阅读说明：本技术 定量织构化多晶涂层 (Quantitatively textured polycrystalline coatings ) 是由 刘振宇 于 2020-05-15 设计创作，主要内容包括：在一个方面,本文描述了制造经涂覆的制品的方法。在一些实施方案中,方法包括提供基体,和通过化学气相沉积(CVD)和/或物理气相沉积(PVD)在基体的表面上方沉积涂层,所述涂层包含至少一个多晶层,其中选择一个或多个CVD和/或PVD条件来诱导多晶层的一种或多种性质。通过二维(2D)X-射线衍射分析来量化多晶层中所述一种或多种性质的存在。(In one aspect, described herein is a method of making a coated article. In some embodiments, a method includes providing a substrate, and depositing a coating over a surface of the substrate by Chemical Vapor Deposition (CVD) and/or Physical Vapor Deposition (PVD), the coating comprising at least one polycrystalline layer, wherein one or more CVD and/or PVD conditions are selected to induce one or more properties of the polycrystalline layer. Quantifying the presence of the one or more properties in the polycrystalline layer by two-dimensional (2D) X-ray diffraction analysis.)

1. A method of making a coated article, the method comprising:

providing a substrate;

depositing a coating on a surface of the substrate by Chemical Vapor Deposition (CVD) or Physical Vapor Deposition (PVD), the coating comprising at least one polycrystalline layer, wherein one or more CVD or PVD conditions are selected to induce one or more properties of the polycrystalline layer; and

quantifying the presence of the one or more properties in the polycrystalline layer via two-dimensional (2D) X-ray diffraction analysis.

2. The method of claim 1, wherein the one or more properties comprise a grain orientation of the polycrystalline layer.

3. The method of claim 2, wherein the one or more deposition conditions are selected to control random grain orientation of the polycrystalline layer.

4. The method of claim 1, wherein less than 50 volume percent of the grains of the polycrystalline layer exhibit random orientation.

5. The method of claim 2, wherein the one or more deposition conditions are selected to control fiber grain orientation in the polycrystalline layer.

6. The method of claim 5, wherein greater than 30 volume percent of the grains of the polycrystalline layer exhibit a fiber orientation.

7. The method of claim 2, wherein the one or more properties comprise a preferred grain orientation.

8. The method of claim 7, wherein the one or more deposition conditions are selected to provide at least one preferred grain orientation of the polycrystalline layer.

9. The method of claim 8, wherein at least one preferred orientation is the (006) growth direction.

10. The method of claim 1, wherein the one or more properties comprise a residual stress of the polycrystalline layer.

11. The method according to claim 10, wherein the polycrystalline layer has a residual stress of 0.2GPa to-3 GPa.

12. The method of claim 1, further comprising adjusting one or more CVD or PVD conditions based on the quantification of the one or more properties by the 2D X-ray diffraction analysis.

13. The method of claim 12, wherein the deposition time is adjusted.

14. The method of claim 1, further comprising quantifying the presence of the one or more properties via Electron Back Scattering Diffraction (EBSD).

15. The method of claim 1, wherein the polycrystalline layer is formed from a refractory ceramic material selected from the group consisting of metal oxides, metal nitrides, metal carbides, metal carbonitrides, and metal oxycarbonitrides.

16. The method of claim 1, wherein the polycrystalline layer comprises one or more metallic elements selected from the group consisting of aluminum and metallic elements of groups IVB, VB, and VIB of the periodic Table and one or more non-metallic elements selected from non-metallic elements of groups IIIA, IVA, VA, and VIA of the periodic Table.

17. A coated article, the coated article comprising:

a substrate; and

a coating comprising an aluminum oxide layer adhered to the substrate, wherein less than 50% by volume of the grains in the aluminum oxide layer have random orientation.

18. The coated article of claim 17, wherein 30 to 90 volume percent of the grains have a fiber orientation.

19. The coated article of claim 17, wherein 10 to 95 volume percent of the grains exhibit a (006) orientation.

20. The coated article of claim 17 having a residual stress of 0.2GPa to-3 GPa.

Technical Field

The present invention relates to refractory coatings, and in particular, to quantitatively textured polycrystalline layers of refractory coatings.

