Reinforced and toughened TiB2-Me nano coating as well as preparation method and application thereof

Abstract

The invention relates to a reinforced and toughened TiB2-Me nano coating as well as a preparation method and application thereof. The reinforced and toughened TiB2-Me nano coating comprises titanium diboride layers and metal layers, wherein the titanium diboride layers and the metal layers are alternately stacked; the titanium diboride layer is made of hexagonal phase titanium diboride; the metal layer is made of any one or a combination of at least two of Zr, Hf and Ti. According to the reinforced and toughened TiB2-Me nano coating provided by the invention, through introduction of the metal layer, a metal intercalation layer is formed between any two adjacent titanium diboride layers, and interfacial atom diffusion, mixing and bonding effects are generated, so that the hardness, toughness and high-temperature oxidation resistance of the coating are improved; the reinforced and toughened TiB2-Me coating can be applied to metal surface treatment or metal processing.

Description

Technical Field

[0001] The invention belongs to the technical field of materials and relates to a coating structure, in particular to a reinforced and toughened TiB 2 -Me nano coating and its preparation method and application. Background Art

[0002] Titanium diboride (TiB 2 ) has a high melting point, good thermal and electrical conductivity, high hardness, high wear resistance and corrosion resistance, and is widely used in tool materials, weapon protection or automotive friction components. There is almost no chemical affinity between titanium diboride and aluminum alloy, and the adhesion between it and the processed material is small, which can avoid the occurrence of built-up edge and cold welding, ensuring the reliability and production efficiency of fine processing. Moreover, the friction coefficient of titanium diboride coating on titanium alloy TC4 at 400°C is less than 0.5, and the oxidation product B produced is 2 O 3 It has good self-lubricating effect, which can alleviate the problems of bonding wear and diffusion wear between titanium alloy material and cutting tool, thereby extending the service life of the cutting tool.

[0003] The conventional preparation method of titanium diboride coating includes magnetron sputtering in argon atmosphere. + With TiB 2 There are mass differences between sputtered particles, B + The escape angle distribution is relatively + Narrow, B + The beam preferentially moves along the normal direction of the target surface, so that the deposited titanium diboride coating usually presents a columnar crystal structure and is overstoichiometric. Excessive B is easily segregated at the grain boundaries, resulting in defects such as large residual stress and poor toughness in the titanium diboride coating.

[0004] Therefore, how to reduce the residual stress of titanium diboride coating and improve its toughness and high-temperature oxidation resistance is a problem that needs to be solved urgently. Summary of the invention

[0005] The object of the present invention is to provide a reinforced and toughened TiB 2 -Me nano coating and its preparation method and application, the enhanced and toughened TiB 2 -Me nano-coating is formed by any two adjacent TiB 2 Introducing a metal layer between them produces interfacial atomic diffusion, mixing and bonding effects, which can improve the hardness, toughness and high-temperature oxidation resistance of the coating and can be widely used in metal surface treatment or metal processing.

[0006] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0007] In the first aspect, the present invention provides a reinforced and toughened TiB 2 -Me nano coating, the reinforced and toughened TiB 2 -Me nano-coating includes titanium diboride layers and metal layers alternately stacked;

[0008] The material of the titanium diboride layer is hexagonal titanium diboride;

[0009] The material of the metal layer is any one of Zr, Hf or Ti, or a combination of at least two of them.

[0010] The reinforced and toughened TiB 2 -Me nano-coating, the molecular formula of titanium diboride in the titanium diboride layer is TiB x , x>2; Me refers to the material of the metal layer.

[0011] When the chemical formula of the titanium diboride layer is TiB x , and when x>2, there is a problem of insufficient toughness of the titanium diboride layer. The enhanced and toughened TiB 2 -Me nano coatings are formed by alternating titanium diboride layers and metal layers, and the metal layers are used to produce interfacial atomic diffusion, mixing and bonding effects, thereby improving the toughening of TiB 2 -Me nano coating has the advantages of hardness, toughness and high temperature oxidation resistance, which enables it to be used in metal surface treatment and metal processing.

