Coating material comprising a ternary phase of Hf—B—C

Abstract

The present disclosure relates to a coated substrate with a coating deposited on at least a part of the substrate surface, said coating comprising at least one metal boron carbide layer, characterized in that the metal boron carbide layer is a ternary compound exhibiting a polycrystalline structure formed of a single phase of hafnium, boron and carbon. Further a method for deposition of such a coating is provided.

Claims

1. Coated substrate with a coating deposited on a surface of the substrate, said coating comprising at least one metal boron carbide layer, wherein the metal boron carbide layer is a ternary compound exhibiting a polycrystalline structure formed of a single phase of hafnium, boron and carbon.

2. Coated substrate of claim 1, wherein the ternary compound has a chemical composition in atomic percentage that can be expressed by the formula Hf.sub.uB.sub.vC.sub.w, wherein u+v+w=100, 0<v<35 at.-%, 0<w<35 at.-% and u<60 at.-%.

3. Coated substrate of claim 1, wherein the single phase exhibits a cubic solid solution structure or an orthorhombic structure.

4. Coated substrate of claim 2, wherein the single phase exhibits a cubic solid solution structure or an orthorhombic structure.

5. Method for producing a coated substrate of claim 1, wherein the method comprises following steps: providing at least one substrate to be coated in a coating chamber, depositing a layer of a ternary compound on at least a portion of the surface of the substrate, wherein said ternary compound layer is produced by using PVD techniques, wherein at least one target comprising a combination of the binary phases HfB.sub.2 and HfC is used as material source for the layer deposition.

6. Method for producing a coated substrate of claim 2, wherein the method comprises following steps: providing at least one substrate to be coated in a coating chamber, depositing a layer of a ternary compound on at least a portion of the surface of the substrate, wherein said ternary compound layer is produced by using PVD techniques, wherein at least one target comprising a combination of the binary phases HfB.sub.2 and HfC is used as material source for the layer deposition.

7. Method of claim 5, wherein the at least one target exhibits binary phase regions with particle sizes of less than 1.5 mm.

8. Method of claim 6, wherein the at least one target exhibits binary phase regions with particle sizes of less than 1.5 mm.

9. Method of claim 5, wherein the substrate temperature during deposition of the ternary compound layer is not higher than 500 C.

10. Method of claim 6, wherein the substrate temperature during deposition of the ternary compound layer is not higher than 500 C.

11. Method of claim 7, wherein a bias voltage is applied at the substrate during deposition of the ternary compound layer, wherein the bias voltage value is between 30 V and 100 V.

12. Method of claim 9, wherein a bias voltage is applied at the substrate during deposition of the ternary compound layer, wherein the bias voltage value is between 30 V and 100 V.

13. Method of claim 5, wherein the pressure in the coating chamber during deposition of the ternary compound layer is between 0.3 and 0.4 Pa.

14. Method of claim 7, wherein the pressure in the coating chamber during deposition of the ternary compound layer is between 0.3 and 0.4 Pa.

15. Method of claim 9, wherein the pressure in the coating chamber during deposition of the ternary compound layer is between 0.3 and 0.4 Pa.

16. Coated substrate of claim 1, wherein the substrate is a sliding component.

17. Coated substrate of claim 2, wherein the substrate is a sliding component.

18. Coated substrate of claim 1, wherein the substrate is a tool for machining operations or a tool for forming operations.

19. Coated substrate of claim 2, wherein the substrate is a tool for machining operations or a tool for forming operations.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows a quasiternary diagram;

(2) FIG. 2 shows an inset of TEM image and SAED analysis;

(3) FIG. 3 shows results for the distribution of chemical composition; and

(4) FIG. 4 shows a diffractogram of an as-deposited film.

DESCRIPTION

(5) Before further explaining the depicted embodiments, it is to be understood that the invention is not limited in its application to the details of the particular arrangements shown, since the invention is capable of other embodiments. It is intended that the embodiments and figures disclosed herein are to be considered illustrative rather than limiting. Also, the terminology used herein is for the purposes of description and not limitation.

