# US 10,246,335 B2 · Methods of modifying surfaces of diamond particles, and related diamond particles and earth-boring tools

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- Number: US 10,246,335 B2
- Document ID: US10246335B2
- Status: Granted
- Kind: B2
- Application number: 15/167,781
- Filed: 2016-05-27
- Published: 2017-11-30
- Granted: 2019-04-02
- Earliest claimed: 2016-05-27
- Assignees: Baker Hughes, A Ge Company, LLC
- Applicants: Baker Hughes, a GE company, LLC
- Inventors: Anthony A. DiGiovanni; Steven W. Webb; Marc W. Bird
- Web page: https://patentgrep.com/patent/US10246335B2

## CPC

- C01B 32/25: Diamond
- C01B 32/28: After-treatment, e.g. purification, irradiation, separation or recovery
- C22C 19/03: based on nickel
- C23C 14/18: on other inorganic substrates
- C23C 14/34: Sputtering
- C23C 14/5806: {Thermal treatment}
- C23C 14/5846: {Reactive treatment}
- C23C 14/5873: {Removal of material}
- E21B 10/46: characterised by wear resisting parts, e.g. diamond inserts
- E21B 10/54: the bit being of the rotary drag type, e.g. fork-type bits
- E21B 10/56: Button-type inserts (E21B10/52 takes precedence)
- C23F 1/18: for etching copper or alloys thereof
- C23F 1/34: for etching copper or alloys thereof
- C23F 1/44: Compositions for etching metallic material from a metallic material substrate of different composition
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- C22C: ALLOYS (treatment of alloys C21D, C22F)
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- E21B: EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- C23F: NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE (working metal by laser beams B23K26/00; desurfacing by applying flames B23K7/00; working of metal by electro-erosion B23H; producing decorative effects by removing surface material, e.g. by engraving, by etching, B44C1/22; electrolytic etching or polishing C25F); INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25

## Abstract

A method of modifying surfaces of diamond particles comprises forming spinodal alloy coatings over discrete diamond particles, thermally treating the spinodal alloy coatings to form modified coatings each independently exhibiting a reactive metal phase and a substantially non-reactive metal phase, and etching surfaces of the discrete diamond particles with at least one reactive metal of the reactive metal phase of the modified coatings. Diamond particles and earth-boring tools are also described.

## Claims

### Claim 1

A method of modifying surfaces of diamond particles, comprising:
forming spinodal alloy coatings over discrete diamond particles while the discrete diamond particles are mobilized by a particle dispersing apparatus;
thermally treating the spinodal alloy coatings to form modified coatings each independently exhibiting a reactive metal phase and a substantially non-reactive metal phase; and
etching surfaces of the discrete diamond particles with at least one reactive metal of the reactive metal phase of the modified coatings.

### Claim 2 (depends on 1)

The method of claim 1, wherein forming spinodal alloy coatings over discrete diamond particles comprises forming a spinodal alloy on each of the discrete diamond particles, the spinodal alloy comprising at least one metal element reactive with diamond at a temperature greater than or equal to about 650° C.

### Claim 3 (depends on 1)

The method of claim 1, wherein forming spinodal alloy coatings over discrete diamond particles comprises forming one or more of a Cu—Ni spinodal alloy, a Cu—Ni—Sn spinodal alloy, and a Cu—Ni—Sn—Co spinodal alloy, a Au—Ni spinodal alloy, a Ni—Pt spinodal alloy, a Ni—Rh spinodal alloy, a Co—Ni—Fe spinodal alloy, a Co—Fe spinodal alloy, a Co—Pt spinodal alloy, and an Fe—Rh spinodal alloy.

### Claim 4 (depends on 1)

The method of claim 1, wherein forming spinodal alloy coatings over discrete diamond particles comprises forming a Cu—Ni spinodal alloy over the discrete diamond particles, the Cu—Ni spinodal alloy comprising from about 50 wt % Ni to about 90 wt % Ni, and from about 10 wt % Cu to about 50 wt % Cu.

### Claim 5 (depends on 1)

The method of claim 1, wherein forming spinodal alloy coatings over discrete diamond particles comprises forming a Cu—Ni—Sn spinodal alloy over the discrete diamond particles, the Cu—Ni spinodal alloy comprising from about 5 wt % Ni to about 35 wt % Ni, from about 6 wt % Sn to about 13 wt % Sn, and from about 52 wt % Cu to about 89 wt % Cu.

### Claim 6 (depends on 1)

The method of claim 1, wherein forming spinodal alloy coatings over discrete diamond particles comprises:
forming a spinodal alloy; and
depositing the spinodal alloy over each of the discrete diamond particles.

