Ti-w-b coating, method for producing the same, and use thereof

Abstract

The present application relates to a kind of Ti-W-B coating and its preparation method and application, the Ti-W-B coating is nanostructured coating, the molecular structure expression of the Ti-W-B coating is Ti 1‑x W x B y Wherein, x=0.06-0.55, y=1.8-3.5;The preparation method includes: under inert atmosphere, using TiB2 Target material is magnetron sputtering to substrate, while using W target material is high-power pulse magnetron sputtering to substrate, is deposited on the surface of substrate and obtains Ti-W-B coating.The Ti-W-B coating and its preparation method provided by the present application can form TiB x / WB x Nano composite structure by introducing high ionization W ion, can improve the hardness, toughness and lubricity of coating, can be widely applied in metal surface treatment or metal processing.

Description

Technical Field

[0001] This invention relates to the field of materials, specifically to a Ti-WB coating, its preparation method, and its application. Background Technology

[0002] With the upgrading of manufacturing technology, the demand for high-quality precision metal cutting is constantly increasing, and efficient, high-speed, and high-precision cutting methods have become the main development direction of machining. In high-speed dry cutting, due to the intense friction between the tool and the workpiece surface, the cutting temperature reaches 900-1200℃, resulting in problems such as tool overheating, poor red hardness, and severe wear. Therefore, depositing a hard coating on the tool surface is the key to achieving high-speed cutting.

[0003] Titanium diboride (TiB2) is a type of hard coating with excellent mechanical, physical, and chemical properties, including a high melting point (approximately 3100℃), good thermal and electrical conductivity, high hardness, high wear resistance, and corrosion resistance. The superior properties of TiB2 are attributed to its crystal structure and atomic bonding. TiB2 crystallizes in a hexagonal structure, where boron atoms reside in the voids between hexagonally arranged Ti atoms, which bond together to form covalent BB bonds, creating a two-dimensional network. Therefore, TiB2 coatings are widely used in tool materials, weapon protection, and automotive friction components, especially in the machining industry, where they provide excellent wear resistance and oxidation protection for the surfaces of cemented carbide tools such as WC-Co, thereby improving tool life. For example, TiB2 has almost no chemical affinity for aluminum alloys and exhibits low adhesion to the workpiece, thus avoiding built-up edges and cold welds, ensuring the reliability and production efficiency of finishing processes. The TiB2 coating achieves a friction coefficient of less than 0.5 against titanium alloy TC4 at 400℃. Its high-temperature oxidation products, such as B2O3, have excellent self-lubricating effects, which can alleviate the problems of severe adhesive wear and diffusion wear between titanium alloy materials and cutting tools, thereby extending the tool's service life.

[0004] TiB2 coatings are typically prepared by sputtering TiB2 targets in an argon atmosphere. The deposited TiB2 coatings usually exhibit a columnar crystal structure and are overstoichiometric, meaning excess boron tends to precipitate at grain boundaries, leading to high residual stress and poor toughness. Therefore, achieving controllable adjustment of the stoichiometry and internal stress of TiB2 coatings is crucial for expanding their applications.

[0005] Currently, a study (“Experiment and simulation of the compositional evolution of Ti–B thin films deposited by sputtering of a compound target”, Neidhardt, J., et al., Journal of Applied Physics, 2008, 104(6):063304.) has revealed the sputtering deposition of TiB. x The mechanism that easily leads to overstoichiometry, namely Ar + There is a mass difference between the sputtered particles and those from the TiB2 target, B + Overflow angle compared to Ti + Concentrate, B + Preferential movement along the normal direction of the target material is preferred, but no method or strategy for controllably adjusting the stoichiometry of the TiB2 coating has been proposed. Another study (“Controlling the boron-to-titanium ratio in magnetron-sputter-deposited TiBx thin films”, Petrov, I., et al., Journal of Vacuum Science and Technology A, 2017, 35(5):050601.) proposed reducing the stoichiometry of TiB2 coating by applying an external magnetic field between the substrate and the target material. x The stoichiometric method involves using an external magnetic field to deflect the ion beam, but this method involves modifications to the equipment's magnetic field and simulation of plasma motion, making it complex and difficult to apply in practice.

[0006] Furthermore, in actual machining processes, besides oxidation resistance and high-temperature mechanical properties, the tribological properties of the coating are also a crucial factor affecting the high-speed dry cutting performance of coated tools. During high-temperature tribological processes, the lubricating oxide B2O3 generated on the TiB2 coating surface is easily scraped or removed after liquefaction, resulting in the TiB2 coating exhibiting a low coefficient of friction and a high wear rate, which also limits the application of TiB2 coatings.