[0012] Preferably, the thickness of any of the metal layers is less than 5 nm.

[0013] Preferably, the reinforced and toughened TiB 2 The total thickness of the -Me nano coating is above 0.5 μm.

[0014] Preferably, the reinforced and toughened TiB 2 The hardness H of the -Me nano coating is 30.8 GPa to 34.6 GPa.

[0015] Preferably, the reinforced and toughened TiB 2 The elastic modulus E of the -Me nano coating is 395 GPa to 426 GPa.

[0016] In a second aspect, the present invention provides a reinforced and toughened TiB 2 -Me nano coating preparation method, the preparation method comprising the following steps:

[0017] In an inert atmosphere, titanium diboride target and metal target are alternately magnetron sputtered to deposit the enhanced and toughened TiB as described in the first aspect on the surface of the substrate. 2 -Me nano coating.

[0018] Preferably, the gas used for the inert atmosphere includes any one of helium, neon, argon or krypton, or a combination of at least two of them.

[0019] Preferably, during the magnetron sputtering, the substrate revolves at a speed of 0.5 rpm to 3 rpm.

[0020] Preferably, during the magnetron sputtering, the bias voltage of the substrate is -50V to -500V.

[0021] Preferably, the deposition temperature during magnetron sputtering is 100°C to 500°C.

[0022] Preferably, the absolute pressure during magnetron sputtering is 0.2Pa to 0.8Pa.

[0023] Preferably, the magnetron sputtering method includes DC magnetron sputtering or high-power pulsed magnetron sputtering.

[0024] Preferably, the magnetron sputtering power of the titanium diboride target is 5 W / cm 2 Up to 20W / cm 2 .

[0025] Preferably, the magnetron sputtering method of the titanium diboride target is high-power pulsed magnetron sputtering, with a peak current density of 0.1 A / cm 2 Up to 1A / cm 2 .

[0026] Preferably, the magnetron sputtering power of the metal target is 5 W / cm 2 Up to 50W / cm 2 .

[0027] Preferably, the magnetron sputtering method of the titanium diboride target is high-power pulsed magnetron sputtering, with a peak current density of 0.1 A / cm 2 Up to 2A / cm 2 .

[0028] In a third aspect, the present invention provides a reinforced and toughened TiB 2 -Me nano coating, the reinforced and toughened TiB 2 -Me nano coating is used for metal surface treatment or metal processing.

[0029] The reinforced and toughened TiB 2 -Me nano coating is the reinforced and toughened TiB 2 -Me nano coating.

[0030] Compared with the prior art, the present invention has the following beneficial effects:

[0031] The reinforced and toughened TiB provided by the present invention 2-Me nano coatings alternately set titanium diboride layers and metal layers, use the metal layer to produce interface atomic diffusion, mixing and bonding effects, use the B component at the boundary between the metal layer and the titanium diboride layer to bond, locally reduce the stoichiometric ratio of the titanium diboride layer, and optimize the B segregation state at the grain boundary, thereby improving the strengthening and toughening of TiB 2 The hardness, toughness and high-temperature oxidation resistance of the -Me nano coating make its hardness H between 30.8GPa and 34.6GPa, and its elastic modulus E between 395GPa and 426GPa, making it applicable to metal surface treatment and metal processing. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 The reinforced and toughened TiB provided by the present invention 2 -Schematic diagram of the preparation principle of Me nanocoating.

[0033] Figure 2 XRD diagrams of the coatings are provided for Comparative Example 1 and Example 1, Example 4, and Example 8 of the present invention.

[0034] Figure 3 SEM images of the coatings are provided for Comparative Example 1 and Examples 1, 4 and 8 of the present invention.

[0035] Figure 4 A cross-sectional TEM image of the coating is provided for Example 1.

[0036] Figure 5 A cross-sectional TEM morphology image of the coating is provided for Comparative Example 1.

[0037] Figure 6 A cross-sectional SEM image of the coating after the antioxidant capacity test is provided for Example 1.

