Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Continued Examination Under 37 CFR 1.114
A request for continued examination under 37 CFR 1.114, including the fee set forth in 37 CFR 1.17(e), was filed in this application after final rejection. Since this application is eligible for continued examination under 37 CFR 1.114, and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114. Applicant's submission filed on May 14, 2025 has been entered.
The amendment filed May 14, 2025 with the RCE submission has been received and entered. With the entry of the amendment, claims 4, 5, 8, 9, 11, 13, 16 and 17 are canceled, claims 12, 18-20, 22-24 and 26-28 are withdrawn, and claims 1-3, 6, 7, 10, 14, 15, 21, 25 and 29 are pending for examination.
Election/Restrictions
Claims 12, 18-20, 22-24 and 26-28 remain withdrawn from further consideration pursuant to 37 CFR 1.142(b), as being drawn to a nonelected invention or species, there being no allowable generic or linking claim. Applicant timely traversed the restriction (election) requirement in the reply filed on July 22, 2020. Group I, claims 1-25, Species A of monotonic (understood to mean monatomic as claimed) oxygen species, Species B of metal/metallic material of the article and surface and Species C of metal/metallic material for the arc spray stream were elected.
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claims 1-3, 6, 7, 10, 14, 15, 21 and 29 are rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Claim 1, and claim 29 now both have “positioning the metal surface of the article to receive the non-thermal plasma stream and to etch organic residues from the metal surface of the article”. This is confusing and indefinite as worded because while the substrate is being “positioned” to etch organic residues, it is not actually worded that the organic residues are actually etched. Is (1) the further treatment with the non-thermal plasma stream also supposed to etch organic residues? Is (2) there supposed to be a separate etching treatment to remove organic residues? Is (3) the etching of organic residues actually optional (and is it even required that organic residues are present)? The specification at page 18 appears to indicate that the plasma treatment is what would etch the organic residues so, it does not seem that a separate etching treatment is intended (and would raise the issue of new matter). On the other hand, dependent claim 2 actually indicates that the treatment with the non0thermal plasma stream etches organic residue from the metal surface, so claim 2 would be not further limiting if the etching had to occur by the non-thermal plasma treatment, so it is unclear what is intended. For the purpose of examination, based on the described process in the disclosure, it is understood that organic residue is supposed to be present and the etching of organic residues would occur with the non-thermal plasma treatment, but applicant should clarify what is intended, such as the presence of organic residue and its removal by the non-thermal plasma treatment, for example, and cancelation of claim 2, without adding new matter. It is noted that claim 29 now has the positioning, but also specifically has the etching occurring with the non-thermal plasma stream treatment, and so is not rejected.
The other dependent claims do not cure the defects of the claims from which they depend and are therefore also rejected.
Claim Rejections - 35 USC § 103
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
Claims 1-3, 6, 7, 10, 14, 15, 21, 25 and 29 are rejected under 35 U.S.C. 103 as being unpatentable over Watchko et al (US 2002/0166682) in view of Hanson (US 8658258), Yancey et al (US 8981251) and Baughman et al (US 5922412), EITHER alone OR optionally, further in view of EITHER von Niessen et al (US 2012/0308733) OR Nagayama et al (US 2004/0144319); and further optionally as evidenced by Hewson et al (US 5958849) and Babu et al (US 5194501).
Claim 1, 2, 6: Watchko describes a method to adhere an arc spray coating to a surface of an article (note 0027-0028, 0023), where the article can be metal and the surface would be metal as the surface of a simply metal material (0012, 0025-0027), where the method can include an initial plasma treatment of surface 18 providing a cleaning and/or etching or otherwise modifying the surface 18 with a plasma generated from the ionization of oxygen, for example (0029), where since the surface 18 of the article is to be treated with the plasma it would have been at least suggested to position the plasma and the surface of the article to receive the plasma for treatment so that actual treatment occurs, noting how in figure 4 and 0034-0036 the surface of the article would be positioned for treatment with the arc spraying, for example. Watchko further describes generating an arc spray coating stream and directing the arc spray coating stream at what would be the plasma treated surface region, where the arc spray coating stream forms an arc spray coating surface associated with what would be the plasma treated surface region of the article (note 0034-0036 and figure 4, where it is noted that it is desired to cover substantially the entire surface of 18, and thus the plasma treated areas of 18, note 0027). Watchko further describes that the arc spray coating stream would spray molten metal to the surface of the article to be coated to deposit the molten metal on the plasma treated surface to provide coating (0027, 0032, 0035-0036, figure 4).