[0007] Therefore, optimizing the TiB2 coating to reduce residual stress and improve toughness and high-temperature wear resistance is a problem that needs to be solved. Summary of the Invention

[0008] To address the above problems, the present invention aims to provide a Ti-WB coating, its preparation method, and its applications. Compared with existing technologies, the present invention introduces highly ionized W ions into the TiB2 coating, forming a TiB coating with microscopic structure.x / WB x Nanocomposite structures can improve the hardness and toughness of coatings and reduce the coefficient of friction, and can be widely used in metal surface treatment or metal processing.

[0009] To achieve this objective, the present invention adopts the following technical solution:

[0010] In a first aspect, the present invention provides a Ti-WB coating, wherein the Ti-WB coating is a nanostructured coating;

[0011] The molecular structure expression of the Ti-WB coating is Ti 1-x W x B y ;

[0012] Where x = 0.06 - 0.55, y = 1.8 - 3.5.

[0013] In this invention, addressing the common issue that magnetron sputtered TiB2 coatings exhibit a columnar crystal structure and are overstoichiometric, leading to excessive boron segregation at grain boundaries and resulting in high residual stress and poor toughness, this invention provides a TiB2 coating with... x / WB x The nanocomposite coating introduces highly ionized W ions, enabling it to... x Interfacial mixing occurs within the layer, and TiB bonds with B; therefore, the coating contains both Ti and B. x Phase, and also exists in WB x Phase, reducing the coating TiB x The high atomic ratio of B / Ti in the phase can increase the strength and toughness of the coating, achieving a superhard effect. Furthermore, during high-temperature friction and wear, when the lubricating oxide B2O3 generated on the TiB2 coating surface evaporates, the W oxide formed by introducing W can provide lubrication in a higher temperature range, achieving a high-temperature self-lubricating effect. In addition, the Ti-WB coating provided in this application can be prepared under low-temperature deposition, reducing growth stress. Therefore, the Ti-WB coating provided by this invention solves the problems of high residual stress, poor toughness, and poor high-temperature wear resistance of existing TiB2 coatings. This invention forms WB through highly ionized W ions. x Compared to introducing W elements into the crystal lattice solely through solid solution or other methods, the TiB phase in this invention... x / WB x The nanocomposite structure exhibits the Hall-Petch effect, which can effectively improve the hardness of the coating.

[0014] The Ti 1-x W x B yIn this context, x = 0.06-0.55, for example, it can be 0.06, 0.08, 0.10, 0.12, 0.14, 0.16, 0.18, 0.20, 0.22, 0.24, 0.26, 0.28, 0.30, 0.32, 0.34, 0.36, 0.38, 0.40, 0.42, 0.43, 0.45, 0.46, 0.48, 0.50, 0.52, 0.54, or 0.55, but is not limited to the listed values; other unlisted values ​​within the range also apply. y = 1.8-3.5, for example, it can be 1.8, 2, 2.2, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.2, 3.4, or 3.5, but is not limited to the listed values; other unlisted values ​​within the range also apply.

[0015] The present invention preferably controls the values ​​of x and y within a specific range, which can further enable the coating to have high hardness, high toughness and high temperature self-lubricating properties.

[0016] As can be seen from the molecular structure expression and the values ​​of x and y provided by this invention, under the condition that the stoichiometric ratio of B-Ti in existing TiB2 coatings is generally >2:1, this invention can achieve an understoichiometric ratio, that is, the stoichiometric ratio of B / (Ti+W) is 1.8, at which point the hardness can reach 29.8 GPa. When the stoichiometric ratio of B / (Ti+W) is 3.5, the hardness can be further improved, reaching 44.6 GPa.

