This invention relates to diamond-coated articles and their production using chemical vapor deposition, and more particularly, to diamond deposition suitable for articles having small dimensions. BACKGROUND OF THE INVENTION

Chemical vapor deposition (CVD) is the method that has been used to deposit diamond thin films. This process involves chemical reaction between two gases or between a volatile compound and gases to produce solid material that deposits atomistically onto a substrate. The various techniques that have been developed to accomplish chemical vapor deposition fall generally into three categories: thermally assisted CVD, plasma assisted CVD and combustion flame diamond deposition. Variations and combinations of these techniques have also been used. The various CVD processes are carried out using a carbon-containing gas such as CH ₄ , C2H ₂ , acetone, CO and CO2. Typically the carbon-containing gas has been used in a hydrogen mixture with the percentage of hydrogen being 95% or higher. Less-dilute mixtures with hydrogen, mixtures with other gases and pure carbon-containing gas have also been used , see e.g., P. K. Bachman et al., Diamond and Related Materials 1, 1 (1991) for a review of CVD. Microwave plasma enhanced CVD has proven particularly useful for achieving diamond deposition at relatively low temperatures. In microwave plasma enhanced chemical vapor deposition, glow discharge plasmas are sustained within the chamber where the chemical vapor deposition reactions occur. The presence

of the plasma promotes the decomposition of the gas molecules into ions, electrons, atoms and molecules so that reactions occur at lower temperatures when plasma enhanced chemical vapor deposition is used in contrast to the often prohibitively high temperatures required when no plasma is used.

Microwave plasma enhanced CVD of diamond is generally carried out with a mixture of a small amount of a carbon-containing gas such as CH ₄ , C ₂ H ₂ , CO and CO ₂ in hydrogen. During the process the carbon-containing gas is decomposed at substrate temperatures of about 700°C to about 900°C in the presence of hydrogen to form diamond. Both diamond and graphite phases may deposit simultaneously. It is important to either prevent the graphite from forming or to selectively remove the graphite leaving behind the diamond. This can be accomplished by supersaturating the plasma with atomic hydrogen. Typically, a diluted mixture of about 0.5 to about 2% of CH ₄ in hydrogen is used. Diamond nucleation rate is a concern in CVD techniques and various attempts have been made to enhance the nucleation rate. It. is well-known that no matter what material is used as the substrate, scratching the surface of the substrate with an abrasive material, particularly diamond powder, greatly enhances the diamond nucleation rate. See, e.g., J. C. Angus et al. , Proc. Second Int'1 . Symp. on Diamond, The Electrochemical Society, Inc., Pennington, NJ, 91-8, 125 (1991) . Typically, this scratching is accomplished by rubbing the surface to be coated with diamond powder or grit. U.S. Patent No. 5,075,094 illustrates this (and also notes that diamond seems to nucleate strongly on areas of substrates with hydrocarbon contamination) . However, the small surface dimensions of articles such as fibers preclude the effective use of conventional

rubbing methods . Accordingly, the use of scratching to enhance nucleation is generally not reported for fibers and the like (see, e.g., Japanese Patent Publication No. 4-5964) ; and there remains a need for effective methods of enhancing nucleations on these types of articles. Another problem which can occur during CVD deposition of diamond into shaped article, particularly microwave enhanced CVD, involves substrate deterioration. Atomic hydrogen generated in the microwave plasma is believed to aid diamond growth and selectively removes any graphite that forms. However, the atomic hydrogen also tends to etch the substrate (see, e.g., G. H. Johnson, Diamond and Diamond-like Materials Synthesis, MRS Symposia Proc, EA-15, 99 (1988)) and whether this etching becomes a problem depends upon the morphology and material of the substrate as well as the diamond nucleation rate. This etching by hydrogen can be especially troublesome when trying to deposit a diamond coating on a shaped article having small dimensions. Examples of such shaped articles are fibers, cylinderical or spherical particles and powder particles. A graphite substrate is among the most difficult since the atomic hydrogen readily interacts with the graphite to form volatile hydrocarbons which are removed from the surface. As a result a graphite shaped article, for example, a graphite fiber, can be etched away before the diamond coating forms on the surface. Accordingly, there remains a need for effective methods of CVD deposition of diamond onto articles made of graphite and the like, before they are subject to undue deterioration from etching.

