技术领域technical field
本发明属于机械加工刀具技术领域，具体为一种复合涂层刀具及其制备方法和应用。The invention belongs to the technical field of mechanical processing cutters, in particular to a composite coating cutter and its preparation method and application.
背景技术Background technique
钛合金、高温合金、耐热不锈钢等材料广泛应用于航空航天、能源等领域高端装备零部件上，现代切削加工要求高效，追求高速切削；提倡环保，少用或不用冷却液，追求绿色干式切削。钛合金、高温合金、耐热不锈钢等材料切削时与刀具接触的局部温度可达1000℃以上，这些材料在高温下仍具有高强度，并且在切削期间产生碎片式切屑，对刀具产生断续的高切削冲击力，高强度、加工硬化和粘附硬化等材料特性对刀具提出了硬而韧的要求。大部分刀具在切削有色金属和不锈钢等材料时，由于材料与刀具的亲和性（刀具与待切削材料间元素互相渗透、反应）导致加工精度低和刀具损坏。为适应上述加工要求，刀具涂层要求摩擦系数低、涂层结合强度高、耐磨性好、亲和性低、高温抗氧化性好、兼具硬度和韧性。Titanium alloys, high-temperature alloys, heat-resistant stainless steel and other materials are widely used in high-end equipment parts in aerospace, energy and other fields. Modern cutting processes require high efficiency and pursue high-speed cutting; advocate environmental protection, use less or no coolant, and pursue green dry methods cutting. When materials such as titanium alloys, high-temperature alloys, and heat-resistant stainless steel are cut, the local temperature in contact with the tool can reach above 1000°C. These materials still have high strength at high temperatures, and produce fragmented chips during cutting, causing intermittent damage to the tool. Material properties such as high cutting impact, high strength, work hardening and adhesion hardening place hard and tough requirements on the cutting tool. When most cutting tools are cutting non-ferrous metals and stainless steel, due to the affinity between the material and the cutting tool (interpenetration and reaction of elements between the cutting tool and the material to be cut), the machining accuracy is low and the cutting tool is damaged. In order to meet the above processing requirements, the tool coating requires low friction coefficient, high coating bonding strength, good wear resistance, low affinity, good high temperature oxidation resistance, and hardness and toughness.
长期以来国内外涂层刀具的研究和应用主要集中在金属氧化物、氮化物、碳化物等二元涂层材料方面。然而，强共价键结合的特性导致这些涂层要么韧性较差、要么抗氧化物性能较差。近年来为有效解决上述缺点，具有复合结构的多元化金属涂层成为主流研究方向。For a long time, the research and application of coated cutting tools at home and abroad have mainly focused on binary coating materials such as metal oxides, nitrides, and carbides. However, the strong covalently bonded nature of these coatings results in either poor toughness or poor oxidation resistance. In recent years, in order to effectively solve the above shortcomings, multiple metal coatings with composite structures have become the mainstream research direction.
评判具有复合结构的多层涂层-复合涂层性能好坏的一个重要指标是涂层结合力的好坏。涂层结合力，是指涂层与涂层之间、及涂层与基体之间的相互粘附能力，也就是将单层涂层从其余涂层中或基体上剥离的难易程度。越难剥离意味着涂层的结合力越好，涂层刀片使用时越能发挥各涂层的特点，使用寿命也更长。涂层结合力问题也是复合涂层首要解决的问题。Judging Multilayer Coatings with Composite Structure - An important indicator of the performance of composite coatings is the quality of coating adhesion. Coating adhesion refers to the mutual adhesion between the coating and the coating, and between the coating and the substrate, that is, the difficulty of peeling a single-layer coating from the rest of the coating or the substrate. The harder it is to peel off, the better the bonding force of the coating, the better the characteristics of each coating can be exerted when the coated blade is used, and the service life is longer. The problem of coating adhesion is also the primary problem to be solved by composite coatings.
上个世纪80年代开始，硼元素掺杂传统涂层的研究就已经开始，得到了一些公认的研究成果：硼元素具有很好的细晶强化作用，它能使涂层晶粒细化从而提高涂层硬度；硼元素与钛、镍、铝等金属的化学反应，使得掺硼涂层有利于有色金属的加工。TiB2涂层具有纳米级晶粒，硬度超过4600HV；与铁基、镍基、钛基等高温合金材料亲和性低，不易产生粘附破坏刀具；摩擦系数低，具有自润滑性，非常适合不使用润滑液的干式切削。但是，TiB2涂层硬而脆，韧性低，难以与其它涂层结合，从而限制了TiB2涂层的应用。Since the 1980s, the research on boron element doping traditional coatings has begun, and some recognized research results have been obtained: boron element has a good fine-grain strengthening effect, which can refine the coating grains and improve the coating quality. Coating hardness; the chemical reaction between boron and titanium, nickel, aluminum and other metals makes boron-doped coatings beneficial to the processing of non-ferrous metals. The TiB2 coating has nano-sized grains, and its hardness exceeds 4600HV; it has low affinity with iron-based, nickel-based, titanium-based and other high-temperature alloy materials, and is not easy to cause adhesion damage to the tool; the friction coefficient is low, and it has self-lubricating properties, which is very suitable for Dry cutting without using lubricant. However, TiB2 coating is hard and brittle, with low toughness, and it is difficult to combine with other coatings, thus limiting the application of TiB2 coating.
