷涂参数优化，喷涂四个阶段，四个阶段步骤如下： The preparation process of the coating is divided into four stages: preparation of TiN agglomerated powder, mold surface pretreatment, spraying parameter optimization, and spraying. The steps of the four stages are as follows:
(1)制备TiN团聚粉末； (1) Prepare TiN agglomerated powder;
(1-1)以粉末粒径为1-5μm的TiN粉末为原料进行雾化； (1-1) Atomize TiN powder with a particle size of 1-5 μm as raw material;
(1-2)对雾化后的TiN粉末和粘结剂进行混料加入到团聚设备内进行团聚，并对团聚后的粉末进行干燥，冷却； (1-2) The atomized TiN powder and binder are mixed and added to the agglomeration equipment for agglomeration, and the agglomerated powder is dried and cooled;
(1-3)将团聚后的粉末通过-200目～400目粉末筛，得到的TiN团聚粉末粒径为40-80微米的微米球状团聚体。 (1-3) passing the agglomerated powder through a powder sieve of -200 mesh to 400 mesh to obtain a TiN agglomerated powder with a particle size of 40-80 microns and micron spherical agglomerates. the
该粉末包括原子分数为Ti-72％和N-28％，其团聚后形成粒径为40～80μm球状团聚体。 The powder includes atomic fractions of Ti-72% and N-28%, and after agglomeration, spherical agglomerates with a particle diameter of 40-80 μm are formed. the
(2)模具表面预处理； (2) Mold surface pretreatment;
(2-1)对模具表面首先进行磨削处理，使模具表面的粗糙度达到Ra＝0.8μm； (2-1) Grinding the mold surface first, so that the roughness of the mold surface reaches Ra=0.8μm;
(2-2)然后对模具表面进行酒精或丙酮清洗，去除模具表面的油污； (2-2) Carry out alcohol or acetone cleaning to mold surface then, remove the oil stain on mold surface;
(2-3)对模具表面进行喷砂处理，喷砂材料选用粒径小于700μm的棕刚玉，喷砂气压为0.7MPa，喷砂角度为45°，喷枪离模具表面距离为0.15m。 (2-3) Perform sandblasting on the surface of the mold. The sandblasting material is brown corundum with a particle size of less than 700 μm. The sandblasting air pressure is 0.7MPa, the sandblasting angle is 45°, and the distance between the spray gun and the mold surface is 0.15m. the
(3)喷涂 (3) Spraying
(3-1)喷涂设备采用超音速等离子喷枪，喷涂参数为，喷涂主气为氩气，气体流量为38L·min-1；次气为氢气气体流量为16L·min-1；送粉气为氩气，喷涂距离为125mm；送粉量为40g·min-1，喷涂电压为46KW；喷涂电流为540A； (3-1) The spraying equipment adopts a supersonic plasma spray gun, and the spraying parameters are as follows: the main gas for spraying is argon, and the gas flow rate is 38L·min-1 ; the secondary gas is hydrogen, and the gas flow rate is 16L·min-1 ; the powder feeding gas is Argon gas, the spraying distance is 125mm; the powder feeding volume is 40g·min-1 , the spraying voltage is 46KW; the spraying current is 540A;
(3-2)在喷涂参数下，利用超音速等离子喷枪对工件表面进行喷涂，扫描过程采用“井”字扫描，扫描速度为1.25m/min； (3-2) Under the spraying parameters, use a supersonic plasma spray gun to spray on the surface of the workpiece. The scanning process uses "well" character scanning, and the scanning speed is 1.25m/min;
(3-3)根据沉积速度对工件表面进行4～6次“井”字扫描，得到厚度约为200μm厚度的涂层； (3-3) Carry out 4 to 6 "well" scans on the surface of the workpiece according to the deposition rate to obtain a coating with a thickness of about 200 μm;
(4)制得TiN涂层 (4) Prepare TiN coating
(4-1)TiN粉末熔点约为2950℃，喷涂粉末TiN团聚粉末在等离子束的高温下熔化，超音速等离子喷涂设备可以使熔化粉末具有高的飞行速度，可以形成较致密的涂层； (4-1) The melting point of TiN powder is about 2950°C. Spray powder TiN agglomerated powder is melted at the high temperature of the plasma beam. The supersonic plasma spraying equipment can make the molten powder have a high flying speed and form a denser coating;
(4-2)喷涂粉末由于沉积到基体上，熔化颗粒在飞行过程中，与周围的空气发生了反应，产生了氧化，生成了TiO，Ti3O，TiO2氧化物，Ti的氧化物相比TiN相强度和硬度较低，可以提高涂层的韧性。 (4-2) Due to the deposition of the spray powder on the substrate, the molten particles reacted with the surrounding air during the flight, resulting in oxidation, and formed TiO, Ti3 O, TiO2 oxides, Ti oxide phases It has lower strength and hardness than TiN phase, which can improve the toughness of the coating.