[0038] Figure 7 A cross-sectional SEM image of the coating after the antioxidant capacity test is provided for Comparative Example 1.

[0039] Figure 8 A cross-sectional SEM image of the coating after the antioxidant capacity test is provided for Comparative Example 2. DETAILED DESCRIPTION

[0040] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0041] A certain embodiment of the present invention provides a reinforced and toughened TiB 2 -Me nano coating, the reinforced and toughened TiB 2 -Me nano-coating includes titanium diboride layers and metal layers alternately stacked;

[0042] The material of the titanium diboride layer is hexagonal titanium diboride;

[0043] The material of the metal layer is any one of Zr, Hf or Ti or a combination of at least two of them. Typical but non-limiting combinations include a combination of Zr and Hf, a combination of Zr and Ti, a combination of Hf and Ti, or a combination of Zr, Hf and Ti.

[0044] The reinforced and toughened TiB 2 -Me nano-coating, the molecular formula of titanium diboride in the titanium diboride layer is TiB x , x>2.

[0045] When the chemical formula of the titanium diboride layer is TiB x , and when x>2, there is a problem of insufficient toughness of the titanium diboride layer. The enhanced and toughened TiB 2 -Me nano coatings are formed by alternating titanium diboride layers and metal layers, and the metal layers are used to produce interfacial atomic diffusion, mixing and bonding effects, thereby improving the toughening of TiB 2 -Me nano coating has the advantages of hardness, toughness and high temperature oxidation resistance, which enables it to be used in metal surface treatment and metal processing.

[0046] In some embodiments, the thickness of any of the metal layers is less than 5 nm.

[0047] In certain embodiments, the reinforced and toughened TiB 2 The total thickness of the -Me nano coating is above 0.5 μm.

[0048] In the present invention, the strengthening and toughening of TiB 2 -The total thickness of the nano-coating has little effect on the performance. In the art, the thickness of the nano-coating is generally controlled to be above 0.5 μm, for example, it can be 0.5 μm, 1 μm, 2 μm, 3 μm, 4 μm, 5 μm or 6 μm, but it is not limited to the listed values, and other values ​​not listed in the numerical range are also applicable.

[0049] In certain embodiments, the reinforced and toughened TiB 2 The hardness H of the -Me nano coating is 30.8 GPa to 34.6 GPa, for example, it can be 30.8 GPa, 31 GPa, 32 GPa, 33 GPa, 34 GPa or 34.6 GPa, but is not limited to the listed values, and other values ​​not listed in the numerical range are also applicable.

[0050] In certain embodiments, the reinforced and toughened TiB 2The elastic modulus E of the -Me nano coating is 395 GPa to 426 GPa, for example, 395 GPa, 400 GPa, 405 GPa, 410 GPa, 420 GPa or 426 GPa, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0051] A certain embodiment of the present invention provides a reinforced and toughened TiB 2 -Me nano coating preparation method, the preparation principle diagram is as follows Figure 1 As shown, the preparation method comprises the following steps:

[0052] In an inert atmosphere, titanium diboride target and metal target are alternately magnetron sputtered to deposit the enhanced and toughened TiB2 as described in any embodiment on the substrate surface. 2 -Me nano coating.

[0053] The preparation method provided by the present invention is used in the preparation of reinforced and toughened TiB 2 -Me nano-coating, through the use of metal targets, highly ionized, high-energy Me metal ions are introduced to form an insertion layer with nanometer thickness, which produces interface atomic diffusion, mixing and bonding effects, thereby improving the strengthening and toughening of TiB 2 The hardness, toughness and high-temperature oxidation resistance of the -Me nano coating make its hardness H range from 30.8GPa to 34.6GPa and its elastic modulus E range from 395GPa to 426GPa.

[0054] In some embodiments, the gas used for the inert atmosphere includes any one of helium, neon, argon or krypton, or a combination of at least two of them. Typical but non-limiting combinations include a combination of helium and neon, a combination of neon and argon, a combination of argon and krypton, a combination of helium, neon and argon, a combination of neon, argon and krypton, or a combination of helium, neon, argon and krypton.