(6) Formation of the stoichiometric phase did not appear to be feasible based on the available phase diagram data, which exhibited a decomposition of liquid HfBC phase to thermodynamically stable solid HfB.sub.2 and HfC binary phases, portrayed in the quasiternary diagram shown in FIG. 1 (taken from: Peter Rogl, Refractory Metal Systems: Phase Diagrams, Crystallographic and Thermodynamic Data, Landolt-Bornstein New Series IV/11E1, Springer 2009). Also, the formation of microcrystalline Hf.sub.2BC was not expected from a magnetron sputtering technique below 600 C., as described in WO2014053209A1 above.

(7) Therefore, it was especially unexpected to form any HfBC ternary compounds capable of being stabilized in a single polycrystalline phase at room temperature. However, a single phase of HfBC was surprisingly synthesized by using the coating parameters and conditions described below.

(8) Unexpectedly, it was possible to synthetize a ternary compound of hafnium, boron and carbon exhibiting a single phase for the first time by using as material source a target comprising a combination of the binary phases HfB.sub.2 and HfC. The target was prepared by using powder metallurgical techniques to obtain a homogeneous source material exhibiting a refined particle size, specifically displaying binary regions having particle sizes less than 1.5 mm each. Accordingly, these targets are shown to be particularly suitable for promoting the single phase formation. The substrate temperature also plays a major role in the formation of the single phase. Experimentation revealed that the use of high substrate temperatures leads to the formation of a coating material comprising the binary phases HfB.sub.2 and HfC instead of the stoichiometric phase Hf.sub.2BC or any single polycrystalline phase formed of hafnium, boron and carbon. According to the present disclosure, substrate temperatures not higher than approximately 450 C. were found to be suitable for the formation of a ternary phase of HfBC. Substrate temperatures not higher than 600 C., preferably not higher than 500 C., was recommended in order to prevent decomposition of the above mentioned ternary phase of HfBC exhibiting a single polycrystalline phase into the binary HfB.sub.2 and HfC phases during deposition.

(9) The synthetized coatings showed a considerably high hardness of approximately 30 GPa which was measured with a depth-sensing nanoindenter equipped with a Berkovich tip.

(10) The coatings were deposited by means of magnetron sputtering of the already previously described targets consisting of a combination of the binary phases HfB.sub.2 and HfC. For the deposition of the HfBC films in one disclosure, at least one target was sputtered in a non-reactive atmosphere comprising argon as process gas. The required sputtering power was provided by using a DC power supply. A negative bias voltage was applied at the substrate to be coated. Different experiments showed that too high bias voltage values can lead to delamination of the coating caused by poor adhesion and even breakage. Particularly good results were obtained by using a bias voltage of 50 V. It is however important to mention that also bias voltage values of 30 V to 100 V could be used depending on the other process parameters. The Ar pressure during the process was kept constant at 0.35 Pa. The production of the coatings could be achieved by use of another inert gas instead of argon, or other inert gases, or a mixture with argon. Likewise, it is recommended to use inert gas pressures of 0.3 to 0.4 Pa during the process. Lower pressures may extinguish the plasma and higher pressures decrease the adatom energy and subsequent surface mobility of film forming species. This can affect the synthesis adversely.

(11) The films were subsequently examined by transmission electron microscopy (TEM) and selected area electron diffraction (SAED). No evidence for the formation of an amorphous phase can be seen from the TEM image and SAED analysis in the inset shown in FIG. 2. Rather, a high degree of crystallinity can be estimated from the relatively sharp diffraction spots. The ring shape of the diffraction spots is attributed to the polycrystalline nature of the investigated ternary phase of HfBC coating sample, which as previously mentioned corresponds to a singular polycrystalline phase formed of the ternary system hafnium, boron and carbon.