[0017] Preferably, the size of the grains in the nanostructure coating is 5-50 nm, for example, it can be 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm or 50 nm, but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0018] Preferably, the hardness of the Ti-WB coating is 29.8-44.6 GPa, for example, it can be 29.8 GPa, 30 GPa, 31 GPa, 32.5 GPa, 33.5 GPa, 34 GPa, 34.5 GPa, 35 GPa, 36 GPa, 37 GPa, 38 GPa, 39 GPa, 40 GPa, 41 GPa, 42 GPa, 43 GPa or 44.6 GPa, but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0019] Preferably, the elastic modulus of the Ti-WB coating is 395-596 GPa, for example, it can be 395 GPa, 400 GPa, 410 GPa, 420 GPa, 440 GPa, 460 GPa, 480 GPa, 498 GPa, 500 GPa, 512 GPa, 520 GPa, 525 GPa, 540 GPa, 560 GPa, 580 GPa, 590 GPa or 596 GPa, but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0020] Preferably, the coefficient of friction of the Ti-WB coating is 0.22-0.65, for example, it can be 0.22, 0.24, 0.26, 0.28, 0.30, 0.32, 0.34, 0.36, 0.38, 0.40, 0.42, 0.45, 0.48, 0.5, 0.52, 0.58, 0.6, 0.62 or 0.65, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0021] In a second aspect, the present invention provides a method for preparing a Ti-WB coating as described in the first aspect of the present invention, the method comprising:

[0022] In an inert atmosphere, a Ti-WB coating is deposited on the substrate by magnetron sputtering with a TiB2 target and high-power pulsed magnetron sputtering with a W target.

[0023] In the preparation method provided by this invention, highly ionized W ions are introduced by high-power pulsed magnetron sputtering, which accelerates the W ions to the substrate surface at high energy and bombards the growing coating, thereby achieving Ti deposition at a lower deposition temperature. 1-x W x B y Coating, W ions can be applied to TiB x Interfacial mixing occurs within the layer, and TiB bonds with B, resulting in the presence of both Ti and B in the coating. x Phase, and also exists in WB x Phase, thereby obtaining a nanocomposite structure, and optimizing the TiB coating x The atomic ratio of B / Ti in the phase is improved to enhance toughness, reduce residual stress, expand the high-temperature self-lubricating temperature range of the coating, and enhance high-temperature wear resistance.

[0024] Preferably, the magnetron sputtering method of the TiB2 target includes DC magnetron sputtering or high-power pulsed magnetron sputtering.

[0025] Preferably, the average sputtering power of the TiB2 target is 5-15 W / cm². 2 For example, it could be 5W / cm 2 6W / cm 27W / cm 2 8W / cm 2 9W / cm 2 10W / cm 2 11W / cm 2 12W / cm 2 13W / cm 2 14W / cm 2 Or 15W / cm 2 However, this does not limit the listed values; other unlisted values ​​within the range are also applicable.

[0026] In this invention, the average sputtering power is controlled to achieve control of Ti. 1-x W x B y The atomic ratio of Ti and B elements in the coating is adjusted to further optimize the coating's hardness, toughness, and wear resistance.

[0027] Preferably, the peak current density of the TiB2 target during high-power pulsed magnetron sputtering is 0.2-0.8 A / cm². 2 For example, it could be 0.2A / cm 2 0.3A / cm 2 0.4A / cm 2 0.5A / cm 2 0.6A / cm 2 0.7A / cm 2 Or 0.8A / cm 2 However, this does not limit the listed values; other unlisted values ​​within the range are also applicable.

[0028] Preferably, the number of working cathodes during TiB2 target sputtering is at least 2, for example, 2, 3 or 4, but not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0029] Preferably, the average sputtering power of the W target is 5-20 W / cm². 2 For example, it could be 5W / cm 2 6W / cm 2 7W / cm 2 8W / cm 2 9W / cm 2 10W / cm 2 11W / cm 2 12W / cm 2 13W / cm 2 14W / cm 2 15W / cm 2 Or 20W / cm 2However, this does not limit the listed values; other unlisted values ​​within the range are also applicable.

[0030] In this invention, the average sputtering power is controlled to achieve control of Ti. 1-x W x B y The atomic percentage of W in the coating is adjusted to further optimize the coating's hardness, toughness, and wear resistance.

[0031] Preferably, the peak current density of the W target material during high-power pulsed magnetron sputtering is 0.2-1.2 A / cm². 2 For example, it could be 0.2A / cm 2 0.3A / cm 2 0.4A / cm 2 0.5A / cm 2 0.6A / cm 2 0.7A / cm 2 0.8A / cm 2 0.9A / cm 2 1A / cm 2 1.1A / cm 2 Or 1.2A / cm 2 However, this does not limit the listed values; other unlisted values ​​within the range are also applicable.

[0032] Preferably, the number of working cathodes during sputtering of the W target is at least 2, for example, 2, 3 or 4, but not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0033] Preferably, the inert atmosphere includes an argon atmosphere.