Background

Cutting tools, including cemented carbide cutting tools, have been used to machine a variety of metals and alloys, both coated and uncoated. To improve the wear resistance, performance and life of cutting tools, one or more layers of refractory material have been applied to the cutting tool surface. For example, TiC, TiCN, TiN, and/or Al have been deposited by Chemical Vapor Deposition (CVD) and Physical Vapor Deposition (PVD)₂O₃Applied to a cemented carbide substrate. While effective in inhibiting wear and extending tool life in various applications, refractory coatings based on single or multi-layer constructions of the aforementioned refractory materials have been increasingly approaching their performance limits, and there is a need to develop new coating constructions for cutting tools, including coatings with various textures and grain orientations to enhance performance.

However, proper characterization of coating architecture and related properties presents significant problems. Current analytical methods are qualitative and subjective in nature, with coating characterization being largely dependent on the particular data set chosen by the laboratory. Texture coefficients of polycrystalline layers measured by Harris' formula are one of many examples in which coating properties can vary significantly based on user input. Harris formula is

Wherein I (hkl) is the measured intensity of the (hkl) reflection, I₀(hkl) is according to the International centre for diffraction data (I)CDD) and N is the number of reflections used in the calculation.

Based on this formula and the associated basic assumptions, the texture coefficient is the average intensity ratio difference of the experiment to the reference. It should be noted that the texture evaluation is arbitrary due to the subjective choice of reference and number of reflection peaks. Different references will result in different reflection peak intensities and thus in deviations of the final calculation of the texture coefficients. Another problem is that there are many peaks in polycrystalline layers such as alumina. Therefore, the operator needs to select the number of reflection peaks for texture analysis. Some operators choose 6 peaks, some 8 peaks, and some even more peaks for calculation. Due to the subjective selection of these numerous input parameters, the calculated texture coefficient values are only of relative significance and not completely quantitative. The texture coefficients of the polycrystalline layer can vary significantly based on the input data, especially when characterizing the "maximum" texture coefficient based on the number of reflections (N) used in the calculation. For example, according to Harris' formula, if the operator selects 5 reflections, the maximum texture coefficient will be 5; if the operator selects 8 reflections, the maximum texture factor will be 8, and so on. Therefore, texture coefficients based on Harris' formula can only lead to meaningful conclusions regarding the coating build and the related coating properties qualitatively, but not completely quantitatively. Such limitations also prevent an accurate description of the crystal evolution in polycrystalline coatings.

Disclosure of Invention

In view of the foregoing, there is a need for quantitative methods of polycrystalline coating development and characterization to understand coating architecture and coating performance characteristics. In one aspect, described herein is a method of making a coated article. In some embodiments, a method includes providing a substrate, and depositing a coating over a surface of the substrate by CVD and/or PVD, the coating comprising at least one polycrystalline layer, wherein one or more CVD and/or PVD conditions are selected to induce one or more properties of the polycrystalline layer. Quantifying the presence of the one or more properties in the polycrystalline layer by two-dimensional (2D) X-ray diffraction analysis. In some embodiments, the method further comprises quantifying the presence of the one or more properties of the polycrystalline layer by Electron Back Scattering Diffraction (EBSD). As further described herein, one or more of the CVD or PVD parameters or conditions may be adjusted based on the quantification of the one or more properties by 2D X-ray analysis. The properties of the polycrystalline layer induced by the deposition conditions and quantified by 2D X-ray analysis are not limited, but may be selected based on a variety of considerations, including the composition of the polycrystalline layer and the desired properties of the polycrystalline layer. In some embodiments, for example, the one or more properties include grain orientation in the polycrystalline layer and/or residual stress of the polycrystalline layer.