### Claim 7 (depends on 1)

The method of claim 1, wherein forming spinodal alloy coatings over discrete diamond particles comprises:
depositing spinodal alloy precursor coatings over each of the discrete diamond particles; and
converting the spinodal alloy precursor coatings into the spinodal alloy coatings.

### Claim 8 (depends on 1)

The method of claim 1, wherein thermally treating the spinodal alloy coatings comprises:
heating the spinodal alloy coatings to a temperature above an upper critical solution temperature of a spinodal alloy thereof to form homogenized spinodal alloy coatings;
cooling the homogenized spinodal alloy coatings to a temperature below a temperature range of a spinodal region of the spinodal alloy to form quenched spinodal alloy coatings; and
heating the quenched spinodal alloy coatings to a temperature within the temperature range of the spinodal region of the spinodal alloy to form spinodally decomposed alloy coatings in accordance with a time-temperature-transition diagram.

### Claim 9

A method of modifying surfaces of diamond particles, comprising:
forming spinodal alloy coatings over discrete diamond particles;
thermally treating the spinodal alloy coatings to form modified coatings each independently exhibiting a reactive metal phase and a substantially non-reactive metal phase;
selectively removing the substantially non-reactive metal phase of the modified coatings; and
etching surfaces of the discrete diamond particles with at least one reactive metal of the reactive metal phase of the modified coatings after selectively removing the substantially non-reactive metal phase of the modified coatings.

### Claim 10 (depends on 9)

The method of claim 9, wherein selectively removing the substantially non-reactive metal phase of the modified coatings comprises contacting the modified coatings with at least one wet etchant formulated to selectively etch the substantially non-reactive metal phase of the modified coatings relative to the reactive metal phase of the modified coatings.

### Claim 11 (depends on 9)

The method of claim 9, wherein selectively removing the substantially non-reactive metal phase of the modified coatings comprises removing a Cu phase of the modified coatings without substantially removing a Ni-containing phase of the modified coatings.

### Claim 12 (depends on 11)

The method of claim 11, wherein removing a Cu phase of the modified coatings without substantially removing a Ni-containing phase of the modified coatings comprises contacting the modified coatings with one or more of a CuCl2 solution, a FeCl3 solution, a K2Cr2O7 solution, a CH3COOH solution, a chromic/sulfuric acid solution, an H2S2O8 solution, an alkaline sodium chlorite solution, an alkaline peroxydisulfate solution, and an alkaline persulfate solution.

### Claim 13 (depends on 1)

The method of claim 1, wherein etching surfaces of the discrete diamond particles with at least one reactive metal of the reactive metal phase of the modified coatings comprises heating the modified coatings to a temperature effectuating destruction of the crystallinity of portions of the discrete diamond particles by the at least one reactive metal.

### Claim 14 (depends on 1)

The method of claim 1, wherein etching surfaces of the discrete diamond particles with at least one reactive metal of the reactive metal phase of the modified coatings comprises etching the surfaces of the discrete diamond particles with Ni.

### Claim 15 (depends on 1)

The method of claim 1, wherein forming spinodal alloy coatings over discrete diamond particles comprises co-sputtering different metal atoms from different metal sources over surfaces of the discrete diamond particles while the discrete diamond particles are mobilized by the particle dispersing apparatus.

### Claim 16 (depends on 1)

The method of claim 1, wherein forming spinodal alloy coatings over discrete diamond particles comprises sequentially sputtering different metal atoms from different metal sources over surfaces of the discrete diamond particles while the discrete diamond particles are mobilized by the particle dispersing apparatus.

### Claim 17 (depends on 1)

The method of claim 1, wherein forming spinodal alloy coatings over discrete diamond particles while the discrete diamond particles are mobilized by a particle dispersing apparatus comprises forming the spinodal alloy coatings over the discrete diamond particles while the discrete diamond particles are mobilized by a vibrating structure.

### Claim 18 (depends on 1)

The method of claim 1, wherein forming spinodal alloy coatings over discrete diamond particles while the discrete diamond particles are mobilized by a particle dispersing apparatus comprises forming the spinodal alloy coatings over the discrete diamond particles while the discrete diamond particles are mobilized by a fluidized bed.

### Claim 19 (depends on 1)

The method of claim 1, further comprising removing the modified coatings from the etched surfaces of the discrete diamond particles.

### Claim 20 (depends on 19)

The method of claim 19, wherein removing the modified coatings from the etched surfaces of the discrete diamond particles comprises treating the discrete diamond particles with at least one acid.