SUMMARY OF THE INVENTION

This invention provides a process for the chemical vapor deposition of diamond onto a shaped article and

diamond-coated shaped articles produced by that process. The process comprises the steps of placing the shaped article in a suspension of an abrasive powder (e.g., diamond powder) in a liquid (e.g., methanol) , the material of said powder having a hardness greater than the hardness of the material of said shaped article; agitating this suspension containing the shaped article for a time sufficient for the surface of the shaped article to become abraded; removing the shaped article from the suspension and drying it; and depositing a diamond coating on the shaped article by chemical vapor deposition. This process is especially useful for the chemical vapor deposition of diamond onto shaped articles having at least two dimensions which are small and/or shaped articles made of materials which are susceptible to etching during prolonged CVD (e.g., graphite fibers) . This invention provides diamond- coated graphite fibers which have diameters less than about 100 microns. BRIEF DESCRIPTION OF THE FIGURES

Figure 1 is a secondary electron micrograph of a diamond-coated graphite fiber prepared in Example 1.

Figure 2 is a secondary electron micrograph of diamond-coated graphite fibers prepared in Example 2. Figure 3 is the Raman spectrum for one of the diamond-coated graphite fibers prepared in Example 2.

Figure 4 is a secondary electron micrograph of diamond-coated graphite fibers prepared in Example 3.

Figure 5 is the Raman spectrum for one of the diamond-coated graphite fibers prepared in Example 3.

Figure 6 is a secondary electron micrograph of diamond-coated graphite fibers prepared in Example .

Figure 7A is a secondary electron micrograph of one of the diamond-coated silicon carbide fibers prepared in Example 5.

Figure 7B is a secondary electron, micrograph of silicon carbide fibers of Comparative Experiment D.

DETAILED DESCRIPTION This invention provides a method for enhancing the diamond nucleation rate on the surface of a shaped article during chemical vapor deposition, even where the article has small dimensions; and thereby provides an advantageous process for the chemical vapor deposition of diamond onto such a shaped article. The method for diamond nucleation enhancement of the instant invention comprises agitating the shaped article in a suspension of an abrasive powder in a liquid for a time sufficient ^• for the surface of the shaped article to become abraded. The shaped article is then dried and a diamond coating is then deposited onto the shaped article by CVD. The steps of placing the shaped article in the suspension, agitating the suspension to abrade the surface of the shaped article, and drying the shaped article after removing it from the suspension, represent a pre- treatment of shaped articles which can be generally used before diamond deposition to improve conventional processes for depositing diamond onto shaped articles by CVD.

The difficulty involved with scratching shaped articles having at least two dimensions that are small by pressing abrasives against them, generally increases as the dimensions become smaller. The method of this invention is especially useful for a shaped article having at least two dimensions less than about 1 mm, and even more useful for a shaped article having at least two dimensions less than about 100 μm (e.g., from 3 μm to 15 μm) . The shaped article can be a fiber or a particle with spherical, cylindrical or a less regular shape. The shaped article can be made of graphite,

silicon carbide, silicon, copper or any other substrate material on which diamond can be grown.

The abrasive powder used for the suspension consists essentially of a material harder than the material of the shaped article. Examples include alumina, silica, silicon carbide, and diamond, as long as the powder material is harder than the material of the shaped article. Hardness designations for various materials are well known (e.g., the Mohs Hardness Scale) . Diamond powder is the preferred abrasive powder. The amount of abrasive powder used to make the suspension is from about 0.01 g to about 1 g of abrasive powder per 100 mL of liquid, preferably about 0.1 g of abrasive powder per 100 mL of liquid. The particle size of the abrasive powder is preferably from about 0.25 μm to about 1 μm.