[0034] Preferably, the pressure of the argon atmosphere is 0.2-0.8 Pa, for example, it can be 0.2 Pa, 0.3 Pa, 0.4 Pa, 0.5 Pa, 0.6 Pa, 0.7 Pa or 0.8 Pa, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0035] In this invention, by controlling the pressure of the argon atmosphere within a specific range, sufficient Ar ions can be provided to bombard the target surface, thus acting as a sputtering target, maintaining a high growth rate for the thin film and densifying the coating. If the pressure is too high, it will increase the number of collisions before the sputtered ions reach the substrate, thereby affecting the thin film growth efficiency.

[0036] Preferably, the deposition temperature is 50-500℃, for example, it can be 50℃, 60℃, 70℃, 80℃, 90℃, 100℃, 120℃, 140℃, 150℃, 160℃, 180℃, 200℃, 250℃, 300℃, 350℃, 400℃, 450℃ or 500℃, but is not limited to the listed values, and other unlisted values ​​within the range are also applicable.

[0037] In this invention, by using high-power pulsed magnetron sputtering to introduce highly ionized W ions, the deposition temperature can be reduced, and coating deposition can be achieved even at 50°C, thereby reducing the growth stress of the coating.

[0038] Preferably, the orbital speed of the substrate during deposition is 0.5-3 rpm, for example, it can be 0.5 rpm, 1 rpm, 1.5 rpm, 2 rpm, 2.5 rpm or 3 rpm, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0039] Preferably, the bias voltage of the substrate during deposition is -50 to -300V, for example, it can be -50V, -80V, -100V, -120V, -150V, -180V, -200V, -220V, -250V, -280V or -300V, but is not limited to the listed values. Other unlisted values ​​within the range are also applicable.

[0040] The present invention preferably controls the bias voltage of the substrate within a specific range during deposition, which can regulate the energy of ion bombardment of the substrate, thereby regulating the microstructure and properties of the coating. Moreover, the W ions (heavy metals) bombard the substrate more rapidly under the bias voltage, which can provide additional energy for atomic migration during coating growth, replacing the energy provided by substrate heating, thereby achieving low-temperature growth.

[0041] In this invention, the substrate includes any one of cemented carbide, steel, or titanium alloy.

[0042] Preferably, the substrate is pretreated before deposition.

[0043] Preferably, the pretreatment includes any one or a combination of at least two of mechanical grinding, polishing, or cleaning.

[0044] Preferably, the cleaning includes any one or a combination of at least two of solvent cleaning, glow discharge cleaning, or ion etching cleaning.

[0045] In this invention, the solvent cleaning method is not particularly limited, and any solvent cleaning method used in the art for cleaning Ti-WB coatings can be used. For example, it can be: first ultrasonic cleaning with deionized water for 15-30 min, and then ultrasonic cleaning with 95-98% alcohol solution for 15-30 min. In this invention, the glow discharge cleaning method is not particularly limited, and any glow discharge cleaning method used in the art for cleaning Ti-WB coatings can be used. For example, it can be: cleaning the substrate with substrate glow discharge in an argon atmosphere for 40-50 min, with a working pressure of 0.3-0.5 Pa, a substrate bias voltage of -600 to -700 V, and a frequency of 25-35 kHz. In this invention, the ion etching cleaning method is not particularly limited, and any ion etching cleaning method used in the art for cleaning Ti-WB coatings can be used. For example, it can be: cleaning with Ar... + The substrate is cleaned with an ion source for 25-35 minutes at an ambient pressure of 0.2-0.4 Pa and a substrate bias voltage of -150 to -250 V.

[0046] As a preferred embodiment of the second aspect of the present invention, the preparation method includes the following steps:

[0047] The substrate is pretreated, the pretreatment including any one or a combination of at least two of mechanical grinding, polishing or cleaning, and the cleaning including any one or a combination of at least two of solvent cleaning, glow discharge cleaning or ion etching cleaning.

[0048] The pretreated substrate was subjected to DC magnetron sputtering or high-power pulsed magnetron sputtering using a TiB2 target under an argon atmosphere with a pressure of 0.2-0.8 Pa. At the same time, a W target was used to perform high-power pulsed magnetron sputtering on the substrate to deposit a Ti-WB coating on the substrate surface. The deposition temperature was 50-500℃, the orbital speed of the substrate during deposition was 0.5-3 rpm, and the bias voltage of the substrate during deposition was -50 to -300V.