[0055] In some embodiments, in order to alternately stack titanium diboride layers and metal layers on the surface of the substrate, it is necessary to alternately magnetron sputter titanium diboride targets and metal targets. The specific alternating magnetron sputtering method includes fixing the titanium diboride target and the metal target, and then causing the substrate to revolve. When the substrate revolves to the position of the corresponding target, magnetron sputtering deposition of the corresponding target is achieved.

[0056] The revolution speed affects the residence time of the substrate at the corresponding target position. The faster the revolution speed, the smaller the thickness of the single titanium diboride layer or metal layer; the slower the revolution speed, the thicker the single titanium diboride layer or metal layer.

[0057] In some embodiments, during the magnetron sputtering, the substrate revolves at a speed of 0.5 rpm to 3 rpm, for example, 0.5 rpm, 1 rpm, 1.5 rpm, 2 rpm, 2.5 rpm or 3 rpm, but is not limited to the listed values, and other values ​​not listed in the numerical range are also applicable. Within the numerical range of the revolution speed, the thickness of any metal layer obtained can be less than 5 nm.

[0058] Strengthened and toughened TiB obtained by magnetron sputtering 2 The thickness of the -Me nano-coating is related to the time of magnetron sputtering. The longer the time is, the more revolutions the substrate makes, and the more layers of titanium diboride and metal layers are obtained by magnetron sputtering.

[0059] During the magnetron sputtering process, a bias voltage is applied to the substrate, and under the action of the negative bias voltage, positive ions in the plasma are attracted to bombard the substrate, thereby improving the quality of deposition, the deposition rate and the uniformity of deposition.

[0060] In some embodiments, during the magnetron sputtering, the bias voltage of the substrate is -50V to -500V, for example, -50V, -100V, -200V, -300V, -400V or -500V, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0061] In some embodiments, the deposition temperature during magnetron sputtering is 100°C to 500°C, for example, it can be 100°C, 150°C, 200°C, 250°C, 300°C, 350°C, 400°C, 450°C or 500°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0062] In some embodiments, the absolute pressure during magnetron sputtering is 0.2Pa to 0.8Pa, for example, 0.2Pa, 0.3Pa, 0.4Pa, 0.5Pa, 0.6Pa or 0.8Pa, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0063] In certain embodiments, the magnetron sputtering method includes direct current magnetron sputtering (DCMS) or high power impulse magnetron sputtering (HiPIMS).

[0064] In some embodiments, the magnetron sputtering power of the titanium diboride target is 5 W / cm 2 Up to 20W / cm 2 , for example, it can be 5W / cm 2 , 8W / cm 2 , 10W / cm 2 、12W / cm 2 , 15W / cm 2、18W / cm 2 or 20W / cm 2 , but not limited to the listed values, the remaining values ​​not listed in the numerical range are also applicable.

[0065] In some embodiments, the magnetron sputtering method of the titanium diboride target is high-power pulsed magnetron sputtering with a peak current density of 0.1 A / cm 2 Up to 1A / cm 2 , for example, it can be 0.1A / cm 2 , 0.3A / cm 2 , 0.5A / cm 2 , 0.6A / cm 2 , 0.8A / cm 2 or 1A / cm 2 , but not limited to the listed values, the remaining values ​​not listed in the numerical range are also applicable.

[0066] In some embodiments, the magnetron sputtering power of the metal target is 5 W / cm 2 Up to 50W / cm 2 , for example, it can be 5W / cm 2 , 10W / cm 2 , 20W / cm 2 、30W / cm 2 、40W / cm 2 or 50W / cm 2 , but not limited to the listed values, other values ​​not listed in the numerical range are also applicable, preferably 5W / cm 2 Up to 10W / cm 2 .

[0067] The magnetron sputtering power in the present invention refers to the average magnetron sputtering power.