专利CN103060653A中利用磁控溅射的方法使用TiB2靶和Cu靶制备出二硼化钛-铜韧性硬质涂层，该涂层具有高硬度、高韧性的特点，但是在加工有色金属材料时会出现粘刀破坏刀具。专利CN107740043A中利用磁控溅射和射频溅射的方法同时沉积TiB2和CaF2，该方法改善了TiB2涂层的韧性使得掺杂CaF2的TiB2涂层与基体结合良好，但也不可避免的降低了TiB2涂层本身的硬度。并且这些方法使用的都是物理气相沉积技术，不具备化学气相沉积技术涂层的高硬度、高涂层结合力的特点。In patent CN103060653A, TiB2 target and Cu target are used to prepare titanium diboride-copper tough hard coating by magnetron sputtering method. This coating has the characteristics of high hardness and high toughness, but when processing non-ferrous metal materials There will be sticking knife damage knife. In the patent CN107740043A, magnetron sputtering and radio frequency sputtering are used to simultaneously depositTiB2 andCaF2 . This method improves the toughness of theTiB2 coating and makes theCaF2- dopedTiB2 coating bond well with the substrate, but it cannot Avoid reducing the hardness of theTiB2 coating itself. Moreover, these methods all use physical vapor deposition technology, which does not have the characteristics of high hardness and high coating adhesion of chemical vapor deposition technology coatings.
由此，目前需要有一种方案来解决现有技术中存在的技术问题。Therefore, there is currently a need for a solution to solve the technical problems in the prior art.
发明内容Contents of the invention
为解决现有技术存在的问题，本发明的主要目的是提出一种复合涂层刀具及其制备方法和应用。In order to solve the problems existing in the prior art, the main purpose of the present invention is to propose a composite coating tool and its preparation method and application.
为解决上述技术问题，根据本发明的一个方面，本发明提供了如下技术方案：In order to solve the above technical problems, according to one aspect of the present invention, the present invention provides the following technical solutions:
一种采用化学气相沉积技术制备的复合涂层刀具，其中，包括基体和依次设置在所述基体表面的复合涂层；所述复合涂层自基体向外依次包括第一子涂层、Ti-B-N过渡层、第二子涂层TiB2层，所述Ti-B-N过渡层中的硼含量自第一子涂层向第二子涂层方向梯度增加，硼含量在0~50at.%之间变化，且Ti-B-N过渡层表层硼含量不高于所述第二子涂层TiB2层的硼含量，Ti-B-N过渡层硬度在2500~5000HV之间变化；所述Ti-B-N过渡层中的面心立方结构fcc-TiN相自第一子涂层向第二子涂层方向由大于85vol.%含量逐步减小到0，密排六方结构hcp-TiB2相由0含量逐步提高到50vol.%以上；所述第二子涂层TiB2层的物相组成包含密排六方结构hcp-TiB2和非晶相a-TiB，其中hcp-TiB2的体积分数不低于85%、a-TiB体积分数为5~15%。A composite coating cutting tool prepared by chemical vapor deposition technology, which includes a substrate and a composite coating sequentially arranged on the surface of the substrate; the composite coating sequentially includes a first sub-coating layer, a Ti- BN transition layer, second sub-coating TiB2 layer, the boron content in the Ti-BN transition layer increases from the first sub-coating to the second sub-coating direction gradiently, and the boron content is between 0~50at.%. change, and the boron content of the surface layer of the Ti-BN transition layer is not higher than the boron content of the TiB2 layer of the second sub-coating layer, and the hardness of the Ti-BN transition layer varies between 2500~5000HV; in the Ti-BN transition layer The face-centered cubic structure fcc-TiN phase gradually decreases from more than 85vol.% to 0 from the first sub-coating to the second sub-coating, and the content of the hexagonal close-packed hcp-TiB2 phase gradually increases from 0 to 50vol. .% or more; the phase composition of the TiB2 layer of the second sub-coating layer includes hexagonal close-packed structure hcp-TiB2 and amorphous phase a-TiB, wherein the volume fraction of hcp-TiB2 is not less than 85%, a -TiB volume fraction is 5~15%.
作为本发明所述的一种采用化学气相沉积技术制备的复合涂层刀具的优选方案，其中：所述第一子涂层选自TiN、TiC、TiCN、Ti1-xAlxN、Al2O3中的一种或多种。As a preferred solution of a composite coated tool prepared by chemical vapor deposition technology according to the present invention, wherein: the first sub-coating is selected from TiN, TiC, TiCN, Ti1-x Alx N, Al2 One or more of O3 .
作为本发明所述的一种采用化学气相沉积技术制备的复合涂层刀具的优选方案，其中：所述第一子涂层为Ti1-xAlxN，x≥0.7，Ti1-xAlxN的物相组成包含面心立方结构fcc-TiN、面心立方结构fcc-AlN和密排六方结构hcp-AlN，且fcc-AlN的体积分数不低于80%，所述第一子涂层的纳米硬度为2600~3000HV。As a preferred solution of a composite coated tool prepared by chemical vapor deposition technology according to the present invention, wherein: the first sub-coating is Ti1-x Alx N, x ≥ 0.7, Ti1-x Al The phase composition ofx N includes face-centered cubic structure fcc-TiN, face-centered cubic structure fcc-AlN and hexagonal close-packed structure hcp-AlN, and the volume fraction of fcc-AlN is not less than 80%, the first sub-coating The nano hardness of the layer is 2600~3000HV.
作为本发明所述的一种采用化学气相沉积技术制备的复合涂层刀具的优选方案，其中：所述第二子涂层的纳米硬度为4000~5000HV。As a preferred solution of the composite coating cutting tool prepared by chemical vapor deposition technology in the present invention, wherein: the nanohardness of the second sub-coating is 4000-5000HV.