[0049] The average sputtering power of the TiB2 target is 5-15 W / cm². 2 The peak current density of the TiB2 target during high-power pulsed magnetron sputtering is 0.2-0.8 A / cm². 2 The number of working cathodes during TiB2 target sputtering is at least two;

[0050] The average sputtering power of the W target is 5-20 W / cm². 2 The peak current density of the W target material during high-power pulsed magnetron sputtering is 0.2-1.2 A / cm³. 2 The number of working cathodes during sputtering of the W target is at least two.

[0051] Thirdly, the present invention provides an application of the Ti-WB coating as described in the first aspect of the present invention, wherein the Ti-WB coating is used for metal surface treatment or metal processing.

[0052] The Ti-WB coating provided by this invention is used for metal surface treatment or metal processing and has good strength, toughness and lubricity.

[0053] Compared with the prior art, the present invention has the following beneficial effects:

[0054] The Ti-WB coating and its preparation method provided by this invention introduce highly ionized W ions using high-power pulsed magnetron sputtering, enabling the coating to achieve high efficiency in TiB coatings. x Interfacial mixing occurs within the layer, and TiB bonds with B; therefore, the coating contains both Ti and B. x Phase, and also exists in WB x Phase, to obtain TiB x / WB x Nanocomposite structure reduces the coating TiB x The atomic ratio of B / Ti in the phase can increase the strength and toughness of the coating; the introduction of the W component can expand the high-temperature self-lubricating temperature range of the coating and enhance its high-temperature wear resistance; moreover, it can reduce the deposition temperature and growth stress, thereby obtaining a Ti coating with high hardness, high toughness and low coefficient of friction. 1-x W x B y coating. Attached Figure Description

[0055] Figure 1 This is a SEM image of the coating described in Embodiment 1 of the present invention;

[0056] Figure 2 This is a SEM image of the coating described in Embodiment 2 of the present invention;

[0057] Figure 3 This is a SEM image of the coating described in Embodiment 3 of the present invention;

[0058] Figure 4 This is a SEM image of the coating described in Embodiment 4 of the present invention;

[0059] Figure 5 This is a SEM image of the coating described in Embodiment 5 of the present invention;

[0060] Figure 6 This is a SEM image of the coating described in Embodiment 6 of the present invention;

[0061] Figure 7 This is a SEM image of the coating described in Embodiment 7 of the present invention;

[0062] Figure 8 This is a SEM image of the coating described in Comparative Example 1 of the present invention;

[0063] Figure 9 This is a TEM image of the coating described in Embodiment 1 of the present invention;

[0064] Figure 10 These are XRD patterns of the coatings described in Examples 1-7 and Comparative Example 1 of the present invention;

[0065] Figure 11 These are hardness result diagrams of the coatings described in Examples 1-7 and Comparative Example 1 of the present invention;

[0066] Figure 12 These are the elastic modulus results of the coatings described in Examples 1-7 and Comparative Example 1 of the present invention;

[0067] Figure 13 These are the friction coefficient results of the coatings described in Examples 1-7 and Comparative Example 1 of the present invention. Detailed Implementation

[0068] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.

[0069] Example 1

[0070] This embodiment provides a Ti-WB coating, the molecular structure of which is represented by the formula Ti. 1-x W x B y The coating was tested using XPS, and the results were x = 0.55 and y = 1.8.

[0071] This embodiment also provides a method for preparing the above-mentioned Ti-WB coating, the method comprising the following steps:

[0072] (1) Matrix pretreatment:

[0073] First, the substrate is mechanically ground with sandpaper, then the surface of the substrate is polished with polishing fluid (LD2.0 from Dongguan Yingxin Semiconductor Materials Co., Ltd., diamond particle size 2.0μm), and then cleaned.

[0074] The cleaning process includes sequential solvent cleaning, glow discharge cleaning, or ion etching cleaning. Solvent cleaning involves ultrasonic cleaning with deionized water for 20 minutes, followed by ultrasonic cleaning with 98% alcohol solution for 20 minutes. Glow discharge cleaning involves cleaning the substrate with substrate glow discharge in an argon atmosphere for 45 minutes at a working pressure of 0.4 Pa, a substrate bias voltage of -650 V, and a frequency of 30 kHz. Ion etching cleaning involves using Ar... +The substrate was cleaned with an ion source for 30 minutes at an ambient pressure of 0.3 Pa and a substrate bias voltage of -200 V.