制得的TiN涂层如图1所示，涂层较致密，有少量空隙，与基体结合良好，厚度约200μm，采用压痕法测量涂层断裂韧性为The prepared TiN coating is shown in Figure 1. The coating is relatively dense, has a small amount of voids, and is well combined with the substrate. The thickness is about 200 μm. The fracture toughness of the coating measured by the indentation method is
实施例2喷涂参数的影响 The influence of embodiment 2 spraying parameters
喷涂参数中的喷涂功率，喷涂距离是影响涂层的主要指标，采用了10种不同工艺参数来对涂层进行优化，具体如表1和表2所示，优化指标的评判标准为硬度和断裂韧性。 The spraying power and spraying distance in the spraying parameters are the main indicators affecting the coating. 10 different process parameters are used to optimize the coating. The details are shown in Table 1 and Table 2. The evaluation criteria for optimization indicators are hardness and fracture toughness. the
表1 不同喷涂功率下喷涂参数 Table 1 Spraying parameters under different spraying power
表2 不同喷涂距离下喷涂参数 Table 2 Spraying parameters at different spraying distances
通过改变ST1-ST5五种工艺参数，不同喷涂功率对硬度的结果如下，在ST4工艺参数下，喷涂功率为46KW时，涂层硬度最高，为1402HV0.1，ST5，ST3，ST1，ST2工艺下，涂层的硬度依次减小，分别为1248HV0.1，1096HV0.1，1012HV0.1，985HV0.1。 By changing the five process parameters of ST1-ST5, the results of different spraying power on hardness are as follows. Under ST4 process parameters, when the spraying power is 46KW, the coating hardness is the highest, which is 1402HV0.1, ST5, ST3, ST1, ST2 process , the hardness of the coating decreases in turn, respectively 1248HV0.1, 1096HV0.1, 1012HV0.1, 985HV0.1. the
通过改变ST6-ST10五种工艺参数，在最佳喷涂功率下，不同喷涂距离是造成涂层中氧化物含量不同的主要原因，从而导致了涂层的断裂韧性差异。在ST8工艺参数下，涂层的氧化物含量为16％左右时，涂层的断裂韧性最大，为 在ST10，ST7，ST9，ST6工艺参数下，涂层的断裂韧性依次降 低，分别为By changing the five process parameters of ST6-ST10, under the optimal spraying power, different spraying distances are the main reason for the different oxide content in the coating, which leads to the difference in the fracture toughness of the coating. Under ST8 process parameters, when the oxide content of the coating is about 16%, the fracture toughness of the coating is the largest, which is Under the process parameters of ST10, ST7, ST9, and ST6, the fracture toughness of the coating decreases in turn, respectively
通过改变涂层的喷涂参数，喷涂功率的改变对涂层中孔隙率有直接影响，影响结果如3所示： By changing the spraying parameters of the coating, the change of the spraying power has a direct impact on the porosity in the coating, and the results are shown in 3:
表3 不同喷涂功率下涂层孔隙率的大小 Table 3 The porosity of the coating under different spraying power
喷涂功率的减小，涂层内孔隙率出现先增大后减小的趋势，喷涂功率为46KW时涂层内孔隙率最小，具体如图2所示。 As the spraying power decreases, the porosity in the coating first increases and then decreases. When the spraying power is 46KW, the porosity in the coating is the smallest, as shown in Figure 2. the
实施例3 喷涂距离对氧化物含量的影响 Embodiment 3 The influence of spraying distance on oxide content
利用三种参数检测喷涂距离对氧化物含量的影响，具体如表4所示。 Three parameters were used to detect the effect of spraying distance on oxide content, as shown in Table 4. the
表4 喷涂距离对氧化物含量的影响三种参数下涂层FDS结果 Table 4 Effect of spraying distance on oxide content Coating FDS results under three parameters
喷涂距离的增大，涂层内氧化物出现先减小后增大的趋势，喷涂距离为125mm时涂层内氧化物含量最少，具体参见图3。 As the spraying distance increases, the oxides in the coating tend to decrease first and then increase. When the spraying distance is 125 mm, the oxide content in the coating is the least, see Figure 3 for details. the
实施例4 实施例1中涂层的性能 The performance of coating in embodiment 4 embodiment 1