The suspension is formed by dispersing the abrasive powder in a liquid. Water can be used as the liquid as can organic solvents such as the alcohols (e.g., isopropanol, ethanol, methanol) . Since the shaped article must be dried after the agitation step, it is convenient to use a liquid which is easily removed, preferably by evaporation. Methanol is a preferred liquid. The suspension containing the shaped article is agitated for a time sufficient to abrade the surface of the shaped article. A convenient method of agitating the suspension is to vibrate it ultrasonically. Typically about 5 to about 60 minutes is sufficient when ultrasonic vibration is used with diamond powder as the abrasive, and the shaped articles are graphite or silicon carbide fibers. Preferably, the method of agitation is chosen to provide sufficient impact between the shaped article and the suspended abrasive to efficiently provide the desired surface abrasion.

The shaped article is removed from the suspension after the surface abrasion, and dried prior to diamond deposition by CVD. Any convenient method for drying can be used, e.g., allowing the liquid of the suspension to evaporate in air, heating the article above the boiling point of the liquid or blotting the shaped article dry with absorbent towels.

For shaped articles made of materials which suffer little or no hydrogen atom or other etching during CVD, the diamond nucleation enhancement provided by the instant process will result in greatly improved, faster growth of the diamond coating on the surface of the article. Silicon carbide is an example of such a material. For shaped articles made of materials which suffer severe hydrogen atom or other etching during CVD, the nucleation enhancement provided by the instant process will make possible the growth of a diamond coating on the surface of articles which might otherwise be completely etched away before the diamond coating forms. Graphite is an example of a material that suffers severe etching and, as a consequence, the process of this invention makes possible the deposition of diamond coatings onto graphite shaped articles including small shaped articles such as graphite fibers. ^• The advantages of the instant invention may be further illustrated in connection with a particular microwave plasma enhanced CVD system using a 2.45 GHz source, wherein shaped articles are placed on a heater block in the deposition chamber and heated to a temperature in the range of about 700-900°C. When using a CVD mixture of about 0.3-5% CH ₄ in H ₂ and a discharge chamber pressure of about 10-75 Torr, fibers of graphite and graphite coated with silicon can be etched away completely or in part soon after the ignition of the plasma and before any deposition of diamond occurs.

Agitating graphite fibers before CVD in methanol without abrasive powder can result in some improvement in nucleation; but etching of the fibers during CVD still generally results in diamond crystals only on isolated regions of the portions of the fibers which survive the etching. In contrast, graphite fibers pretreated before CVD according to the process of the instant invention by agitation in a suspension of diamond powder in methanol, typically show complete and continuous coating of diamond ranging in thicknesses from about 0.1 μm to about 20 μm, depending on the time of deposition. The coating of diamond may be confirmed using Raman spectra which show a characteristic diamond peak at 1332 cm" ¹ . Typically, these Raman spectra contain only slight evidence of the broad band in the range of 1500-1600 cm ^-1 which is characteristic of graphite or other non- diamond carbon, indicating that graphite or other non- diamond carbon is either not present in the coatings produced by the process, or exists in a very small quantity.

This invention includes diamond-coated shaped articles produced by the process of this invention. Diamond is a material which is relatively inert in the presence of many reactive chemicals, which is relatively strong when subjected to various mechanical stresses, and which has a high thermal conductivity. Accordingly, the process of this invention may be used to provide coated articles requiring effective chemical protection, mechanical protection and/or heat dissipation. Of particular note are diamond-coated fibers having fiber diameters of less than about 100 microns (e.g., 3 to 15 μm) which are made by this process.