[0075] (2) Sedimentation

[0076] The pretreated substrate was subjected to high-power pulsed magnetron sputtering using a TiB2 target and a W target under an argon atmosphere with a pressure of 0.6 Pa. A Ti-WB coating was deposited on the substrate surface. The deposition temperature was 150℃, the orbital speed of the substrate was 1 rpm, and a pair of TiB2-W targets were used for coating deposition. The bias voltage of the substrate was -60V during deposition.

[0077] The average sputtering power of the TiB2 target is 5 W / cm². 2 The peak current density of the TiB2 target during high-power pulsed magnetron sputtering is 0.35 A / cm². 2 The number of working cathodes during the sputtering of the TiB2 target is 2;

[0078] The average sputtering power of the W target is 20 W / cm². 2 The W target material has a peak current density of 0.8 A / cm² when subjected to high-power pulsed magnetron sputtering. 2 The number of working cathodes during sputtering of the W target is 2.

[0079] Example 2

[0080] This embodiment provides a Ti-WB coating, the molecular structure of which is represented by the formula Ti. 1-x W x B y The coating was tested using XPS, and the results were x = 0.42 and y = 2.8.

[0081] This embodiment also provides a method for preparing the above-mentioned Ti-WB coating, the method comprising the following steps:

[0082] (1) Matrix pretreatment: The operation is the same as step (1) in Example 1;

[0083] (2) Sedimentation

[0084] The pretreated substrate was subjected to high-power pulsed magnetron sputtering using a TiB2 target and a W target under an argon atmosphere with a pressure of 0.6 Pa. A Ti-WB coating was deposited on the substrate surface. The deposition temperature was 150℃, the orbital speed of the substrate was 1 rpm, and a pair of TiB2-W targets were used for coating deposition. The bias voltage of the substrate was -60V during deposition.

[0085] The average sputtering power of the TiB2 target is 10 W / cm². 2 The peak current density of the TiB2 target during high-power pulsed magnetron sputtering is 0.63 A / cm². 2 The number of working cathodes during the sputtering of the TiB2 target is 2;

[0086] The average sputtering power of the W target is 10 W / cm². 2 The W target material has a peak current density of 0.62 A / cm² when subjected to high-power pulsed magnetron sputtering. 2 The number of working cathodes during sputtering of the W target is 2.

[0087] Example 3

[0088] This embodiment provides a Ti-WB coating, the molecular structure of which is represented by the formula Ti. 1-x W x B y The coating was tested using XPS, and the results were x = 0.06 and y = 3.5.

[0089] This embodiment also provides a method for preparing the above-mentioned Ti-WB coating. The only difference between this method and Example 2 is that the average sputtering power of the TiB2 target is 15 W / cm². 2 The average sputtering power of the W target is 5 W / cm². 2 .

[0090] Example 4

[0091] This embodiment provides a Ti-WB coating, the molecular structure of which is represented by the formula Ti. 1-x W x B y The coating was tested using XPS, and the results were x = 0.43 and y = 2.6.

[0092] This embodiment also provides a method for preparing the above-mentioned Ti-WB coating, the only difference from Example 2 is that the bias voltage of the substrate is -100V during deposition.

[0093] Example 5

[0094] This embodiment provides a Ti-WB coating, the molecular structure of which is represented by the formula Ti. 1-x W x B y The coating was tested using XPS, and the results were x = 0.45 and y = 2.5.

[0095] This embodiment also provides a method for preparing the above-mentioned Ti-WB coating. The only difference between the preparation method and Example 2 is that the bias voltage of the substrate is -300V and the deposition temperature is 50°C during deposition.

[0096] Example 6

[0097] This embodiment provides a Ti-WB coating, the molecular structure of which is represented by the formula Ti. 1-x W x B y The coating was tested using XPS, and the results were x = 0.44 and y = 2.9.

[0098] This embodiment also provides a method for preparing the above-mentioned Ti-WB coating. The only difference between this method and Example 2 is that the pressure of the argon atmosphere is 0.2 Pa.

[0099] Example 7

[0100] This embodiment provides a Ti-WB coating, the molecular structure of which is represented by the formula Ti. 1-x W x B y The coating was tested using XPS, and the results were x = 0.45 and y = 2.7.

[0101] This embodiment also provides a method for preparing the above-mentioned Ti-WB coating. The only difference between this method and Example 2 is that the pressure of the argon atmosphere is 0.8 Pa.