为了测量涂层中相成分和相结构，采用BRUKER公司D8型X射线分析衍射仪(XRD)对实施例1制得的涂层进行相成分分析，衍射靶材为Cu靶，波长为0.154056nm，测试结果如图4所示所示。 In order to measure phase composition and phase structure in coating, adopt BRUKER company D8 type X-ray analysis diffractometer (XRD) to carry out phase composition analysis to the coating that embodiment 1 makes, diffraction target material is Cu target, and wavelength is 0.154056nm, The test results are shown in Figure 4. the
图4所示为TiN涂层XRD图谱，经过对比PDF卡片，图中的三强峰相为TiN相，TiN相具有强烈的(200)取向，存在部分TiO、TiO2和Ti3O氧化物相，这是由于等离子喷涂过程中TiN高温下发生了氧化，生成了Ti的氧化物。涂 层内TiO和Ti3O亚稳相的存在是由于等离子喷涂过程中TiN的氧化不充分沉积形成。TiN相三强峰的强度远大于氧化物相的强度，说明涂层中主要为TiN相。 Figure 4 shows the XRD spectrum of the TiN coating. After comparing the PDF card, the three strong peak phases in the figure are the TiN phase. The TiN phase has a strong (200) orientation, and there are some TiO, TiO2 and Ti3 O oxide phases. , which is due to the oxidation of TiN at high temperature during the plasma spraying process to form Ti oxides. The existence of TiO and Ti3 O metastable phases in the coating is due to the insufficient deposition of TiN during the plasma spraying process. The intensity of the triple peak of the TiN phase is much greater than that of the oxide phase, indicating that the coating is mainly composed of the TiN phase.
为了确定涂层中各元素的分布情况，采用Nova NanoSEM450型扫描电子显微镜所采用的EDS能谱仪对TiN涂层进行了元素分析，具体如图5和表5所示，以确定涂层中各相之间的结合情况。 In order to determine the distribution of each element in the coating, the EDS energy spectrometer used in the Nova NanoSEM450 scanning electron microscope was used to analyze the elements of the TiN coating, as shown in Figure 5 and Table 5, to determine the elements in the coating. The connection between the phases. the
表5涂层EDS结果 Table 5 coating EDS results
从截面扫描照片图5中可以看出，涂层中存在明暗相层状分布，在层状结构内部和层状结构结合处有少量孔隙。从元素面扫描分布图中可以看出Ti元素在整个截面中分布较均匀，N元素和O元素呈区域性分布，SEM图片中颜色较暗的A区富含成分为Ti和N，以及少量的O，相反，颜色较亮的B区富含成分为Ti、O和少量的N。结合XRD结果，可以分析A区主要成分为TiN相，而B区的主要成分为Ti氧化物相和少量TiN相。A和B颜色的不同，主要可能是氧化物相含量的不同所致。 It can be seen from the cross-sectional scanning photo in Figure 5 that there is a layered distribution of light and dark phases in the coating, and there are a small amount of pores inside the layered structure and at the junction of the layered structure. From the element surface scanning distribution diagram, it can be seen that the Ti element is evenly distributed in the entire section, and the N element and O element are regionally distributed. In the SEM image, the darker A area is rich in Ti and N, and a small amount of O, on the contrary, the brighter B region is rich in Ti, O and a small amount of N. Combined with the XRD results, it can be analyzed that the main component of area A is TiN phase, while the main component of area B is Ti oxide phase and a small amount of TiN phase. The difference in color between A and B may be mainly due to the difference in the content of the oxide phase. the
采用HVS-1000型数显维氏硬度计测试涂层显微硬度，显微硬度加载载荷为100g，加载时间15S，测试点个数为10个点，涂层的平均硬度达到1210HV0.1，可以看出涂层具有较高的硬度，具体如图6所示。 HVS-1000 digital display Vickers hardness tester is used to test the microhardness of the coating. The microhardness load is 100g, the loading time is 15S, the number of test points is 10 points, and the average hardness of the coating reaches 1210HV0.1 . You can see The resulting coating has relatively high hardness, as shown in Figure 6.