(A) As to using the plasma to create an energized surface region comprising a plasma treated surface of the article with a non-thermal plasma stream at atmospheric pressure, and as to the treatment of the energized surface region of the metal surface with the non-thermal plasma stream for a time such that the energized surface region comprises a metal oxide region/species having a higher surface energy than the metal surface of the article and being grown from a base metal of the article being treated (claim 1), and the metal oxide region comprises an outer oxide surface having the higher surface energy than the metal surface of the article (claim 6), and forming by the non-thermal plasma stream chemical bonding sites of the energized surface region, the chemical bonding sites promoting chemical bonding with the energized surface region,
Watchko notes that the article treated can be metal such as aluminum, steel, etc. (0025) and that it is desired for surface 18 to be at ambient temperature to avoid heat distortion, etc. (0030). Hanson describes how it is known to provide metal substrates (including aluminum, steel, etc.) that form oxides on exposure to ambient conditions (column 2, line 55 through column 5, line 20), where the substrate is treated with plasma by placing (so positioning) in a plasma atmosphere, where reactive species of the plasma (electrons, cations radicals) believed to react with contaminants, such as cutting oils, lubricants, corrosion inhibitors, adhesive products, etc and remove them as gaseous reaction products (e.g. CO2) while leaving the inorganic component, i.e. metal, metal oxide groups relatively unscathed, which would at least clean the surface, and any plasma source can be used, but atmospheric pressure generated plasmas preferred, where the plasma can be provided as a plasma jet and be derived from a feed gas that can include oxygen or air (column 3, lines 15-65), where it is further indicated that plasma conditions, including power density, feed gas flow rates, dwell time, and temperature can be controlled and selected to provide controlled removal of contaminant, and can maintain or increase the oxide content on the substrate surface (column 4, lines 10-32) and preferably the plasma has oxygen containing gas that is believed to generate metal oxide groups on the metal substrate (column 3, lines 55-60). Since the article/substrate is placed in the plasma atmosphere to treat, it is understood that the surface of the article would be positioned to receive the plasma stream/jet for the reaction treatment.
Furthermore, Yancey further describes an atmospheric pressure plasma can be provided as a plasma stream or plume or jet that would be directed towards a substrate and coating to remove a coating on a substrate by having components of the coating react with energetic species of the plasma (figures 2, 3, column 2, lines 10-25, where as shown the substrate would be positioned to receive the plasma stream that would be generated), where the substrate can be metallic and there is no limit on the coating type or composition that can be removed (column 6, lines 30-35), and the plasma plume etches the coating (column 7, lines 20-25), where the plasma can be a cold, or non-thermal, plasma and have reactive oxygen species in the plasma to react with the coating (column 7,lines 30-65), and where operating parameters can be controlled and there would be a time of treatment (column 8, lines 1-40), and where oxygen or air can be supplied to the plasma to give oxygen species (column 5, lines 1-10) and where removal described as etching and can remove with forming CO2 for example (column 7, lines 10-65).