作为本发明所述的一种采用化学气相沉积技术制备的复合涂层刀具的优选方案，其中：所述复合涂层的总厚度为5.0~20.0μm，优选10~15.0μm；As a preferred solution of a composite coated tool prepared by chemical vapor deposition technology according to the present invention, wherein: the total thickness of the composite coating is 5.0-20.0 μm, preferably 10-15.0 μm;
所述第一子涂层的厚度为3.0~10.0μm，优选为5.0~8.0μm；The thickness of the first sub-coating layer is 3.0-10.0 μm, preferably 5.0-8.0 μm;
所述Ti-B-N过渡层的厚度为0.50~4.0μm，优选为1.0~3.0μm；The thickness of the Ti-B-N transition layer is 0.50-4.0 μm, preferably 1.0-3.0 μm;
所述第二子涂层TiB2层的厚度为1.0~10.0μm，优选为2.0~5.0μm。The thickness of the TiB2 layer of the second sub-coating layer is 1.0-10.0 μm, preferably 2.0-5.0 μm.
作为本发明所述的一种采用化学气相沉积技术制备的复合涂层刀具的优选方案，其中：所述复合涂层还包括沉积在所述基体表面和所述第一子涂层之间的结合层，所述结合层为TiN、TiC、TiCN中的一种或多种，优选为TiN，结合层厚度为0.1~1.0μm。As a preferred solution of a composite coated tool prepared by chemical vapor deposition technology according to the present invention, wherein: the composite coating also includes a bond deposited between the surface of the substrate and the first sub-coating layer, the bonding layer is one or more of TiN, TiC, TiCN, preferably TiN, and the thickness of the bonding layer is 0.1-1.0 μm.
作为本发明所述的一种采用化学气相沉积技术制备的复合涂层刀具的优选方案，其中：所述基体的材料为硬质合金、高速钢、金属陶瓷、聚晶金刚石、立方氮化硼中的一种。As a preferred solution of the composite coating tool prepared by chemical vapor deposition technology according to the present invention, wherein: the material of the substrate is hard alloy, high-speed steel, cermet, polycrystalline diamond, cubic boron nitride, etc. kind of.
一种上述的复合涂层刀具的制备方法，所述结合层通过采用化学气相沉积技术，在750~1000℃、50~200mbar条件下，以包括TiCl4、N2、H2为原料，在所述基体表面发生化学反应而获得；A preparation method of the above-mentioned composite coated cutting tool, the bonding layer adopts chemical vapor deposition technology, under the conditions of 750~1000°C and 50~200mbar, using TiCl4 , N2 , H2 as raw materials, in the obtained by a chemical reaction on the surface of the substrate;
和/或所述第一子涂层通过采用化学气相沉积技术，在700~900℃、4~30mbar条件下，以包括H2、TiCl4、AlCl3、NH3、N2、Ar为原料，在所述结合层的表面发生化学反应而获得；And/or the first sub-coating layer is made of H2 , TiCl4 , AlCl3 , NH3 , N2 , and Ar under the conditions of 700-900° C. and 4-30 mbar by using chemical vapor deposition technology, obtained by a chemical reaction on the surface of the binding layer;
和/或所述Ti-B-N过渡层通过化学气相沉积技术，在700~900℃、4~30mbar条件下，以包括H2、TiCl4、BCl3、N2、Ar为原料，并逐渐增加BCl3的比例，在所述第一子涂层的表面发生化学反应而获得；And/or the Ti-BN transition layer adopts chemical vapor deposition technology under the conditions of 700~900°C and 4~30mbar, using H2 , TiCl4 , BCl3 , N2 , Ar as raw materials, and gradually increasing BCl The ratio of3 is obtained by chemical reaction on the surface of the first sub-coating;
和/或所述第二子涂层TiB2层通过化学气相沉积技术，在700~900℃、4~30mbar条件下，以包括H2、TiCl4、BCl3、Ar为原料，在所述过渡层的表面发生化学反应而获得。And/or the TiB2 layer of the second sub-coating layer adopts chemical vapor deposition technology, under the conditions of 700~900°C and 4~30mbar, using H2 , TiCl4 , BCl3 , Ar as raw materials, in the transition It is obtained by a chemical reaction on the surface of the layer.
一种上述复合涂层刀具用于对钛合金、镍基高温合金、耐热不锈钢中任一种材料进行高速切削或/和干式切削的应用。An application of the above-mentioned composite coating tool for high-speed cutting or/and dry cutting of any material among titanium alloy, nickel-based superalloy, and heat-resistant stainless steel.
本发明的有益效果如下：The beneficial effects of the present invention are as follows:
1、本发明的复合涂层刀具的复合涂层采用化学气相沉积技术制备而成，复合涂层中的第一子涂层Ti-Al-N涂层，铝含量达到80%时，涂层中仍不会出现hcp-AlN相，本发明制备的Ti-Al-N涂层具有优秀的综合性能，尤其是抗高温氧化性能。1. The composite coating of the composite coating cutting tool of the present invention is prepared by chemical vapor deposition technology, the first sub-coating Ti-Al-N coating in the composite coating, when the aluminum content reaches 80%, the Still no hcp-AlN phase will appear, and the Ti-Al-N coating prepared by the invention has excellent comprehensive properties, especially high-temperature oxidation resistance.
2、本发明制备的具有TiB2涂层且具有高结合力的涂层刀具，采用本发明方法制备TiB2涂层，采用梯度变化的过渡层，使得TiB2涂层有效地与其它涂层结合，为有效地使用TiB2涂层提供了一种方法。提高涂层间的结合力，解决了TiB2涂层由于其硬度高、脆性大的特点而导致的与其它涂层结合困难的技术问题。2. The coated tool withTiB2 coating and high binding force prepared by the present invention adopts the method of the present invention to prepareTiB2 coating, and adopts a gradient transition layer to makeTiB2 coating effectively combine with other coatings , providing a method for the efficient use ofTiB2 coatings. Improve the binding force between coatings, and solve the technical problem that the TiB2 coating is difficult to combine with other coatings due to its high hardness and high brittleness.