[0102] Comparative Example 1

[0103] This comparative example provides a TiB x The coating was tested using XPS, and the result was x = 3.2.

[0104] This comparative example also provides the aforementioned TiB x The coating preparation method is as follows: TiB is deposited using only a DC magnetron sputtering TiB2 target. x The coating was applied using a DC magnetron sputtering TiB2 target with an average power density of 4.5 W / cm². 2 Bias voltage -60V, deposition pressure 0.4Pa.

[0105] The Ti obtained in Examples 1-7 was detected using XPS. 1-x W x B y The component content in the coating was determined, and the values ​​of x and y were obtained. The obtained values ​​of x and y, along with the main process parameters, are shown in Table 1. XPS was used to detect the TiB content in Comparative Example 1. xThe coating yielded x = 3.2.

[0106] The microstructure of the coatings obtained in Examples 1-7 and Comparative Example 1 was measured using SEM. The results for Examples 1-7 are as follows: Figure 1-7 As shown, from Figure 1-7 It can be seen that when the W% content (x value) in the coating is low, the columnar crystal structure of the coating is obvious; when a larger bias voltage is applied, the columnar structure of the coating is not obvious, and the coating is denser; the results of Comparative Example 1 are as follows. Figure 8 As shown, from Figure 8 As can be seen from the data, TiB prepared by DC magnetron sputtering deposition... x The coating has a relatively loose cross-sectional structure.

[0107] Taking the coating of Example 1 as an example, the coating was subjected to TEM testing, and the results are as follows: Figure 9 As shown, from Figure 9 It can be seen that the coating is TiB. x and WB x The nanocomposite phase structure.

[0108] The phase structure and phase composition of the coatings obtained in Examples 1-7 and Comparative Example 1 were determined by XRD, and the results are as follows: Figure 10 As shown, from Figure 10 It can be seen that the out-of-plane direction (growth direction) of the coating is mainly TiB2(001) and (101).

[0109] The hardness and elastic modulus of the coatings obtained in Examples 1-7 and Comparative Example 1 were characterized using a nanoindentation instrument. The test methods and procedures were performed in accordance with the international standard ISO-14577. The results are shown in Table 1.

[0110] The hardness results of Examples 1-7 are as follows: Figure 11 As shown, from Figure 11 It can be seen that the coating hardness of Examples 1-7 is in the range of 29.8-44.6 GPa, with Example 3 reaching the highest at 44.6 GPa, while the coating hardness of Comparative Example 1 only reaches 27.9 GPa; the elastic modulus of Examples 1-7 and Comparative Example 1 is as follows: Figure 12 As shown, from Figure 12 As can be seen from the data, the elastic modulus of the coatings in Examples 1-7 is in the range of 395-596 GPa, with Example 3 reaching the highest of 596 GPa, while the elastic modulus of the coating in Comparative Example 1 only reaches 340 GPa.

[0111] The friction coefficients of the coatings obtained in Examples 1-7 and Comparative Example 1 were tested using a friction and wear testing machine. The test load was 5 N, the grinding ball was Al2O3 with a diameter of 6 mm, and the linear velocity was 0.1 m / s. The results are shown in Table 1 and... Figure 13 As shown, from Figure 13 It can be seen that the coefficient of friction of the coating in Examples 1-7 ranges from 0.22 to 0.68. The addition of sufficient W (Example 1) reduces the coefficient of friction of the coating to as low as 0.22, and the coefficient of friction further decreases with the increase of friction time (wear track distance). The coefficient of friction of Comparative Example 1 is much higher than that of Examples 1-7, reaching 0.82.

[0112] Table 1

[0113]

[0114] In summary, the Ti-WB coatings provided in Examples 1-7 and the TiB coatings provided in Comparative Example 1 demonstrate the superior performance of the Ti-WB coatings. x The performance comparison of the coatings shows that the Ti-WB coating provided in this application can significantly improve hardness and elastic modulus, and has a lower coefficient of friction, which has broad application prospects in the fields of metal surface treatment or metal processing.

[0115] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.

Claims

1. A Ti-WB coating, characterized in that, The Ti-WB coating is a nanostructured coating; The molecular structure expression of the Ti-WB coating is Ti 1-x W x B y ; in, x =0.06-0.55, y =1.8-3.5; The Ti-WB coating was prepared using the following method: In an inert atmosphere, a Ti-WB coating was deposited on the substrate by magnetron sputtering with a TiB2 target and high-power pulsed magnetron sputtering with a W target. The high-power pulsed magnetron sputtering introduces highly ionized W ions to form TiB. x / WB x Nanocomposite structures; The average sputtering power of the W target is 5-20 W / cm². 2 ; The peak current density of the W target material during high-power pulsed magnetron sputtering is 0.2-1.2 A / cm³. 2 .