Therefore it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Watchko to use a non-thermal plasma stream that is generated and at atmospheric pressure and to position the surface of the article to receive this non-thermal plasma stream and treating the surface of the article with this stream as suggested by Hanson and Yancey to provide a desirable surface cleaning/etching treatment and modification before the arc spraying, since Watchko teaches treating a metal surface such as aluminum or steel with plasma generated from oxygen gas, for example, to clean/etch/modify the surface before the arc spraying, and also teaches that it is desired to avoid heat distortion, etc. of the surface, and Hanson teaches that an atmospheric pressure plasma that generates plasma using oxygen gas for example, can be used to clean (remove contaminants) a metal surface such as aluminum or steel that forms oxides by placing it in the plasma atmosphere which can be a jet of plasma to react with the contaminants and remove them and can also increase the oxide content of the metal surfaces, and Yancey teaches that a form of atmospheric plasma using oxygen radicals that can also be used to similarly clean/etch/ remove coating on a surface that can be metal by reacting can be a non-thermal atmospheric plasma, where articles would be provided and placed for Hanson and Yancey so that the surface can be treated with the plasma. As to the treatment providing an energized surface region comprising a plasma treated surface of the article, it would be understood that this would be indicated to occur by Hanson and Yancey since the surface would be exposed to an energized reacting plasma as described by applicant, and so the area exposed would be energized, and as well, Hanson indicates that further oxidation can occur, and noting original claims 5, 14, for example it is indicated as energized region a metal oxide region, so it is understood that the oxidation at least would give an energized surface region to the extent claimed where occurs, and that would occur over time, noting the dwell time control indicted by Hanson and time of treatment indicated as used by Yancey, such that the energized surface region is treated over time, where the Watchko materials are such that would also be indicated to get oxides on the surface as indicated by Hanson as materials that form oxides in ambient, and also when providing suggested plasma cleaning etc, and Watchko allows surface modification with the plasma, so it would be understood that the oxides would be acceptably provided on the surface before the arc spray coating, and as well does not prevent exposure to ambient and so would not prevent oxides from being present as well, and this oxide formation would meet the requirement of the energized surface region comprises a metal oxide region/species. Furthermore, as to the oxide surface region/species being grown from a base metal of the surface, since the reaction is with the surface to increase oxide content on the substrate surface, the oxide content would be understood to be grown from a base metal of the substrate article, and would have an outer oxide surface on the top. With reaction and growth, it would be further understood there would be a time of growth, to allow the reaction. Furthermore, it would be suggested to provide such oxide formation and growth, since Hanson indicates how this is a process that desirably occurs with the plasma treatment (note column 3, lines 55-60) that includes the cleaning process (note column 3, lines 15-30). As to the oxide content having a higher surface energy than the metal surface, since the surface is energized by the treatment, it is understood to provide the higher surface energy claimed. Furthermore, since the process is the same described by applicant for the higher surface energy, the same results as claimed would be expected.
Furthermore, as to the non-thermal plasma stream forming chemical bonding sites on the energized surface region, the chemical bonding sites promoting chemical bonding with the energized surface region as claimed, the process as discussed above would indicate forming oxides on the surface, and this is understood to form a chemical bonding sites that would promote chemical bonding with the energized surface region as claimed since applicant indicates providing the oxide formation to enhance bonding and the process giving chemical bonding in the specification as filed, and Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established. In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433 (CCPA 1977). Watchko also allows chemical bonding (oo28).
Optionally, further using EITHER von Niessen OR Nagayama, von Niessen further describes a process for applying a thermally sprayed coating using a plasma spraying (abstract) where the substrate is typically metallic (0018), and where a pretreatment cleaning is performed on the substrate with a plasma treatment, and an oxide layer is generated on the substrate (note for example, 0020, 0028, 0038), and where this oxide layer gives a better adhesion of the coating structure on the substrate (note 0028). Nagayama further describes a substrate can be provided of a metal such as an aluminum alloy (note 0031), where the substrate is provided with a pretreatment using plasma to form an oxidation of the surface (note 0029, 0034-0035) and then the surface is thermally sprayed by a process such as plasma spraying (note 0036, 0042), where the oxidation pre-treatment helps improve the adhesion of the thermally sprayed coating (0029).