3、本发明在沉积形成过渡层Ti-B-N时，通过控制反应气体的流量比，即逐渐增加BCl3的比例，可灵活调整过渡层中硼元素的含量，使过渡层的硼含量呈梯度变化。硼含量梯度变化的Ti-B-N涂层，Ti-B-N晶粒尺寸随硼含量的增加逐渐变小，硬度随硼含量增加而逐渐提高，很好地完成Ti-Al-N粗晶粒、低硬度到TiB2细晶粒、高硬度的过渡。另外，随着硼含量的增加Ti-B-N涂层中逐渐由fcc-TiN晶相占主导转变为由hcp-TiB2晶相主导，从涂层结构上很好地完成Ti-Al-N涂层到TiB2涂层的过渡。硼含量梯度变化的过渡层能实现晶粒尺寸、晶相、硬度方面的梯度变化，能有效衔接两个子涂层，提高涂层结合力。同时，在加工材料时，也能对高频断续的高冲击力起到缓冲作用，提高涂层寿命。3. When the present invention deposits and forms the transition layer Ti-BN, by controlling the flow ratio of the reaction gas, that is, gradually increasing the proportion ofBCl3 , the content of boron element in the transition layer can be flexibly adjusted, so that the boron content of the transition layer changes in a gradient . The Ti-BN coating with a gradient change in boron content, the Ti-BN grain size gradually decreases with the increase of boron content, and the hardness gradually increases with the increase of boron content, which is a good way to complete the Ti-Al-N coarse grain and low hardness Transition toTiB2 fine-grained, high hardness. In addition, with the increase of boron content, the fcc-TiN crystal phase in the Ti-BN coating gradually changes to the hcp-TiB2 crystal phase, and the Ti-Al-N coating is well completed from the coating structure. Transition toTiB2 coating. The transition layer with a gradient change in boron content can realize gradient changes in grain size, crystal phase, and hardness, can effectively connect two sub-coatings, and improve coating adhesion. At the same time, when processing materials, it can also buffer the high-frequency intermittent high-impact force and improve the coating life.
4、由于本发明方法制备Ti-B-N、TiB2涂层温度较高，通常大于700℃，且硼原子半径小，Ti-B-N涂层中的硼原子易扩散至WC-Co基等硬质合金基体内部，形成W3CoB3等脆性相，降低刀具的韧性。因此，本发明在采用CVD方法沉积形成含硼涂层前，先沉积形成其他致密的不含硼涂层（如第一子涂层），可显著减少硼元素向基体扩散。4. Due to the high temperature of the Ti-BN andTiB2 coatings prepared by the method of the present invention, usually greater than 700 ° C, and the boron atomic radius is small, the boron atoms in the Ti-BN coating are easy to diffuse into hard alloys such as WC-Co base Inside the matrix, brittle phases such as W3 CoB3 are formed, reducing the toughness of the tool. Therefore, in the present invention, other dense boron-free coatings (such as the first sub-coating layer) are deposited first before the boron-containing coating is deposited by CVD method, which can significantly reduce the diffusion of boron element to the substrate.
附图说明Description of drawings
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图示出的结构获得其他的附图。In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only These are some embodiments of the present invention. For those skilled in the art, other drawings can also be obtained according to the structures shown in these drawings without creative effort.
图1为本发明一种复合涂层刀具的剖面结构示意图。Fig. 1 is a schematic cross-sectional structure diagram of a composite coating tool according to the present invention.
附图标号说明：Explanation of reference numbers:
10、基体，20、复合涂层，21、结合层，22、第一子涂层，23、Ti-B-N过渡层，24、第二子涂层。10. Substrate, 20. Composite coating, 21. Bonding layer, 22. First sub-coating, 23. Ti-B-N transition layer, 24. Second sub-coating.
本发明目的的实现、功能特点及优点将结合实施例，参照附图做进一步说明。The realization of the purpose of the present invention, functional characteristics and advantages will be further described in conjunction with the embodiments and with reference to the accompanying drawings.
具体实施方式Detailed ways
下面将结合实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。A clear and complete description will be made below in conjunction with the technical solutions in the embodiments. Apparently, the described embodiments are only some of the embodiments of the present invention, but not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without creative efforts fall within the protection scope of the present invention.
本发明提供一种带涂层的切削刀具及其制备方法，通过多种合金元素的掺杂，形成多元涂层体系，提高了刀具的硬度、自润滑、能耐高温氧化性能，也提高了涂层结合力。The invention provides a coated cutting tool and a preparation method thereof. By doping a variety of alloy elements, a multi-component coating system is formed, which improves the hardness, self-lubrication, and high-temperature oxidation resistance of the tool, and also improves the coating Binding force.