In another aspect, a coated article is provided. As further described herein, properties of the coated article can be induced by associated CVD or PVD parameters and quantified by 2D X-ray diffraction. For example, a coated article comprises a substrate and a coating comprising an aluminum oxide layer deposited by CVD over the substrate, wherein less than 50 volume percent of the grains of the aluminum oxide layer exhibit random orientation. In some embodiments, greater than 30 volume percent of the grains of the aluminum oxide layer exhibit fiber orientation. Additionally, the grains of the aluminum oxide layer may exhibit one or more preferred orientations, including the (006) growth (e.g., 0001 or basal) direction. In some embodiments, for example, 15-50% by volume of the grains in the aluminum oxide layer exhibit a (006) texture.

In addition to grain orientation properties, the aluminum oxide layer may exhibit various levels of residual stress, quantified by 2D X-ray diffraction, depending on the CVD parameters or conditions. In some embodiments, the aluminum oxide layer exhibits a residual stress of 0.2GPa to-3 GPa. As known to the skilled person, positive values of residual stress indicate tensile stress, while negative values indicate compressive stress.

These and other embodiments are further described in the detailed description that follows.

Drawings

Fig. 1 provides a cross-sectional Scanning Electron Micrograph (SEM) of the coated substrate and a schematic representation of each coated substrate detailed in the examples herein.

FIG. 2 illustrates Al according to some embodiments₂O₃Residual stress evolution in layer with layerThe change in thickness.

FIG. 3 illustrates Al according to some embodiments₂O₃The grain orientation/texture evolution in the layer varies with the layer thickness.

Detailed Description

The embodiments described herein can be understood more readily by reference to the following detailed description and examples and the preceding and following description thereof. However, the elements, devices, and methods described herein are not limited to the specific embodiments presented in the specific embodiments and examples. It should be recognized that these embodiments are merely illustrative of the principles of the present invention. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the spirit and scope of the invention.

In one aspect, described herein is a method of making a coated article. In some embodiments, a method includes providing a substrate, and depositing a coating over a surface of the substrate by CVD and/or PVD, the coating comprising at least one polycrystalline layer, wherein one or more CVD and/or PVD conditions are selected to induce one or more properties of the polycrystalline layer. Quantifying the presence of the one or more properties in the polycrystalline layer by 2D X-ray diffraction analysis. In some embodiments, the method further comprises quantifying the presence of the one or more properties of the polycrystalline layer by EBSD.

As further described herein, one or more of the CVD or PVD parameters or conditions may be adjusted based on the quantification of the one or more properties by 2D X-ray analysis. In some embodiments, the one or more properties of the polycrystalline layer are not detected or are not present at a desired level in the polycrystalline layer, for example, by 2D X-ray analysis. The CVD or PVD parameters may be adjusted until the one or more properties at a desired level are achieved in the polycrystalline layer. Adjusting CVD or PVD parameters to induce desired properties in polycrystals may require an iterative process in which samples of the polycrystallme layer are deposited and subsequently analyzed by 2D X-ray analysis. This iterative process may yield information about the evolution of properties in the polycrystalline layer relative to various deposition parameters. In this way, a library can be developed for deposition conditions that induce a desired coating configuration.

The properties of the polycrystalline layer induced by the deposition conditions and quantified by 2D X-ray analysis are not limited, but may be selected based on a variety of considerations, including the composition of the polycrystalline layer and the desired properties of the polycrystalline layer. In some embodiments, for example, the one or more properties include grain orientation in the polycrystalline layer and/or residual stress of the polycrystalline layer. Further, the one or more CVD parameters that may be changed or adjusted to induce or achieve a desired property in the polycrystalline layer may include reactant partial pressure, gas flow rate into and out of the CVD reactor, CVD reactor temperature, deposition/growth rate of the polycrystalline, and/or deposition time of the polycrystalline layer. The one or more PVD parameters that may be varied may include cathode composition, substrate bias voltage, cathode placement relative to the substrate, cathode and/or substrate rotation, substrate temperature, deposition/growth rate of the polycrystalline, and/or deposition time of the polycrystalline layer.

