The present invention relates to methods of thermo-chemical treatment and composite material fabrication for metals which can form ceramic structures such as nitrides, carbides, and mixtures thereof.
Several hardening methods are described in the literature that are implemented in static environments. In particular, there is plasma nitriding by means of a low temperature plasma gas intensified by a thermionic emission source (U.S. Pat. Nos. 5,294,264 and 5,443,663), a bath of salts (U.S. Pat. Nos. 5,518,605; 6,645,566), powder (U.S. Pat. No. 6,105,374), and by means of low temperature ion nitriding (U.S. Pat. No. 6,179,933). A technique of ion implantation has been proposed (U.S. Pat. Nos. 5,383,980; 6,602,353).
There also exists a non-static method in which a laser beam that is movable relative to the substrate is directed onto the substrate and produces surface melting in the impact zone. Nitrogen is blown onto the substrate in a direction that remains fixed relative to the direction of the laser beam, and an inert gas is also blown onto the piece (EP-A-0 491 075). In that method, the nitrogen is mixed with the inert gas and both the laser beam and the nitrogen-inert gas jet converge on the piece so that the gaseous mixture strikes the liquid zone. To prevent said zone being converted into a spray, it is necessary to limit the pressure of the gas jet. This method has made it possible to obtain hardening of a Ti alloy over a thickness of 400-1000 microns.
U.S. Pat. No. 3,944,443 describes the application of a high temperature induction plasma with a combination of nitrogen gas with either propane or BF3 to achieve hard surface layers up to 250 microns. The object to be coated must be electrically isolated.
U.S. Pat. No. 4,244,751 describes melting the surface (but does not describe ionizing the nitrogen molecules) of Al with a plasma torch (TIG) to obtain a hard surface. The thickness of the surface layer is <200 microns.
U.S. Pat. Nos. 5,366,345 and 4,451,302 describe hardening of a metal substrate using a laser or e-beam with melting of the surface in nitrogen.
A method of thermo-chemical treatment of the surface of metal substrates by nitriding, carbiding, and carbonitriding. The basis of the method is the use of a high temperature ionized gas arc plasma stream at ambient pressure. The method of the invention makes it possible to obtain hardening over a much greater thickness (up to but not limited to 10,000 microns), at a much faster rate and using much simpler and less expensive means than would be required for a laser or other arc type device. This can be accomplished with or without melting of the surface.
Nitrogen or a nitrogen containing gas mixture is directed into the plasma stream wherein the work piece is one electrode of the plasma source. At very high plasma temperatures, nitrogen molecules split into atoms and the atoms ionize to ions. The ions are blended with a gas plasma stream, typically Ar or He, or a mixture of Ar and H2, and reach the metal substrate surface in a very energetically active ion state of high energy. Absorption and reaction of the ions occurs much more rapidly than for the corresponding non-ionized molecules. In addition, since the metal work piece is one electrode that creates the plasma, the plasma stream heats the metal substrate surface very fast and the surface can reach temperatures near to the melting point of the metal in fractions of second, on the order of hundredths of a second.
Without surface melting, the converted layer of the substrate can be up to 1 or more mm thick. With melting of the surface, the converted layer can be up to 6 or more mm thick. For a Ti-6Al-4V substrate, the hardness obtained without melting can range from about 45-85 as measured by the Rockwell C method.
The method can be used for Ti and Ti alloys as well for Al, Cr, Fe, Co, Ni, Nb, Ta, V, Zr, Mo, W, Si and their alloys. These metals form very hard nitrides and carbides.
The invention is now described in greater detail with reference to a particular embodiment given by way of non-limiting example and shown in the accompanying drawings, in which:
Referring to
By adjusting the velocity of the nitrogen stream (5) to within the range from about 0.1 meters per second (m/s) to about 10 m/s, the nitrogen is caused to penetrate into the plasma mixing zone (8) resulting in an active argon plasma containing nitrogen ions. Changing the nitrogen stream speed results in a change in the nitrogen content of the treated layer (9).