如图1所示，一种采用化学气相沉积技术制备的复合涂层刀具，包括基体10和依次设置在所述基体表面的复合涂层20；所述复合涂层20自基体向外依次包括第一子涂层22、Ti-B-N过渡层23、第二子涂层24，第二子涂层24为TiB2层，所述Ti-B-N过渡层中的硼含量自第一子涂层向第二子涂层方向梯度增加，硼含量在0~50at.%之间变化，且Ti-B-N过渡层表层硼含量不高于所第二子涂层TiB2层的硼含量，Ti-B-N过渡层硬度在2500~5000HV之间变化；所述Ti-B-N过渡层中的面心立方结构fcc-TiN相自第一子涂层向第二子涂层方向由大于85vol.%含量逐步减小到0，密排六方结构hcp-TiB2相由0含量逐步提高到50vol.%以上；所述第二子涂层TiB2层的物相组成包含密排六方结构hcp-TiB2和非晶相a-TiB，其中hcp-TiB2的体积分数不低于85vol.%、a-TiB体积分数为5~15vol.%。As shown in Figure 1, a kind of composite coated cutting tool that adopts chemical vapor deposition technology to prepare comprises substrate 10 and the composite coating 20 that is arranged on the surface of described substrate successively; One sub-coating 22, Ti-BN transition layer 23, the second sub-coating 24, the second sub-coating 24 is a TiB2 layer, and the boron content in the described Ti-BN transition layer is from the first sub-coating to the second sub-coating The direction gradient of the second sub-coating increases, the boron content varies between 0 and 50 at.%, and the boron content of the surface layer of the Ti-BN transition layer is not higher than the boron content of the TiB2 layer of the second sub-coating, and the Ti-BN transition layer The hardness varies between 2500 and 5000HV; the face-centered cubic structure fcc-TiN phase in the Ti-BN transition layer gradually decreases from more than 85vol.% to 0 in the direction from the first sub-coating to the second sub-coating , the hexagonal close-packed structure hcp-TiB2 phase gradually increases from 0 to more than 50vol.%; the phase composition of the second sub-coating TiB2 layer includes a close-packed hexagonal structure hcp-TiB2 and an amorphous phase a- TiB, wherein the volume fraction of hcp-TiB2 is not less than 85vol.%, and the volume fraction of a-TiB is 5~15vol.%.
优选地，所述第一子涂层选自TiN、TiC、TiCN、Ti1-xAlxN、Al2O3中的一种或多种。Preferably, the first sub-coating layer is selected from one or more of TiN, TiC, TiCN, Ti1-x Alx N, Al2 O3 .
优选地，所述第一子涂层为Ti1-xAlxN，x≥0.7，Ti1-xAlxN的物相组成包含面心立方结构fcc-TiN、面心立方结构fcc-AlN和密排六方结构hcp-AlN，且fcc-AlN的体积分数不低于80vol.%，所述第一子涂层的纳米硬度为2600~3000HV。Preferably, the first sub-coating layer is Ti1-x Alx N, x ≥ 0.7, and the phase composition of Ti1-x Alx N includes face-centered cubic structure fcc-TiN, face-centered cubic structure fcc-AlN and hcp-AlN with a hexagonal close-packed structure, and the volume fraction of fcc-AlN is not less than 80vol.%, and the nanohardness of the first sub-coating layer is 2600-3000HV.
优选地，所述第二子涂层的纳米硬度为4000~5000HV。Preferably, the nanohardness of the second sub-coating layer is 4000-5000HV.
优选地，所述复合涂层的总厚度为5.0~20.0μm，优选10~15.0μm。Preferably, the total thickness of the composite coating is 5.0-20.0 μm, preferably 10-15.0 μm.
优选地，所述第一子涂层的厚度为3.0~10.0μm，优选为5.0~8.0μm。Preferably, the thickness of the first sub-coating layer is 3.0-10.0 μm, preferably 5.0-8.0 μm.
优选地，所述Ti-B-N过渡层的厚度为0.50~4.0μm，优选为1.0~3.0μm。Preferably, the thickness of the Ti-B-N transition layer is 0.50-4.0 μm, preferably 1.0-3.0 μm.
优选地，所述第二子涂层TiB2层的厚度为1.0~10.0μm，优选为2.0~5.0μm。Preferably, the thickness of the TiB2 layer of the second sub-coating layer is 1.0-10.0 μm, preferably 2.0-5.0 μm.
优选地，所述复合涂层还包括沉积在所述基体表面和所述第一子涂层之间的结合层，所述结合层为TiN、TiC、TiCN中的一种或多种，优选为TiN，结合层厚度为0.1~1.0μm。Preferably, the composite coating also includes a bonding layer deposited between the substrate surface and the first sub-coating layer, the bonding layer is one or more of TiN, TiC, TiCN, preferably TiN, the bonding layer thickness is 0.1~1.0μm.
优选地，所述基体的材料为硬质合金、高速钢、金属陶瓷、聚晶金刚石、立方氮化硼中的一种。Preferably, the material of the substrate is one of cemented carbide, high-speed steel, cermet, polycrystalline diamond, and cubic boron nitride.
一种上述的复合涂层刀具的制备方法，所述结合层通过采用化学气相沉积技术，在750~1000℃、50~200mbar条件下，以包括TiCl4、N2、H2为原料，在所述基体表面发生化学反应而获得；A preparation method of the above-mentioned composite coated cutting tool, the bonding layer adopts chemical vapor deposition technology, under the conditions of 750~1000°C and 50~200mbar, using TiCl4 , N2 , H2 as raw materials, in the obtained by a chemical reaction on the surface of the substrate;
和/或所述第一子涂层通过采用化学气相沉积技术，在700~900℃、4~30mbar条件下，以包括H2、TiCl4、AlCl3、NH3、N2、Ar为原料，在所述结合层的表面发生化学反应而获得；And/or the first sub-coating layer is made of H2 , TiCl4 , AlCl3 , NH3 , N2 , and Ar under the conditions of 700-900° C. and 4-30 mbar by using chemical vapor deposition technology, obtained by a chemical reaction on the surface of the binding layer;
和/或所述Ti-B-N过渡层通过化学气相沉积技术，在700~900℃、4~30mbar条件下，以包括H2、TiCl4、BCl3、N2、Ar为原料，并逐渐增加BCl3的比例，在所述第一子涂层的表面发生化学反应而获得；And/or the Ti-BN transition layer adopts chemical vapor deposition technology under the conditions of 700~900°C and 4~30mbar, using H2 , TiCl4 , BCl3 , N2 , Ar as raw materials, and gradually increasing BCl The ratio of3 is obtained by chemical reaction on the surface of the first sub-coating;
和/或所述第二子涂层TiB2层通过化学气相沉积技术，在700~900℃、4~30mbar条件下，以包括H2、TiCl4、BCl3、Ar为原料，在所述过渡层的表面发生化学反应而获得。And/or the TiB2 layer of the second sub-coating layer adopts chemical vapor deposition technology, under the conditions of 700~900°C and 4~30mbar, using H2 , TiCl4 , BCl3 , Ar as raw materials, in the transition It is obtained by a chemical reaction on the surface of the layer.