(12) The distribution of the chemical composition was measured precisely by Atom probe. The results are shown in the FIG. 3. From these results it is clear that the formation of the binary phases can be excluded. The uniform distribution of the chemical elements suggests that a ternary phase formed of hafnium boron and carbon, exhibiting a single phase of the present disclosure is formed. However, chemical composition does not give enough information to identify precisely which kind of crystallographic structure it is. It could be, for example, the orthorhombic structure of the stoichiometric Hf.sub.2BC phase or the cubic HfB.sub.xC.sub.1x phase.

(13) The chemical composition of the synthesized ternary phase comprising coatings of the present disclosure can be expressed by using the formula Hf.sub.100bcB.sub.bC.sub.c, with 100bc>>b and 100bc>>c, with the coefficients b and c in atomic percentage.

(14) According to a preferred embodiment of the present disclosure, b and c are not higher than 35 at.-% and preferably 100bc is not higher than 60 at.-%.

(15) According to a further preferred embodiment of the present disclosure, b and c fulfil the condition b<30 at.-%, c<30 at.-%. Good properties were observed by coatings in which c>b.

(16) The chemical composition of the synthesized ternary phase comprising coatings of the present disclosure can in equivalent manner be expressed by using the formula Hf.sub.uB.sub.vC.sub.w, with u+v+w=100 and u>>v>0 and u>>w>0. According to a preferred embodiment of the present disclosure, v and w are not higher than 35 at. % and preferably u is not higher than 60 at. %. A preferred embodiment of the present disclosure is produced when using this formula for expressing the chemical composition of the coatings, where then v and w fulfil the condition 0<v<35 at.-%, 0<w<35 at.-%.

(17) Unavoidable impurities of metallic or non-metallic residuals can be included up to maximum 2 at. % and should not be considered in the chemical composition of the single phase Hf.sub.uB.sub.vC.sub.w. Such impurities can arise from other metallic elements in the target, like Ti, Zr, V, Nb, Ta, Cr, Mo, W which stem from target production, or e.g. from contamination of the target-/substrate-/chamber-surface by oxygen or nitrogen, as well as unavoidable incorporation of the process gasses like e.g. Ar, He, Ne, Kr.

(18) In particular, very good coating properties were exhibited by coatings having chemical composition in atomic percentage corresponding to Hf.sub.50B.sub.21C.sub.29.

(19) All synthesized coatings showed a high crystallinity and they were investigated by XRD examinations in order to determine the crystal structure present in the polycrystalline coatings.

(20) FIG. 4 shows a diffractogram of an as-deposited film. The peak intensities corresponding to a theoretically predicted orthorhombic Hf.sub.2BC phase, whose 2theta and intensities were calculated by using quantum mechanics calculation methods, are indicated as squares. The peak positions of HfB.sub.2 (hexagonal), HfC (cubic) and HfB (cubic) phases are indicated as triangles, circles and stars, respectively, based on the powder diffraction files available from JCPDS database.

(21) By analysis of only the initial XRD examinations of the HfBC coatings having chemical composition given by the formula Hf.sub.100bcB.sub.bC.sub.c or Hf.sub.uB.sub.vC.sub.w as explained above, it was not possible to determine exactly which kind of single phase of hafnium formed; boron and carbon was also formed, but more exactly, it was not possible to determine if the deposited films exhibit a cubic polycrystalline structure or an orthorhombic polycrystalline structure. Therefore, a more detailed analysis of the XRD and TEM examinations would be necessary for determining the exact crystal structure present in the polycrystalline coatings exhibiting a ternary phase of HfBC of the present disclosure. In other words, until now it remained difficult to distinguish if the films consisting essentially of a ternary compound of Hf, B and C showing a single phase, exhibit a cubic HfB.sub.xC.sub.1x solid solution structure or an orthorhombic Hf.sub.2BC structure.

(22) Magnetron sputtering was found to be a suitable PVD method for producing the ternary phase films of HfBC, characterized by exhibiting a single phase formed of hafnium, boron and carbon of the present disclosure. However, the methods for depositing the films are not limited to conventional DC magnetron sputtering but can also include for example HiPIMS and are PVD or other PVD methods.