[0068] In some embodiments, the magnetron sputtering method of the titanium diboride target is high-power pulsed magnetron sputtering with a peak current density of 0.1 A / cm 2 Up to 2A / cm 2 , for example, it can be 0.1A / cm 2 , 0.5A / cm 2 , 0.8A / cm 2 , 1A / cm 2 , 1.2A / cm 2 , 1.5A / cm 2 , 1.8A / cm 2 or 2A / cm 2 , but not limited to the listed values, the remaining values ​​not listed in the numerical range are also applicable.

[0069] In certain embodiments, the substrate is pre-treated before magnetron sputtering.

[0070] The pretreatment includes mechanical grinding, polishing and cleaning performed in sequence.

[0071] In some embodiments, the cleaning includes solvent cleaning, glow cleaning, and ion etching cleaning performed sequentially.

[0072] A certain embodiment of the present invention provides a reinforced and toughened TiB 2 -Me nano coating, the reinforced and toughened TiB 2 -Me nano coating is used for metal surface treatment or metal processing.

[0073] The reinforced and toughened TiB 2 -Me nano coating is the enhanced and toughened TiB 2 -Me nano coating.

[0074] In order to clearly illustrate the technical solution of the present invention, the substrate used in the following embodiments and comparative examples is a pretreated cemented carbide substrate, wherein the pretreatment includes: firstly mechanically grinding the substrate with sandpaper, then polishing the surface of the substrate with polishing liquid (Dongguan Yingxin Semiconductor Materials Co., Ltd., average diamond particle size 2 μm), and then cleaning.

[0075] The cleaning includes solvent cleaning, glow cleaning and ion etching cleaning in sequence; the solvent cleaning includes: using deionized water for ultrasonic cleaning for 20 minutes, and then using anhydrous ethanol for ultrasonic cleaning for 20 minutes; the glow cleaning includes: in an argon atmosphere, using glow discharge cleaning for 30 minutes, the working absolute pressure is 0.3Pa, the substrate bias is -600V, and the frequency is 30kHz; the ion etching cleaning includes: using Ar + The ion source cleans the substrate for 30 min, the absolute pressure is 0.3 Pa, and the substrate bias is -200V.

[0076] The above description of the substrate is not to be regarded as a further limitation of the technical solution of the present invention.

[0077] Example 1

[0078] This embodiment provides a reinforced and toughened TiB 2 -Me nano coating, the reinforced and toughened TiB 2 -Me nano coating includes titanium diboride layers and metal layers which are alternately stacked; wherein the material of the titanium diboride layer is hexagonal titanium diboride, and the material of the metal layer is Zr.

[0079] In this embodiment, the reinforced and toughened TiB 2 The preparation method of the -Me nano coating comprises the following steps:

[0080] In an argon atmosphere, high-power pulsed magnetron sputtering is used to alternately magnetron sputter a titanium diboride target and a metal Zr target, and titanium diboride layers and metal layers alternately stacked are deposited on the surface of a substrate.

[0081] The deposition temperature during high-power pulsed magnetron sputtering was 350°C, the substrate bias voltage was -100V, the absolute pressure was 0.6Pa, the substrate revolution speed was 1rpm, and the time was 3h.

[0082] When high-power pulsed magnetron sputtering titanium diboride targets, the average magnetron sputtering power of titanium diboride targets is 10W / cm 2 , peak current density is 0.5A / cm 2 .

[0083] When high-power pulsed magnetron sputtering metal Zr target, the average magnetron sputtering power of metal Zr target is 5W / cm 2 , peak current density is 0.4A / cm 2 .

[0084] The total power of high power pulsed magnetron sputtering was 4.5 kW, the frequency was 600 Hz and the pulse width was 70 μs.

[0085] The reinforced and toughened TiB obtained in Example 1 2 -XRD pattern of Me nano coating Figure 2 As shown in the SEM images Figure 3 As shown, the cross-sectional TEM morphology is shown Figure 4 As shown, the cross-sectional SEM image after the antioxidant capacity test is as follows Figure 6 shown.