This invention includes diamond-coated graphite fibers which have graphite fiber diameters of less than about 100 μm. Diamond-coated graphite fibers with fiber

diameters of from 3 to 15 μm are preferred. These fibers can be produced using chemical vapor deposition as described herein. Diamond-coated graphite fibers are considered advantageous materials for use in composites for making products requiring thermal management (e.g., automobile radiators) and/or structural strength (e.g., aircraft, automobile and bridge components) .

Practice of the invention will become further apparent from the following non-limiting examples. EXAMPLE 1

Approximately 100 graphite fibers, 7 μm in diameter and 2 to 3 inches in length were placed in a suspension of 0.1 g of 0.25 μm diamond paste in 100 mL of methanol. The suspension containing the fibers was ultrasonically vibrated for 30 minutes. The fibers were removed from the suspension and blotted dry with absorbent paper towels .

A microwave plasma enhanced ASTEX® CVD system was used for the CVD. This system uses a 2.45 GHz source. The graphite fibers were placed on the heater block in the deposition chamber. The pressure in the chamber was reduced to 1 mTorr by means of a mechanical pump. The fibers were then heated to 850°C. The H2 flow into the chamber was initiated and the plasma ignited. The applied power was 1.5 kW and the reflected power was 1 W. After the plasma stabilized, CH ₄ was introduced into the chamber and the deposition commenced. Pressure in the chamber was maintained at about 40 Torr (+/- 0.05 Torr) during the deposition by a closed loop feed-back system. H2 (99.99% pure) and CH (99.0% pure) were introduced into the gas manifold through mass flow controllers and the flow rates were maintained at 500 standard cubic centimeter per minute (seem) for H ₂ and 3 seem for CH ₄ to form a mixture of 0.6% CH ₄ and 99.4% H ₂ . Deposition continued for 5 hours at which time the flow

of CH ₄ was stopped and the microwave and heater powers were turned off. The fibers were allowed to cool to ambient temperature inside the chamber before they were removed. The fibers with the deposited coatings were analyzed by secondary electron microscopy (SEM) . Figure 1 is a secondary electron micrograph which shows a graphite fiber with diamond deposited on it.

EXAMPLE 2 Approximately 100 graphite fibers, 7 μm in diameter and 2 to 3 inches in length were placed in a suspension of 0.1 g of 0.25 μm diamond paste in 100 mL of methanol. The suspension containing the fibers was ultrasonically vibrated for 30 minutes. The fibers were removed from the suspension and blotted dry with absorbent paper towels. The fibers were then coated with diamond following essentially the same CVD procedure used in Example 1 with the exception that the time of deposition was 22 hours instead of 5 hours. The fibers with the deposited coatings were analyzed by SEM. Figure 2 is a secondary electron micrograph which shows a complete and continuous coating of diamond on the graphite fibers. Figure 3 shows the Raman spectrum for one of these fibers. It has the characteristic diamond peak at 1332 cm ^-1 .

EXAMPLE 3 Approximately 100 graphite fibers, 7 μm in diameter and 2 to 3 inches in length were placed in a suspension of 0.1 g of 0.25 μm diamond paste in 100 mL of methanol. The suspension containing the fibers was ultrasonically vibrated for 30 minutes. The fibers were removed from the suspension and blotted dry with absorbent paper towels. The fibers were then coated with diamond following essentially the same CVD procedure used in Example 1 with the exception that the reflected power

was 2 W instead of 1 W and the time of deposition was 30 hours instead of 5 hours.

The fibers with the deposited coatings were analyzed by SEM. Figure 4 is a secondary electron micrograph which shows a complete and continuous coating of diamond on the graphite fibers . Figure 5 shows the Raman spectrum for one of these fibers . It has the characteristic diamond peak at 1332 cm ^-1 .