(23) It is however clearly visible from FIG. 4 that the deposited HfBC coating material is present in the form of a single phase solid solution with high crystallinity.

(24) The application of the HfBC coating material with a chemical composition specified by the formulas as previously depicted are primarily observed as protective coatings on tools or components like machining operations such as drilling or milling for example, but can also form operations of metals at moderate temperatures such as cold forming or extrusion of aluminium-, copper- or iron-alloys for example. Additional fields of application can be found as protective coating on dies or moulds in metal casting, or as low-friction coatings on components of sliding members in dry and lubricated conditions with a high load collective.

(25) The present disclosure depicts a coated substrate with a coating deposited on a surface of the substrate. Said coating is comprised of at least one metal boron carbide layer, wherein the metal boron carbide layer is a ternary compound exhibiting a polycrystalline structure formed of a single phase of hafnium, boron and carbon.

(26) The ternary compound preferably has a chemical composition in an atomic percentage that can be expressed by the formula Hf.sub.uB.sub.vC.sub.x, wherein u+v+w=100, 0<v<35 at.-%, 0<w<35 at.-% and u<60 at.-%.

(27) The single phase preferably exhibits a cubic solid solution structure or an orthorhombic structure.

(28) The present disclosure discloses also a method for producing the previously depicted coated substrate, wherein the method is comprised of at least the following steps: providing at least one substrate to be coated in a coating chamber, depositing a layer of a ternary compound on at least a portion of the surface of the substrate, wherein said ternary compound layer is produced by using PVD techniques, wherein at least one target comprising a combination of the binary phases HfB.sub.2 and HfC is used as material source for the layer deposition.

(29) Preferably, at least one target exhibits binary phase regions with particle sizes of less than 1.5 mm.

(30) Preferably, the substrate temperature during deposition of the ternary compound layer is not higher than 500 C.

(31) Preferably, a bias voltage is applied at the substrate during deposition of the ternary compound layer, wherein the bias voltage value is between 30 V and 100 V.

(32) Preferably, the pressure in the coating chamber during deposition of the ternary compound layer is between 0.3 and 0.4 Pa.

(33) In particular, a coated substrate according to the present disclosure is a sliding component coated with a coating of the previously depicted embodiments.

(34) In such a case the coated sliding component can be used under unlubricated or lubricated conditions. Moreover, the coating deposited on at least some parts of the sliding component can be designed to comprise of at least one layer of hafnium, boron and carbon, further consisting of a dense, single phase structure of Hf.sub.uB.sub.vC.sub.w with high crystallinity, wherein u+v+w=100 and 30>v>0 at. % and 30>w>0 and u<60 at. %.

(35) Also, a coated substrate of the present disclosure can be a tool for machining operations or a tool for forming operations coated with a coating of the previously depicted embodiments.

(36) The invention was described based on exemplary embodiments. A person skilled in the art will derive numerous embodiments for implementing the invention without departing from the scope of the present claims. While several aspects and embodiments have been discussed above, those of skill in the art will recognize certain modifications, permutations, additions and sub-combinations therefore. It is therefore intended that the following appended claims hereinafter introduced are interpreted to include all such modifications, permutations, additions and sub-combinations, which are within their true spirit and scope. Each embodiment described herein has numerous equivalents.

(37) The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, although the present disclosure has been specifically disclosed by preferred embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims. Whenever a range is given in the specification, all intermediate ranges and subranges, as well as all individual values included in the ranges given are intended to be included in the disclosure. When a Markush group or other grouping is used herein, all individual members of the group and all combinations and sub-combinations possible of the group are intended to be individually included in the disclosure.

(38) In general, the terms and phrases used herein have their art-recognized meaning, which can be found by reference to standard texts, journal references and contexts known to those skilled in the art. The above definitions are provided to clarify their specific use in the context of the invention.