Therefore, it further would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention that when providing the process of Watchko in view of Hanson and Yancey to specifically optimize the conditions to provide the oxide formation as taught by Hanson, for example, to help with adhesion of the further sprayed coating (thermally sprayed) of Watchko as suggested by EITHER von Niessen OR Nagayama, since Hanson indicates how the plasma treatment with cleaning can also be used to provide oxide on the surface, and EITHER von Niessen OR Nagayama would indicate how it is known that providing oxide on the surface of a metal substrate can help with better adhesion of a further applied thermal sprayed coating. Additionally, both von Niessen and Nagayama notes further plasma spraying can be used to apply the coating, and section (B) below would further suggest the use of plasma in the arc spraying process.
(B) Furthermore, as to the arc spray coating stream comprising a stream of molten metal surrounded by a sheath of air plasma such that molten metal surfaces of the molten metal are plasma treated, Watchko would provide that the arc spraying would provide an arc spray stream of molten metal being propelled towards the metal surface of the article (note 0035-0036, 0027, 0032, figure 4), where the stream would have molten droplets and thus molten metal surfaces of these droplets (0035-0036, figure 4). Watchko would indicate gas 84 provides atomization giving the droplets (note 0034-0036). Watchko notes that a secondary stream gas can be provided that would provide a sheath of gas around the molten metal stream and further atomization noting the exits at 92 in figure 4 for additional gas 88 (0035).
Baughman further indicates that it is also known to provide wire arc spraying where a plasma provided with air as a creating gas (so air plasma), for example, is directed to pass to a continuously fed wire tip along with an arc to the tip where additional air is funneled around the plasma plume and also intersects the formed spray to accelerated atomize and shroud the metal droplets (column 2, lines 30-50). As shown by figure 1, the melting with the arc and plasma intersecting the wire would give stream of molten metal, where given the plasma plume would be expected to be at least acceptably surrounded by a sheath of plasma gas (at the least, before the additional air, and there would still be a stream of plasma headed to the surface as well), and as well the droplets of molten metal would also be exposed to the plasma and thus be treated by the plasma while being propelled to the surface of the article being coated (note figure 1, showing the plasma plume travelling with the droplets to the substrate surface).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Watchko in view of Hanson and Yancey, EITHER alone OR further in view of EITHER von Niessen OR Nagayama to either use air plasma for atomizing gas 84 as in Watchko or use a wire arc system as in Baughman from the teachings of Baughman with an expectation of providing a predictably acceptable spraying, since Watchko provides arc spraying, and Baughman provides that arc spraying can further be conventionally provided with a central air plasma gas that forms a stream of molten metal from a wire tip and where there is a further secondary stream of gas that provides atomization, where when the plasma gas impacts the wire and forms a molten stream it would be understood to provide a sheath of plasma around the molten stream as the plasma plume would be indicated as surrounding the wire tip and metal or at least be expected to predictably and acceptably be provided to do so from the plasma plume shape shown, and as well the plasma would treat the metal surfaces of the droplets formed in the molten stream while being propelled to the surface as described above.
(C) Furthermore, as to applying an auxiliary gas onto the metal surface of the article (claims 1, 11), where the gas can comprise an inert gas (claim 1), for example,
Yancey would further indicate how auxiliary gas can be provided to shape the plasma (for the non-thermal plasma stream), providing a focused stream that may increase removal rate, and also can assist in cooling the substrate during application of the plasma (note column 9, lines 1-65, and figures 5-9, where auxiliary gas can be provided on one side of the plasma flame as gas curtain or air knife 568, on the other side as gas curtain or air knife 768, or auxiliary gas can be provided with two streams, 568 and 768 at the same time, noting figure 9). The auxiliary gas can be inert gas (column 9, lines 39-40, described for 768, but understood to apply to 568 as well, since 768 is used for the same purpose as 568, note column 9,lines 45-50). It is understood that the auxiliary gas used as described in Yancey would be applied onto the surface of the article, since it follows and shapes and flows alongside the non-thermal plasma (note figures 5-9) that would be directed to the surface of the article to treat the surface, and as well, it is indicated as providing cooling to the substrate, so indicted to be directed to the surface to impact and cool the surface of the substrate, or at least be suggested to do so to give the desired treatment.