[0086] Example 2

[0087] This embodiment provides a reinforced and toughened TiB 2 -Me nano coating, the reinforced and toughened TiB 2 -Me nano coating includes titanium diboride layers and metal layers which are alternately stacked; wherein the material of the titanium diboride layer is hexagonal titanium diboride, and the material of the metal layer is Zr.

[0088] In this embodiment, the reinforced and toughened TiB 2 The preparation method of the -Me nano coating comprises the following steps:

[0089] In an argon atmosphere, high-power pulsed magnetron sputtering is used to alternately magnetron sputter a titanium diboride target and a metal Zr target, and titanium diboride layers and metal layers alternately stacked are deposited on the surface of a substrate.

[0090] The deposition temperature during high-power pulsed magnetron sputtering was 100°C, the substrate bias voltage was -500V, the absolute pressure was 0.2Pa, the substrate revolution speed was 0.5rpm, and the time was 3h.

[0091] When high-power pulsed magnetron sputtering titanium diboride targets, the average magnetron sputtering power of titanium diboride targets is 5W / cm 2 , peak current density is 0.3A / cm 2 .

[0092] When high-power pulsed magnetron sputtering metal Zr target, the average magnetron sputtering power of metal Zr target is 5W / cm 2 , peak current density is 0.4A / cm 2 .

[0093] The total power of high power pulsed magnetron sputtering was 4.5 kW, the frequency was 600 Hz and the pulse width was 70 μs.

[0094] Example 3

[0095] This embodiment provides a reinforced and toughened TiB 2 -Me nano coating, the reinforced and toughened TiB 2 -Me nano coating includes titanium diboride layers and metal layers which are alternately stacked; wherein the material of the titanium diboride layer is hexagonal titanium diboride, and the material of the metal layer is Zr.

[0096] In this embodiment, the reinforced and toughened TiB 2 The preparation method of the -Me nano coating comprises the following steps:

[0097] In an argon atmosphere, high-power pulsed magnetron sputtering is used to alternately magnetron sputter a titanium diboride target and a metal Zr target, and titanium diboride layers and metal layers alternately stacked are deposited on the surface of a substrate.

[0098] The deposition temperature during high-power pulsed magnetron sputtering was 500°C, the substrate bias voltage was -50V, the absolute pressure was 0.8Pa, the substrate revolution speed was 3rpm, and the time was 3h.

[0099] When high-power pulsed magnetron sputtering titanium diboride targets, the average magnetron sputtering power of titanium diboride targets is 20W / cm 2 , peak current density is 0.8A / cm 2 .

[0100] When high-power pulsed magnetron sputtering metal Zr target, the average magnetron sputtering power of metal Zr target is 5W / cm 2 , peak current density is 0.4A / cm 2 .

[0101] The total power of high power pulsed magnetron sputtering was 4.5 kW, the frequency was 600 Hz and the pulse width was 70 μs.

[0102] Example 4

[0103] This embodiment provides a reinforced and toughened TiB 2 -Me nano coating, except for high power pulsed magnetron sputtering of metal Zr target, the average magnetron sputtering power of metal Zr target is 10W / cm 2 Except for this, the rest are the same as in Example 1.

[0104] The reinforced and toughened TiB obtained in Example 1 2 -XRD pattern of Me nano coating Figure 2 As shown in the SEM images Figure 3 shown.

[0105] Example 5

[0106] This embodiment provides a reinforced and toughened TiB 2 -Me nano coating, except for high power pulsed magnetron sputtering of metal Zr target, the average magnetron sputtering power of metal Zr target is 30W / cm 2 Except for this, the rest are the same as in Example 1.

[0107] Example 6

[0108] This embodiment provides a reinforced and toughened TiB 2 -Me nano coating, except for high power pulsed magnetron sputtering of metal Zr target, the average magnetron sputtering power of metal Zr target is 50W / cm 2 Except for this, the rest are the same as in Example 1.