Another possible method to change the composition and structure of the surface layer is to change the torch motion parameters during scanning, including rate of forward travel, and oscillation speed and width. At a constant plasma stream (4) power, the nitrogen content in the surface layer has an inverse proportionality relationship to torch speed. A forward travel rate of about 10 mm/min to about 500 mm/min is within a range that produces useful results.
For the case of a Ti-6Al-4V substrate, the ratio of N atoms to Ti atoms in the surface layer after treatment without melting is about 5% to about 49%, based on pure TiN having a ratio of 50%, and pure Ti having a ratio of 0%. The surface hardness after treatment without melting is up to about 85 HRC. In the treated samples the hardness of the surface layer decreases as the distance from the surface increases. This decrease is proportional to a corresponding decrease in the ratio of TiN to Ti atoms as the distance from the surface increases. This is illustrated in
The nitrided surface has a 3 phase structure consisting of alpha Ti, beta Ti and TiN crystals. In addition, a slightly harder beta-type structure of said alloy that is derived from fast thermal transformation during cooling which may be interposed between the nitrided portion and the alpha/beta-type Ti-6Al-4V structure.
In some special applications, conventional processing for surface layer deposition cannot be utilized to produce a coating and in particular carbide coatings. In vacuum carburizing a typical precursor is a hydrocarbon such as cyclohexane which contains hydrogen. Many steels and titanium are sensitive to hydrogen and can't be treated by the conventional processing, whereas the PTA surface treatment modification process can utilize a solid carbon source such as carbon black or fullerenes to carbonize and eliminate any adverse reactions with hydrogen and the substrate.
The invention will now be described with reference to the following non-limiting examples.
A Ti-6-4 substrate was placed in the inert chamber of a rapid prototyping apparatus in which a plasma transferred arc (PTA) welding torch was used as the heat source. The torch position and operating parameters were controlled by a computer operated 3-D CNC positioning means. The torch operating parameters were also controlled by the same computer. The inert gas chamber of the rapid manufacturing apparatus was purged with Ar gas until the oxygen level reached 25 ppm of oxygen. Ar gas was flowed through the torch gas holes of the PTA torch and nitrogen gas was flowed through the shield gas holes. No gas was flowed through the powder feed channels. The amperage for the PTA torch was set at 52 amps and torch forward speed was set at 0.3 IPM. The surface of the Ti-6Al-4V substrate was scanned with the torch, so as to avoid melting of the substrate surface. After cooling to room temperature, the Rockwell C hardness (RC) of the substrate was measured as 38, the same as an untreated Ti-6-4 substrate. This clearly illustrates that in the absence of a reactive gas to form e.g. a carbide or nitride, no surface layer of increased hardness is formed.
Example 1 was repeated with a nitrogen flow of 7 SCFH through the powder feed holes. After cooling to room temperature, the RC was measured as 65.
A Ti 6-4 work piece was treated with a PTA torch using two different conditions. The resultant work piece is shown in
Example 2 was repeated with a torch amperage of 52 amps, a nitrogen flow through the powder feed holes of 7 SCFH, and a torch travel speed of 0.15 IPM. After cooling to room temperature, the RC was measured as 70.
Example 2 was repeated with a torch amperage of 52 amps, a nitrogen flow through the powder feed holes of 5 SCFH, and a torch travel speed of 0.3 IPM. After cooling to room temperature, the RC was measured as 55.
Example 2 was repeated using a steel substrate with 2% C, with a torch amperage of 45 amps, a nitrogen flow through the powder feed holes of 7 SCFH, and a torch travel speed of 0.15 IPM. After cooling to room temperature, the RC was measured as 33. The RC of the original untreated steel substrate was 23.
Example 2 was repeated using an Al substrate, with a torch amperage of 55 amps, a nitrogen flow through the powder feed holes of 7 SCFH, and a torch travel speed of 0.15 IPM. After cooling to room temperature, the RC was measured as 15. The RC of the original untreated Al substrate was 11.
Example 2 was repeated with a torch amperage of 25 amps, a flow of a 50/50 mixture of nitrogen and propane fed through the powder feed holes of 5 SCFH, and a torch travel speed of 0.2 IPM. The composition of the surface conversion was a mixture of TiN and TiC which included a solid solution of TiCN.