EXAMPLE 4 - COMPARATIVE EXPERIMENT A Approximately 100 graphite fibers, 7 μm in diameter and 2 to 3 inches in length were placed in a suspension of 0.1 g of 0.25 μm diamond paste in 100 mL of methanol. The suspension containing the fibers was ultrasonically vibrated for 30 minutes. The fibers were removed from the suspension and blotted dry with absorbent paper towels. The fibers (Example 4) were then coated with diamond following essentially the same CVD procedure used in Example 1 with the exception that the reflected power was 2 W instead of 1 W and the time of deposition was 15 hours and 10 minutes instead of 5 hours. The fibers with the deposited coatings were analyzed by SEM. Figure 6 is a secondary electron micrograph which shows a complete and continuous coating of diamond on the graphite fibers . For comparison (Comparative Experiment A) , approximately 100 other graphite fibers, 7 μm in diameter and 2 to 3 inches in length were placed in 100 mL of methanol which contained no diamond paste or other abrasive powder. The methanol containing the fibers was ultrasonically vibrated for 30 minutes. The fibers were removed from the suspension and blotted dry with absorbent paper towels. An attempt was made to coat these fibers with diamond. The fibers were placed in the CVD system and essentially the same CVD procedure used for the other fibers coated in this Example was

followed. While the methanol treatment provided some improvement in nucleation, it was not enough to stop the etching. The result was complete etching of most of the fibers. A few surviving portions of fibers show diamond crystals on isolated regions .

COMPARATIVE EXPERIMENT B An attempt was made to coat approximately 100 graphite fibers, 7 μm in diameter and 2 to 3 inches in length with diamond. The fibers were placed in the CVD system and essentially the same CVD procedure described in Example 1 was followed with the exception that the reflected power was 2 W instead of 1 W, the flow rate was maintained at 5.1 seem for CH ₄ to form a mixture of 1.0% CH ₄ and 99% H ₂ and the time of deposition was 24 hours instead of 5 hours. The fibers completely etched away.

COMPARATIVE EXPERIMENT C

An attempt was made to coat approximately 100 graphite fibers, 7 μm in diameter and 2 to 3 inches in length with diamond. The fibers were placed in the CVD system and essentially the same CVD procedure used in Comparison B was followed with the exception that the fibers were heated to 700°C instead of 850°C and the time of deposition was 40 minutes instead of 24 hours. The fibers completely etched away.

EXAMPLE 5 - COMPARATIVE EXPERIMENT D

Approximately 100 silicon carbide fibers, 7 μm in diameter and 2 to 3 inches in length were placed in a suspension of 0.1 g of 0.25 μm diamond paste in 100 mL of methanol. The suspension containing the fibers was ultrasonically vibrated for 30 minutes. The fibers were removed from the suspension and blotted dry with absorbent paper towels . These abraded fibers (Example 5) were placed on the heater block in the deposition chamber side by side with approximately 100 silicon

carbide fibers, 7 μm in diameter and 2 to 3 inches in length which had not been abraded (Comparative Experiment D) . Essentially the same CVD procedure described in Example 1 was followed with the exception that the time of deposition was 6 hours instead of 5 hours .

Both sets of fibers were analyzed by SEM. Figure 7A is a secondary electron micrograph of a fiber of Example 5. It shows a complete and continuous coating of diamond on a silicon carbide fiber. Figure 7B is a secondary electron micrograph of the untreated fibers of Comparative Experiment D. It shows only a small amount of diamond on the untreated silicon carbide fibers .

Example 5 and Comparison D show the advantage of the diamond nucleation enhancement provided by the instant process. It results in greatly improved, faster growth of the diamond coating on the surface of the article.

Particular embodiments of the invention are illustrated in the examples. Other embodiments will become apparent to those skilled in the art from a consideration of the specification or practice of the invention disclosed herein. For example, while microwave plasma enhanced CVD was used and the diamond coatings were deposited on graphite and silicon carbide fibers for the purposes of demonstrating the advantages of the instant invention, the method of the instant invention will provide diamond nucleation enhancement for any of the CVD techniques and for other shaped article materials as well. It is understood that the invention is not confined to the particular formulations and examples herein illustrated, but it embraces such modified forms thereof as come within the scope of the following claims .