一种上述复合涂层刀具刀具用于对钛合金、镍基高温合金、耐热不锈钢中任一种材料进行高速切削或/和干式切削的应用。An application of the above-mentioned composite coating cutting tool for high-speed cutting or/and dry cutting of any material among titanium alloy, nickel-based superalloy, and heat-resistant stainless steel.
以下结合具体实施例对本发明技术方案进行进一步说明。The technical solutions of the present invention will be further described below in conjunction with specific embodiments.
实施例1Example 1
基体采用WC-Co基硬质合金，结合层为TiN，第一子涂层为Ti0.17Al0.83N，过渡层为Ti-B-N涂层、硼含量在0~50at.%之间，第二子涂层为TiB2。复合涂层的结构为：TiN+Ti0.17Al0.83N+Ti-B-N+TiB2。复合涂层刀具通过以下步骤S1-S4制得，以下各涂层均采用化学气相沉积技术（CVD）制备：The substrate is made of WC-Co-based cemented carbide, the bonding layer is TiN, the first sub-coating is Ti0.17 Al0.83 N, the transition layer is Ti-BN coating, the boron content is between 0~50at.%, the second sub-coating The coating is TiB2 . The structure of the composite coating is: TiN+Ti0.17 Al0.83 N+Ti-B-N+TiB2 . Composite coated tools are prepared through the following steps S1-S4, and the following coatings are prepared by chemical vapor deposition (CVD):
S1：制备结合层TiN，沉积温度850℃，沉积压力90mbar，反应材料包括TiCl4、N2、H2，各反应材料的纯度大于99%，沉积时间100min，涂层厚度0.6μm；S1: Preparation of bonding layer TiN, the deposition temperature is 850°C, the deposition pressure is 90mbar, the reaction materials include TiCl4 , N2 , H2 , the purity of each reaction material is greater than 99%, the deposition time is 100min, and the coating thickness is 0.6μm;
S2：制备第一子涂层Ti0.17Al0.83N，沉积温度800℃，沉积压力10mbar，反应材料包括H2、TiCl4、AlCl3、NH3、N2、Ar，各反应材料的纯度大于99%，沉积时间150min，涂层厚度5μm；S2: Prepare the first sub-coat layer Ti0.17 Al0.83 N, deposition temperature 800°C, deposition pressure 10mbar, reaction materials include H2 , TiCl4 , AlCl3 , NH3 , N2 , Ar, and the purity of each reaction material is greater than 99% %, deposition time 150min, coating thickness 5μm;
S3：制备过渡层Ti-B-N层，沉积温度850℃，沉积压力60mbar，反应材料包括H2、TiCl4、BCl3、NH3、N2、Ar，各反应材料的纯度大于99%，BCl3流量逐步提高，且BCl3最大流量小于制备第二子涂层时BCl3的流量，沉积时间100min，涂层厚度1.2μm；S3: Prepare the transition layer Ti-BN layer, the deposition temperature is 850°C, the deposition pressure is 60mbar, the reaction materials include H2 , TiCl4 , BCl3 , NH3 , N2 , Ar, and the purity of each reaction material is greater than 99%, BCl3 The flow rate is gradually increased, and the maximum flow rate of BCl3 is less than the flow rate of BCl3 when preparing the second sub-coating, the deposition time is 100min, and the coating thickness is 1.2μm;
S4：制备第二子涂层TiB2，沉积温度850℃，沉积压力60mbar，反应材料包括H2、TiCl4、BCl3、Ar，各反应材料的纯度大于99%，沉积时间200min，涂层厚度3.0μm。S4: Prepare the second sub-coating TiB2 , the deposition temperature is 850°C, the deposition pressure is 60mbar, the reaction materials include H2 , TiCl4 , BCl3 , Ar, the purity of each reaction material is greater than 99%, the deposition time is 200min, and the coating thickness 3.0 μm.
实施例2Example 2
基体采用WC-Co基硬质合金，涂层结构为：TiN+Ti-B-N+TiB2。结合层TiN参照实施例1中步骤S1实施；Ti-B-N层参照实施例1中步骤S3实施；TiB2层参照实施例1中步骤S4实施。The substrate is made of WC-Co-based hard alloy, and the coating structure is: TiN+Ti-B-N+TiB2 . The TiN layer is implemented referring to step S1 in Example 1; the Ti-BN layer is implemented referring to Step S3 in Example 1; the TiB2 layer is implemented referring to Step S4 in Example 1.
对比例1Comparative example 1
基体采用WC-Co基硬质合金，涂层结构为：TiN+Ti0.17Al0.83N+TiB2。结合层TiN参照实施例1中步骤S1实施；Ti0.17Al0.83N层参照实施例1中步骤S2实施；TiB2层参照实施例1中步骤S4实施。The substrate is made of WC-Co-based hard alloy, and the coating structure is: TiN+Ti0.17 Al0.83 N+TiB2 . The TiN bonding layer is implemented referring to step S1 in Example 1; the Ti0.17 Al0.83 N layer is implemented referring to Step S2 in Example 1; the TiB2 layer is implemented referring to Step S4 in Example 1.
对比例2Comparative example 2
基体采用WC-Co基硬质合金，涂层结构为：TiN+TiB2。结合层TiN参照实施例1中步骤S1实施；TiB2层参照实施例1中步骤S4实施。The substrate is made of WC-Co-based hard alloy, and the coating structure is: TiN+TiB2 . The bonding layer TiN is implemented referring to step S1 in Example 1; the TiB2 layer is implemented referring to Step S4 in Example 1.