In some embodiments, for example, one or more deposition conditions are selected to control the random grain orientation of the polycrystalline layer. In some embodiments, less than 50 volume percent of the grains of the polycrystalline layer may exhibit random orientation. The deposition conditions may also control the fiber orientation of the grains in the polycrystalline layer. As used herein, fiber orientation refers to grains having a crystallographic axis parallel to the normal of the substrate. In some embodiments, greater than 30 volume percent of the grains, such as 30 to 90 volume percent, exhibit fiber orientation. In addition, the deposition conditions may also control one or more preferred grain orientations in the polycrystalline layer, including (006) orientation. In some embodiments, for example, 10-95 volume% or 15-50 volume% of the grains in the aluminum oxide layer exhibit a (006) texture.

In addition to controlling grain orientation as quantified by 2D X-ray analysis, the deposition parameters may also control the residual stress of the polycrystalline layer. In some embodiments, the polycrystalline layer has a residual stress in a range of 0.2GPa to-3 GPa.

The polycrystalline layers of the methods and compositions described herein may have any desired composition. In some embodiments, the polycrystalline layer is formed from a refractory ceramic material comprising a metal oxide, nitride, carbide, carbonitride or oxycarbonitride. The polycrystalline layer may comprise one or more metallic elements selected from the group consisting of aluminum and metallic elements of groups IVB, VB and VIB of the periodic table and one or more non-metallic elements selected from non-metallic elements of groups IIIA, IVA, VA and VIA of the periodic table. In some embodiments, for example, the polycrystalline layer comprises alumina, such as alpha alumina, kappa alumina, or mixtures thereof. In addition, the coatings described herein may comprise a single polycrystalline layer or multiple polycrystalline layers. The layer thickness of the individual polycrystalline layers can generally be in the range from 0.5 μm to 20 μm.

Coated articles according to the methods described herein may comprise any substrate not inconsistent with the objectives of the present invention. For example, the substrate may be a cutting tool or tooling used in wear applications. Cutting tools include, but are not limited to, indexable cutting inserts, end mills, or drills. The indexable cutting insert can have any desired ANSI standard geometry for milling or turning applications. The substrate of the coated articles described herein may be formed of cemented carbide, ceramic, cermet, steel, or other alloys. In some embodiments, the cemented carbide substrate comprises tungsten carbide (WC). WC may be present in the cutting tool matrix in an amount of at least about 80 wt% or in an amount of at least about 85 wt%. Additionally, the metallic binder of the cemented carbide may comprise cobalt or a cobalt alloy. For example, cobalt may be present in the cemented carbide matrix in an amount in the range of 1 to 15 wt%. In some embodiments, the cobalt is present in the cemented carbide matrix in an amount in the range of 5-12 wt% or 6-10 wt%. Additionally, the cemented carbide substrate may have a binder-rich zone beginning at and extending inwardly from the substrate surface.

The cemented carbide substrate may further comprise one or more additives, such as one or more of the following elements and/or compounds thereof: titanium, niobium, vanadium, tantalum, chromium, zirconium and/or hafnium. In some embodiments, titanium, niobium, vanadium, tantalum, chromium, zirconium, and/or hafnium form solid solution carbides with the WC of the substrate. In such embodiments, the matrix may comprise one or more solid solution carbides in an amount in the range of 0.1 to 5 weight percent. Additionally, the cemented carbide substrate may comprise nitrogen.

These and other embodiments are further illustrated in the following non-limiting examples.

Example 1-control of residual stress and grain orientation via 2D-XRD

Four identical grade cemented carbide substrates were coated to provide CVD coatings according to table I.

TABLE I coated cemented carbide substrate

As provided in Table I, only Al₂O₃The thickness of the layers varied and the remaining layers exhibited substantially similar thicknesses between samples under the same deposition conditions. FIG. 1 provides a cross-sectional scanning electron micrograph of the coated substrate and a schematic representation of each coated substrate according to Table I. Each coating was deposited according to the parameters of tables II and III, the main difference being that Al was brought to the thickness values listed in Table I₂O₃Layer deposition time. Al (Al)₂O₃The deposition time of the layer is in the range of 1.8 to 10 hours at a rate of 1-1.5 μm/hr. Bonding layer comprising HT-TiCN and TiOCN with Al for enhanced adhesion₂O₃The layers are adjacent.