采用HVS-1000型数显维氏硬度计压出压痕，如图7和表6所示，并利用压痕法的如下公式计算了涂层的断裂韧性： The HVS-1000 digital display Vickers hardness tester was used to press out the indentation, as shown in Figure 7 and Table 6, and the fracture toughness of the coating was calculated using the following formula of the indentation method:
式(1)中：a为对角线压痕长度的一半；P为加载载荷；式(2)中：E为杨氏模量；c为从压痕中心到裂纹边径向裂纹的长度。 In formula (1): a is half of the length of the diagonal indentation; P is the loading load; in formula (2): E is Young's modulus; c is the length of the radial crack from the center of the indentation to the edge of the crack. the
表6 涂层断裂韧性KIC计算参数 Table 6 Calculation parameters of coating fracture toughness KIC
涂层内喷涂参数对孔隙率和氧化物的影响，对硬度和断裂韧性也有影响 Influence of spraying parameters in the coating on porosity and oxides, also on hardness and fracture toughness
涂层内孔隙率对硬度的影响趋势图如图8所示，可以看出，三种工艺下，随涂层内孔隙率增大，涂层硬度呈明显降低趋势。孔隙率较小时涂层的硬度最高，为1402HV0.1。 The influence trend diagram of the porosity in the coating on the hardness is shown in Figure 8. It can be seen that under the three processes, as the porosity in the coating increases, the hardness of the coating decreases significantly. When the porosity is small, the hardness of the coating is the highest, which is 1402HV0.1. the
涂层内氧化物对断裂韧性的影响趋势，如图9所示。可以看出，随氧化物含量增加涂层的断裂韧性呈先增加后降低的趋势，，在氧化物含量为16％左右时，涂层的断裂韧性值最大，为The influence trend of oxides in the coating on fracture toughness is shown in Fig. 9. It can be seen that as the oxide content increases, the fracture toughness of the coating increases first and then decreases. When the oxide content is about 16%, the fracture toughness of the coating is the largest, which is
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。 The above is only a preferred embodiment of the present invention, it should be pointed out that for those of ordinary skill in the art, without departing from the technical principle of the present invention, some improvements and modifications can also be made. These improvements and modifications It should also be regarded as the protection scope of the present invention. the
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410539638.2ACN104372284A (en) | 2014-10-13 | 2014-10-13 | Preparation method of plasma sprayed TiN coating layer having relatively good hardness and toughness |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410539638.2ACN104372284A (en) | 2014-10-13 | 2014-10-13 | Preparation method of plasma sprayed TiN coating layer having relatively good hardness and toughness |
| Publication Number | Publication Date |
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| CN104372284Atrue CN104372284A (en) | 2015-02-25 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410539638.2APendingCN104372284A (en) | 2014-10-13 | 2014-10-13 | Preparation method of plasma sprayed TiN coating layer having relatively good hardness and toughness |
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