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Watchko in view of Hanson, Yancey and Braughman, EITHER alone OR further in view of EITHER von Niessen OR Nagayama to provide an inert gas auxiliary gas that shapes the non-thermal plasma and cools the substrate and would be directed onto the metal surface of the article as suggested by Yancey with an expectation of providing a desirable non-thermal-plasma stream for use, since Watchko in view of Hanson, Yancey and Braughman, EITHER alone OR further in view of EITHER von Niessen OR Nagayama would already suggest the providing of a non-thermal plasma stream as discussed above, with Yancey already describing how a non-thermal plasma stream can be provided for use, and Yancey would further suggest as discussed above, how when providing non-thermal plasma streams for treating a surface, an inert auxiliary gas can be provided that helps shape the plasma and also can help cool the substrate, and that this auxiliary gas would also be directed onto the metal surface of the article. Note that the application of auxiliary gas can occur as worded, at any point in the overall process, including during the treating with the non-thermal plasma stream.
(D) Furthermore, as to the positioning of the metal surface of the article to receive the non-thermal plasma stream and to etch organic residues from the metal surface of the article as well, where the treating with the non-thermal plasma stream also etching organic residues from the metal surface of the article (as now for claims 1 and 2), Watchko specifically notes that the initial plasma treatment can provide cleaning and/or etching (note 0029). Hanson further notes that the surfaces can have contaminant residues to remove in the form of cutting oils or adhesive products, for example, which would be removed/etched by the plasma treatment, which leaves the inorganic component relatively unscathed (or even increasing metal oxide content, that is, the metal oxide formation can occur at the same time as contaminant removal) (where since “inorganic” unscathed, the removed material such as cutting oil and adhesive is understood to be organic) (note column 2, lines 15-25, and column 4, lines 15-30, where it is also noted that polymeric coating (so organic) can be removed; and note column 10, lines 25-30, noting PSA residues, and cutting oils left (residues)). Yancy also describes the plasma process etching materials of the surface (column 7, lines 35-65, where the etching can be of an adhesive layer, and it is noted that polymeric material can be removed and etching (note column 3, line 65 to column 4, line 5, where the polymeric material would be organic).
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the clamed invention to modify Watchko in view of Hanson, Yancey and Baughman, EITHER alone, or optionally further in view of EITHER von Niessen OR Nagayama to specifically provide organic residue initially present in the form of cutting oil and/or adhesive product/polymer residue on the substate surface and that the non-thermal plasma stream treatment of the substrate surface would also etch such organic residue from the metal surface of the article and to provide the etching treatment the metal surface of the article would be positioned to receive the non-thermal plasma stream to also perform such etching, as suggested by Watcko, Hanson and Yancey with an expectation of providing a desired surface prepared for further treatment, since Watchko indicates that a plasma pretreatment of the surface can be for cleaning and/or etching (that indicating that something can be present on the surface to be cleaned/etched), Hanson describes that the metal surface to be treated with the plasma can conventionally have residues of cutting oil/adhesive/ polymer present (which would be understood to be organic material as described by Hanson) that is to be removed with the plasma treatment, as well as oxide layer formation, and Yancey also indicates that the non-thermal treatment can etch materials on the surface, including adhesive and polymeric material (organic), and by removing such material, the desired cleaning of such material from the surface would be indicated, giving a clean surface with the treated energized surface regions, where since the non-thermal plasma treatment is to also etch the organic residues from the metal surface of the article, the metal surface of the article would also be positioned to provide such etching.
Optionally, Hewson evidences that cutting oils would conventionally be provided with organic material, including polymerized material (note the abstract, claim 1, column 2, line 45 to column 2, lines 55).