2. The Ti-WB coating according to claim 1, characterized in that, The size of the grains in the nanostructured coating is 5-50 nm.

3. The Ti-WB coating according to claim 1, characterized in that, The hardness of the Ti-WB coating is 29.8-44.6 GPa.

4. The Ti-WB coating according to claim 1, characterized in that, The elastic modulus of the Ti-WB coating is 395-596 GPa.

5. The Ti-WB coating according to claim 1, characterized in that, The coefficient of friction of the Ti-WB coating is 0.22-0.

65.

6. A method for preparing a Ti-WB coating as described in any one of claims 1-5, characterized in that, The preparation method includes: In an inert atmosphere, a Ti-WB coating was deposited on the substrate by magnetron sputtering with a TiB2 target and high-power pulsed magnetron sputtering with a W target. The average sputtering power of the W target is 5-20 W / cm². 2 ; The peak current density of the W target material during high-power pulsed magnetron sputtering is 0.2-1.2 A / cm³. 2 .

7. The preparation method according to claim 6, characterized in that, The magnetron sputtering method for the TiB2 target includes DC magnetron sputtering or high-power pulsed magnetron sputtering.

8. The preparation method according to claim 7, characterized in that, The average sputtering power of the TiB2 target is 5-15 W / cm². 2 .

9. The preparation method according to claim 7, characterized in that, The peak current density of the TiB2 target during high-power pulsed magnetron sputtering is 0.2-0.8 A / cm³. 2 .

10. The preparation method according to claim 7, characterized in that, The number of working cathodes during TiB2 target sputtering is at least two.

11. The preparation method according to claim 6, characterized in that, The number of working cathodes during sputtering of the W target is at least two.

12. The preparation method according to claim 6, characterized in that, The inert atmosphere includes an argon atmosphere.

13. The preparation method according to claim 12, characterized in that, The pressure of the argon atmosphere is 0.2-0.8 Pa.

14. The preparation method according to claim 6, characterized in that, The deposition temperature is 50-500℃.

15. The preparation method according to claim 6, characterized in that, The orbital speed of the substrate during deposition is 0.5-3 rpm.

16. The preparation method according to claim 6, characterized in that, The substrate bias voltage during deposition is -50 to -300V.

17. The preparation method according to claim 6, characterized in that, The substrate is pretreated before deposition.

18. The preparation method according to claim 17, characterized in that, The pretreatment includes any one or a combination of at least two of mechanical grinding, polishing, or cleaning.

19. The preparation method according to claim 18, characterized in that, The cleaning process includes any one or a combination of at least two of solvent cleaning, glow discharge cleaning, or ion etching cleaning.

20. The preparation method according to claim 6, characterized in that, The preparation method includes the following steps: The substrate is pretreated, the pretreatment including any one or a combination of at least two of mechanical grinding, polishing or cleaning, and the cleaning including any one or a combination of at least two of solvent cleaning, glow discharge cleaning or ion etching cleaning. The pretreated substrate was subjected to DC magnetron sputtering or high-power pulsed magnetron sputtering using a TiB2 target under an argon atmosphere with a pressure of 0.2-0.8 Pa. At the same time, a W target was used to perform high-power pulsed magnetron sputtering on the substrate to deposit a Ti-WB coating on the substrate surface. The deposition temperature was 50-500℃, the orbital speed of the substrate during deposition was 0.5-3 rpm, and the bias voltage of the substrate during deposition was -50 to -300V. The average sputtering power of the TiB2 target is 5-15 W / cm². 2 The peak current density of the TiB2 target during high-power pulsed magnetron sputtering is 0.2-0.8 A / cm². 2 The number of working cathodes during TiB2 target sputtering is at least two; The average sputtering power of the W target is 5-20 W / cm². 2 The peak current density of the W target material during high-power pulsed magnetron sputtering is 0.2-1.2 A / cm³. 2 The number of working cathodes during sputtering of the W target is at least two.

21. An application of the Ti-WB coating as described in any one of claims 1-5, characterized in that, The Ti-WB coating is used for metal surface treatment or metal processing.

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