[0109] Example 7

[0110] This embodiment provides a reinforced and toughened TiB 2 -Me nano coating, in addition to preparing enhanced and toughened TiB 2 -Me nano coating, except that the metal Zr target is replaced by the metal Hf target, the rest is the same as in Example 1.

[0111] The reinforced and toughened TiB obtained in this embodiment 2 -Me nano coating includes titanium diboride layers and metal layers which are alternately stacked; wherein the material of the titanium diboride layer is hexagonal titanium diboride, and the material of the metal layer is Hf.

[0112] Example 8

[0113] This embodiment provides a reinforced and toughened TiB 2 -Me nano coating, in addition to preparing enhanced and toughened TiB 2-Me nano coating, except that the metal Zr target is replaced by the metal Ti target, the rest is the same as in Example 1.

[0114] The reinforced and toughened TiB obtained in this embodiment 2 -Me nano coating includes titanium diboride layers and metal layers which are alternately stacked; wherein the material of the titanium diboride layer is hexagonal titanium diboride, and the material of the metal layer is Ti.

[0115] The reinforced and toughened TiB obtained in Example 1 2 -XRD pattern of Me nano coating Figure 2 As shown in the SEM images Figure 3 shown.

[0116] Example 9

[0117] This embodiment provides a reinforced and toughened TiB 2 -Me nano coating, in addition to preparing enhanced and toughened TiB 2 -Me nano-coating, the revolution speed of the substrate is 0.3 rpm, and the rest is the same as in Example 1.

[0118] Example 10

[0119] This embodiment provides a reinforced and toughened TiB 2 -Me nano coating, in addition to preparing enhanced and toughened TiB 2 -Me nano-coating, the revolution speed of the substrate is 3.5 rpm, and the rest is the same as in Example 1.

[0120] Comparative Example 1

[0121] This comparative example provides a TiB 2 coating, the TiB 2 The method for preparing the coating comprises the following steps:

[0122] In an argon atmosphere, high-power pulsed magnetron sputtering of titanium diboride targets was used to deposit TiB on the surface of the substrate. 2 ; The temperature during high-power pulse magnetron sputtering was 350°C, the substrate bias was -100V, the absolute pressure was 0.6Pa, the substrate revolution speed was 1rpm, and the time was 3h.

[0123] During high power pulsed magnetron sputtering, the average magnetron sputtering power of the titanium diboride target is 10W / cm 2 , peak current density is 0.5A / cm 2 .

[0124] The total power of high power pulsed magnetron sputtering was 4.5 kW, the frequency was 600 Hz and the pulse width was 70 μs.

[0125] The TiB obtained in this comparative example 2 The XRD pattern of the coating is shown in Figure 2 As shown in the SEM images Figure 3 As shown, the cross-sectional TEM morphology is shown Figure 5 As shown, the cross-sectional SEM image after the antioxidant capacity test is as follows Figure 7 shown.

[0126] Comparative Example 2

[0127] This comparative example provides a TiB 2 -Me coating, in addition to preparing TiB 2 -Me coating, except that the metal Zr target is replaced by the metal Cr target, the rest is the same as Example 1.

[0128] The TiB obtained in this comparative example 2 The -Me coating includes titanium diboride layers and metal layers which are alternately stacked; wherein the material of the titanium diboride layer is hexagonal titanium diboride, and the material of the metal layer is Cr.

[0129] The TiB obtained in this comparative example 2 The cross-sectional SEM image of the -Me coating after the oxidation resistance test is shown in Figure 2. Figure 8 shown.

[0130] Performance Characterization

[0131] The hardness H, elastic modulus E and antioxidant capacity of the coatings obtained in the above examples and comparative examples were measured, and the results are shown in Table 1. The hardness H was measured by a nanoindentation test method, and the implementation standard was ISO14577-4-2017; the elastic modulus E was measured by a nanoindentation test method, and the implementation standard was ISO14577-4-2017; the antioxidant capacity was measured by oxidation in air at a temperature of 500°C for 2 hours, and the average oxide layer thickness was measured by a cross-sectional SEM image. The thickness of a single metal layer refers to the average thickness of the metal layer.