TABLE II CVD deposition of coatings

TABLE III CVD deposition step

Al on Bruker D8 diffractometer₂O₃Layer residual stress and grain orientationData collection for/texture, the diffractometer with general area detector diffraction system HI-STAR GADDS and rotating anode, operating at 40kV and 20 mA. The core of the GADDS is a 2D area detector, which is a photon counter over a large area. The sample was mounted on a holder (eutentric cradle) in full alignment of chi and phi so that the film was perpendicular to the phi axis. The gantry rotates around a vertical axis, denoted by ω, which changes the orientation of the χ -axis in the horizontal plane. The basic advantages are speed and more diffraction information. Also, 2D may provide better accuracy due to less defocus in the collection process. Due to the low diffraction intensity and the expected sharp texture, pole figure measurements on materials such as polycrystalline thin films or multilayer materials may require long measurement times and high directional resolution in the pole figures. The most efficient diffractogram was determined using an area detector (XRD 2). An X-ray polar map was acquired using filtered copper optics. To characterize the crystallographic texture, three incomplete (0-90 °) pole patterns 001, 100, and 110 were measured. The macroscopic texture Orientation Distribution Function (ODF) was calculated and visualized using the combination software MulTEX.

The component description enables to efficiently concentrate the grain orientation/texture information. A solution for ODF is available that considers only the minimum number of necessary components. It may be appropriate to estimate if the quality or quantity of the measured data does not allow an accurate calculation. The method of determining the texture component requires that the number of available pole figures and the range of measurements be large enough so that any crystal orientation can be unambiguously determined. The amount of texture information most unnecessary in the experimental polar diagram depends only on the crystal symmetry and the type of miller index of the diffraction lattice plane.

The volume fraction of the corresponding grain orientation/texture component was calculated using a dispersion that was 15 ° different from its ideal orientation. The overall strength of the texture is characterized by a corresponding texture index T, which is calculated as follows: t phi [ f (g)]²dg, where/(g) is an orientation density function, g denotes the orientation defined by three euler angles, g ═ pl,<p, (P2). The spherical texture component (peak component) is the volume fraction that does not depend on the rotation of the axis of rotation during X-ray diffraction acquisition.

For residual stress analysis, peak evaluation in two-dimensional XRD was performed using Pearson VII mode, and stress tensor was derived based on the triaxial stress model. Diffraction rings (024), (116), (214), and (300) for residual stress calculation.

FIG. 2 schematically shows Al₂O₃The evolution of residual stress in the layer with increasing thickness of the layer. From this quantitative analysis by 2D XRD, Al can be controlled or set based on the control of layer thickness₂O₃Residual stress in the layer to a desired level. FIG. 3 illustrates Al on coated samples via 2D X-ray diffraction₂O₃Results of grain orientation/texture analysis performed on the layers. As shown in FIG. 3, Al₂O₃The random orientation of the grains decreases with increasing layer thickness. In addition, Al₂O₃The fiber orientation of the grains increases with increasing layer thickness. In view of these results, Al can be increased according to the deposition parameters in tables II and III above₂O₃Controlling Al by layer thickness₂O₃Grain orientation/texture.

Al of the present example₂O₃Quantification of the residual stress and grain orientation/texture of the layer via 2D X-ray diffraction creates the ability to control the coating configuration via selection of appropriate coating deposition parameters. In particular, the quantitative nature of the 2D X-ray diffraction analysis enables reproducibility of the coating structure and eliminates the subjectivity of current qualitative characterization methods such as the Harris equation. Using the methods and compositions described herein, polycrystalline layer properties and associated performance can be elucidated and tailored for a variety of coating applications, including high performance process equipment applications involving cutting inserts and various rotary cutting tools.

Various embodiments of the present invention have been described in the achievement of various objects of the present invention. It should be recognized that these embodiments are merely illustrative of the principles of the present invention. Many modifications and variations thereof will be apparent to those skilled in the art without departing from the spirit and scope of the invention.