对本发明实施例1-2制备的涂层以及对比例1-2制备的涂层进行检测对比，检测方式以及检测结果如下所示。The coatings prepared in Example 1-2 of the present invention and the coatings prepared in Comparative Example 1-2 were tested and compared, and the testing methods and results are as follows.
硬度的检测方法如下：涂层沉积后用直径为20mm的轴承钢球在涂层表面对磨20秒，研磨时加入金刚石研磨剂，将基体表面抛光成镜面。然后采用TTX-NHT2型纳米压痕仪（奥地利安东帕公司）测试磨痕处涂层的硬度（放大100倍），压针为金刚石玻氏压头（Berkovich），最大载荷20mN，加载速率40mN/min，卸载速率为40mN/min，保压时间5秒，为了消除基体对硬度的影响，压入深度小于涂层总厚度的1/10。共测量20个不同点的硬度，取平均值为涂层的硬度。The testing method of hardness is as follows: After the coating is deposited, use a bearing steel ball with a diameter of 20mm to grind the surface of the coating for 20 seconds, add diamond abrasive during grinding, and polish the surface of the substrate to a mirror surface. Then use the TTX-NHT2 nano-indenter (Anton Paar, Austria) to test the hardness of the coating at the wear mark (magnification 100 times), the indenter is a diamond glass indenter (Berkovich), the maximum load is 20mN, and the loading rate is 40mN /min, the unloading rate is 40mN/min, and the holding time is 5 seconds. In order to eliminate the influence of the matrix on the hardness, the indentation depth is less than 1/10 of the total thickness of the coating. The hardness of 20 different points was measured, and the average value was taken as the hardness of the coating.
结合强度的检测方法如下：采用瑞士CSM公司生产的REVETEST划痕测试仪测量涂层与基体的结合强度。划痕试验法是用一个直径约200微米的半球形金刚石压头在涂层表面上滑动，在此过程中通过自动加载机构连续增加垂直载荷L，当L达到其临界载荷Lc时，涂层与基体开始剥离，涂层和基体之间的界面临界载荷Lc即压头完全划透涂层并使之从其基体上连续剥离所需要的最小载荷；同时，压头与涂层和基体的摩擦力F相应发生变化。此时，涂层会产生声发射，通过传感器获取划痕时的声发射信号、载荷的变化量、切向力的变化量，经放大处理，输入计算机经A/D转换将测量结果绘制成图形，在声发射信号-载荷曲线上临界载荷值Lc处对应得出声发射峰，此时临界载荷Lc即为涂层与基体结合强度的判据。测试参数为：线性加载，加载载荷200N，加载速率99N/min，划痕速度5mm/min，划痕长度5mm。The detection method of bonding strength is as follows: the bonding strength between the coating and the substrate is measured with a REVETEST scratch tester produced by Swiss CSM Company. The scratch test method is to use a hemispherical diamond indenter with a diameter of about 200 microns to slide on the surface of the coating. During the process, the vertical load L is continuously increased by the automatic loading mechanism. When L reaches its critical load Lc, the coating and The substrate begins to peel off, and the interface critical load Lc between the coating and the substrate is the minimum load required for the indenter to completely penetrate the coating and make it peel off from the substrate continuously; at the same time, the friction between the indenter and the coating and the substrate F changes accordingly. At this time, the coating will produce acoustic emission, and the acoustic emission signal, the change of load and the change of tangential force are acquired through the sensor, and after amplification processing, the measurement result is drawn into a graph by inputting it into the computer through A/D conversion , the acoustic emission peak is corresponding to the critical load value Lc on the acoustic emission signal-load curve, and the critical load Lc is the criterion for the bonding strength between the coating and the substrate. The test parameters are: linear loading, loading load 200N, loading rate 99N/min, scratch speed 5mm/min, scratch length 5mm.
氧化增重的测试方法如下：将样品置于马弗炉中在空气气氛下加热至1000℃，保温1h，然后将样品取出在空气中冷却至室温。采用精度为0.1mg的高精度电子天平称量样品氧化前后的重量，计算样品的氧化增重。The test method for oxidation weight gain is as follows: put the sample in a muffle furnace and heat it to 1000°C in an air atmosphere, keep it warm for 1 hour, then take the sample out and cool it to room temperature in the air. A high-precision electronic balance with an accuracy of 0.1 mg was used to weigh the weight of the sample before and after oxidation, and calculate the oxidation weight gain of the sample.
摩擦系数测试参照国际标准ASTM G99-2017进行测试。The friction coefficient test is carried out according to the international standard ASTM G99-2017.
表1Table 1
从表1的检测结果可以看出，以硼含量梯度变化的Ti-B-N层作为过渡层，复合涂层的结合强度均超过100N，说明复合涂层中TiB2层与其余各子涂层间结合很好，有效解决了CVD制备TiB2涂层的使用问题；复合涂层中含有Ti-Al-N层，其1000℃氧化1h增重很少，说明复合涂层具有很好的高温抗氧化性能。From the test results in Table 1, it can be seen that the bonding strength of the composite coating exceeds 100 N when the Ti-BN layer with a gradient boron content is used as the transition layer, indicating that theTiB2 layer in the composite coating is bonded to the remaining sub-coatings. Very good, it effectively solves the problem of usingTiB2 coating prepared by CVD; the composite coating contains Ti-Al-N layer, and its weight gain is very small when it is oxidized at 1000°C for 1 hour, which shows that the composite coating has good high temperature oxidation resistance .