[0132] Table 1

[0133]

[0134]

[0135] In summary, the reinforced and toughened TiB 2 -Me nano coatings alternately set titanium diboride layers and metal layers, use the metal layer to produce interface atomic diffusion, mixing and bonding effects, use the B component at the boundary between the metal layer and the titanium diboride layer to bond, locally reduce the stoichiometric ratio of the titanium diboride layer, and optimize the B segregation state at the grain boundary, thereby improving the strengthening and toughening of TiB 2The hardness, toughness and high-temperature oxidation resistance of the -Me nano coating make its hardness H between 30.8GPa and 34.6GPa, and its elastic modulus E between 395GPa and 426GPa, making it applicable to metal surface treatment and metal processing.

[0136] The above description is only a specific implementation mode 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 thought of by those skilled in the art within the technical scope disclosed by the present invention are within the protection scope and disclosure scope of the present invention.

Claims

1. A reinforced and toughened TiB2-Me nano coating, characterized in that: The reinforced and toughened TiB2-Me nano coating comprises titanium diboride layers and metal layers which are alternately stacked; The material of the titanium diboride layer is hexagonal titanium diboride; The material of the metal layer is any one of Zr, Hf or Ti, or a combination of at least two of them.

2. The reinforced and toughened TiB2-Me nano coating according to claim 1, characterized in that: The thickness of any of the metal layers is less than 5 nm; And / or, the total thickness of the reinforced and toughened TiB2-Me nano-coating is greater than 0.5 μm.

3. The reinforced and toughened TiB2-Me nano coating according to claim 1 or 2, characterized in that: The hardness H of the reinforced and toughened TiB2-Me nano coating is 30.8 GPa to 34.6 GPa; And / or, the elastic modulus E of the reinforced and toughened TiB2-Me nano-coating is 395 GPa to 426 GPa.

4. A method for preparing a reinforced and toughened TiB2-Me nano-coating, characterized in that: The preparation method comprises the following steps: In an inert atmosphere, titanium diboride target and metal target are alternately magnetron sputtered to deposit on the surface of a substrate to obtain the reinforced and toughened TiB2-Me nano coating as claimed in any one of claims 1 to 3.

5. The preparation method according to claim 4, characterized in that: The gas used for the inert atmosphere includes any one of helium, neon, argon or krypton, or a combination of at least two of them.

6. The preparation method according to claim 4, characterized in that: During the magnetron sputtering, the substrate revolves at a speed of 0.5 rpm to 3 rpm; And / or, during the magnetron sputtering, the bias voltage of the substrate is -50V to -500V; And / or, the deposition temperature during magnetron sputtering is 100° C. to 500° C.; And / or, the absolute pressure during magnetron sputtering is 0.2Pa to 0.8Pa And / or, the magnetron sputtering time is 2.5 hours to 3.5 hours.

7. The preparation method according to any one of claims 4 to 6, characterized in that: The magnetron sputtering method includes direct current magnetron sputtering or high power pulse magnetron sputtering.

8. The preparation method according to claim 7, characterized in that: The magnetron sputtering power of the titanium diboride target is 5W / cm 2 Up to 20W / cm 2 ; And / or, the magnetron sputtering method of the titanium diboride target is high-power pulsed magnetron sputtering, and the peak current density is 0.1A / cm 2 Up to 1A / cm 2 .

9. The preparation method according to claim 7, characterized in that: The magnetron sputtering power of the metal target is 5W / cm 2 Up to 50W / cm 2 ; And / or, the magnetron sputtering method of the titanium diboride target is high-power pulsed magnetron sputtering, and the peak current density is 0.1A / cm 2 Up to 2A / cm 2 .

10. A use of a reinforced and toughened TiB2-Me nano coating, characterized in that: The reinforced and toughened TiB2-Me nano coating is used for metal surface treatment or metal processing; The reinforced and toughened TiB2-Me nano coating is the reinforced and toughened TiB2-Me nano coating according to any one of claims 1 to 3.

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