Example 2 was repeated with a torch amperage of 25 amps, a flow of propane fed through the powder feed holes of 5 SCFH, and a torch travel speed of 0.4 IPM. The converted surface consisted of TiC which had a hardness of RC65-75.
Example 2 was repeated with a torch amperage of 25 amps, a flow of boron trichloride and hydrogen gasses fed through the powder feed holes of 5 SCFH, and a torch travel speed of 0.4 IPM. The converted surface consisted of titanium boride which had a hardness of RC65-75.
A Ti-6-4 substrate in the form of a 4″ diameter by ½″ thick disc was placed in the chamber of the PTA SFFF unit. A schematic of the PTA SFFF process is shown in
A Ti-6-4 substrate in the form of a 6″×6″×½″ flat plate was placed in the chamber of the PTA SFFF unit. The inert gas chamber was purged with Ar gas until the O2 level was measured as 25 ppm with a Model 1000 Oxygen Analyzer from Advanced Micro Instruments, Inc. The PTA torch was started using Ar as the torch gas and as the shielding gas. A spherical powder of Ti-6-4 with a particle size range between −8/+320 mesh was fed into the torch and melted by the PTA torch so as to deposit onto the Ti substrate. By adjusting the operating parameters of the PTA torch, conditions were established to deposit multiple layers with a size of 1″×4″ of Ti-6-4 on the substrate. The total thickness built up in this was ˜0.5″. The shield gas and inert chamber gas were then switched to N2 and another layer was deposited on the test bar. Upon cooling to room temperature and removal from the PTA unit, the deposit was machined so as to provide a flat top surface. The Rockwell C hardness of the surface layer was measured at 75 Rockwell C.
A Ti-6-4 substrate in the form of a 1″×6″×½″ flat plate was placed in the chamber of the PTA SFFF unit. The inert gas chamber was purged with N2 gas until the O2 level was measured as 25 ppm with a Model 1000 Oxygen Analyzer from Advanced Micro Instruments, Inc. The PTA torch was started using Ar as the torch gas and N2 as the shielding gas. The surface of the Ti-6-4 plate was processed by exposure to the PTA torch operating with a N2 atmosphere, but without the introduction of Ti powder or wire. By adjusting the operating parameters of the PTA torch, conditions were established to produce a surface layer of high TiN content and a total layer thickness of ˜0.1″. Upon cooling to room temperature and removal from the PTA unit, the deposit was machined so as to provide a flat top surface. The plate was machined on the face with the TN so as to provide a flat smooth surface with a thickness of the TiN layer of ˜0.050″. The Rockwell C hardness of the surface layer was measured at 70 Rockwell C. A test bar was machined from the plate with the dimensions of 0.33″×0.33×4.0″. The bar was tested in 4 point bending with the TiN surface up. The load on the bar was increased to 4000 pounds, at which point the test was stopped. The calculated bend stress was 216 Ksi. The bar had deflected and had a curvature of 0.1″. No cracking or delamination of the TiN surface layer or the Ti-6-4 substrate could be observed. A bar was also tested for heat resistance in comparison to Ti-6-4. A sample of each material with dimensions ˜1″×3″×1″ thick was placed in the PTA chamber and exposed to the plasma arc. The voltage was ˜28 volts. The power level was initially set at 50 amps and the samples were subjected to heating by the torch. The power level (heat input) was increased in ˜5 amp increments until melting of the sample was observed. For the Ti-6-4, this occurred at 80 amps. For the TiN surface on Ti-6-4, melting was not observed until the power level was 105 amps, or a 31% increase in heat flux compared to the Ti-6-4. At 100 amps, there did not appear to be any damage or cracking in the TiN surface layer.
It should be understood that the preceding is merely a detailed description of one embodiment of this invention and that numerous changes to the disclosed embodiment can be made in accordance with the disclosure herein without departing from the spirit or scope of the invention, which is defined by the following claims.
This application claims priority from U.S. Provisional Application Ser. No. 60/745,241, filed Apr. 20, 2006, the contents of which are incorporated herein by reference.
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Number | Date | Country | |
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20080000881 A1 | Jan 2008 | US |
Number | Date | Country | |
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60745241 | Apr 2006 | US |