以下对通过本发明实施例1-2和对比例1-2制备得到的切削刀具的切削性能进行试验，分别进行使用寿命和磨损量两方面的测试。In the following, the cutting performance of the cutting tools prepared by the examples 1-2 and the comparative examples 1-2 of the present invention were tested, and the service life and wear amount were tested respectively.
其中，试验条件如下：Among them, the test conditions are as follows:
刀具：WC-Co硬质合金可转位铣刀（型号：XNMU 070508-MM4）Tool: WC-Co Carbide Indexable Milling Cutter (Model: XNMU 070508-MM4)
加工材料：不锈钢316LProcessing material: stainless steel 316L
切削参数：Cutting parameters:
切削速度：VC=220m/minCutting speed: VC=220m/min
进给：fz=0.25mm/zFeed: fz=0.25mm/z
切深：ap=1.0mmCutting depth: ap=1.0mm
切削宽度：ae=80%刀盘直径Cutting width: ae=80% cutter head diameter
切削方式：干切Cutting method: dry cutting
切削不同时间后，刀片后刀面的磨损量VB（单位mm）测量结果见表2，刀片后刀面磨损量采用带刻度标尺的OLYMPUS SZ61光学超景深显微镜测量。After cutting for different times, the measurement results of the blade flank wear VB (in mm) are shown in Table 2. The blade flank wear was measured with an OLYMPUS SZ61 optical ultra-depth-of-field microscope with a scale.
表2Table 2
从表2的对比来看，以硼含量梯度变化的Ti-B-N层作为过渡层，复合涂层的使用寿命是不含Ti-B-N过渡层的2倍以上，且切削过程中没有涂层剥落，表明本发明提供的切削刀具在耐磨性和刀具使用寿命上具有明显优势。From the comparison in Table 2, with the Ti-B-N layer with a gradient change in boron content as the transition layer, the service life of the composite coating is more than twice that of the transition layer without Ti-B-N, and there is no coating peeling off during the cutting process. It shows that the cutting tool provided by the invention has obvious advantages in wear resistance and tool life.
以上所述仅为本发明的优选实施例，并非因此限制本发明的专利范围，凡是在本发明的发明构思下，利用本发明说明书内容所作的等效结构变换，或直接/间接运用在其他相关的技术领域均包括在本发明的专利保护范围内。The above description is only a preferred embodiment of the present invention, and does not limit the patent scope of the present invention. Under the inventive concept of the present invention, the equivalent structural transformation made by using the content of the description of the present invention, or directly/indirectly used in other related All technical fields are included in the patent protection scope of the present invention.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104131250A (en)* | 2014-07-25 | 2014-11-05 | 广东工业大学 | Nanometer composite cutting tool coating with gradient composition design and preparation method thereof |
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| US20170204513A1 (en)* | 2016-01-20 | 2017-07-20 | Sumitomo Electric Hardmetal Corp. | Coating, cutting tool, and method of manufacturing coating |
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| CN109852938A (en)* | 2017-11-30 | 2019-06-07 | 沈阳东青科技有限公司 | A kind of AlTiN-Cu coating |
| CN114196940A (en)* | 2021-12-06 | 2022-03-18 | 赣州澳克泰工具技术有限公司 | Composite coating cutter and preparation method and application thereof |
| CN114592166A (en)* | 2022-03-16 | 2022-06-07 | 株洲钻石切削刀具股份有限公司 | Hard coating cutter containing gradient composite structure and preparation method thereof |
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| US20080102296A1 (en)* | 2006-10-26 | 2008-05-01 | Farshad Ghasripoor | Erosion resistant coatings and methods of making |
| CN101524904A (en)* | 2008-03-07 | 2009-09-09 | 山高刀具公司 | Layered coated cutting tool |
| CN102021516A (en)* | 2009-09-02 | 2011-04-20 | 三菱综合材料株式会社 | Surface-coated cutting tool |
| CN105142831A (en)* | 2013-02-21 | 2015-12-09 | 住友电工硬质合金株式会社 | Surface-coated cutting tool and process for producing same |
| CN104131250A (en)* | 2014-07-25 | 2014-11-05 | 广东工业大学 | Nanometer composite cutting tool coating with gradient composition design and preparation method thereof |
| US20170204513A1 (en)* | 2016-01-20 | 2017-07-20 | Sumitomo Electric Hardmetal Corp. | Coating, cutting tool, and method of manufacturing coating |
| CN109852938A (en)* | 2017-11-30 | 2019-06-07 | 沈阳东青科技有限公司 | A kind of AlTiN-Cu coating |
| CN109652763A (en)* | 2018-12-17 | 2019-04-19 | 艾瑞森表面技术（苏州）股份有限公司 | A kind of periodic multilayer coating and preparation method thereof suitable for carbide chip |
| CN114196940A (en)* | 2021-12-06 | 2022-03-18 | 赣州澳克泰工具技术有限公司 | Composite coating cutter and preparation method and application thereof |
| CN114592166A (en)* | 2022-03-16 | 2022-06-07 | 株洲钻石切削刀具股份有限公司 | Hard coating cutter containing gradient composite structure and preparation method thereof |
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| CN117921042A (en)* | 2024-03-22 | 2024-04-26 | 赣州澳克泰工具技术有限公司 | CVD composite coating cutter and preparation method thereof |
| CN117921042B (en)* | 2024-03-22 | 2024-06-25 | 赣州澳克泰工具技术有限公司 | CVD composite coating cutter and preparation method thereof |
| CN117926215A (en)* | 2024-03-25 | 2024-04-26 | 赣州澳克泰工具技术有限公司 | A cutting tool with CVD coating and preparation method thereof |
| CN117926215B (en)* | 2024-03-25 | 2024-06-07 | 赣州澳克泰工具技术有限公司 | Cutter with CVD coating and preparation method thereof |
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| CN116604057B (en) | 2023-10-20 |
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