Babu evidences that PSA is conventionally used to refer to “pressure-sensitive adhesive” (note column 1, lines 5-20) and can be used for bonding to metal (note column 9, lines 55-60, where organic acrylate can be used, for example, and column 10, lines 15-25, with testing on steel), and that such materials are conventionally made with organic material such as various polymers (note column 2, lines 20-30).
Thus, Hewson would evidence how described cutting oil residue of Hanson would conventionally have organic material including polymer and Babu would evidence how adhesives (such as PSA described by Hanson) would conventionally have organic material including polymer, thus further evidencing that the material indicated as initially present and removable by Hanson and Yancey would be organic/polymer containing material, and by removing such material, the desired cleaning of such material from the surface would be indicated, giving a clean surface with the treated energized surface regions, where since the non-thermal plasma treatment is to also etch the organic residues from the metal surface of the article, the metal surface of the article would also be positioned to provide such etching.
Claim 3: As to the plasma stream comprising monatomic oxygen species, this would be suggested by Yancey which indicates etching using oxygen gas source (column 5, lines 1-10) and providing reactive species of O (so monatomic oxygen) in the plasma gas (column 7 lines 40-45), where Watchko also notes oxygen gas for the plasma (0029).
Claim 7: The arc spray coating of Watchko would be directed to the outer oxide surface region, because the oxides would be formed on the surface as discussed for claims 1, 6, which is where the coating would be applied by arc spraying, and Watchko indicates coating the entirety of surface 18, so the outer oxide region would be coated as well (0027).
Claim 10: The article would be metal and the chemical bonding sites would therefore be formed on the metal surface of the article as discussed for claim 1 above.
Claim 14: Watchko would indicate that the article can be metallic/metal and the surface would be metallic/metal as the surface of a simply metallic material (note 0024 and discussion for claim 1 above). The non-thermal plasma stream would be suggested to comprise an energetic species chemically reactive with the metal surface, since Hanson indicates how the surfaces such as aluminum, steel discussed for Watchko can form oxides in ambient conditions (which would react with oxygen) and have oxide groups on the surface and further can increase with the plasma treatment metal oxide content on the substrate surface (column 4, lines 25-32, column 2, line 55 through column 3, line 15), where Hanson indicates using oxygen for the plasma that generates metal oxide groups on the metal substrate (column 3, lines 55-65) and Yancey further indicates using oxygen species and oxygen feed gas (column 7, lines 40-48, column 5, lines 1-10).
Claim 15: Yancey would further suggest that the non-thermal plasma stream have a gas curtain associated the plasma stream to help shape the stream, where this can be the auxiliary gas (such as 568 or 768) or one of 568 and 768 can be the auxiliary gas and the other considered the gas curtain (note column 9, lines 1-65, and figures 5-9).
Claim 21: As to the non-thermal plasma stream comprising monatomic oxygen species (a monatomic chemical species), this would be suggested by Yancey which indicates etching using oxygen gas source (column 5, lines 1-10) and providing reactive species of O (monatomic oxygen) in the plasma gas (column 7 lines 40-45), where Watchko also notes oxygen gas for the plasma (0029).
Claim 25: All the features of claim 25 would be shown by Watchko in view of Hanson, Yancey and Baughman, EITHER alone OR further in view of EITHER von Niessen OR Nagayama, and optionally as evidenced by Hewson and Babu, where the generated non-thermal plasma stream at atmospheric pressure and comprising monatomic oxygen would be indicated as discussed for claims 1 and 3, and the positioning the metal surface to receive the non-thermal plasma stream indicated and to etch organic residues from the metal surface of the article as discussed for claim 1. Treating the metal surface with the non-thermal plasma stream to create a metal oxide region/species with an outer oxide surface, higher surface energy (energized surface region), chemical bonding sites promoting chemical bonding with the energized surface region, etc. as claimed and etching organic residues indicated as discussed for claims 1, 2, 6. Generating a metallic arc-spray coating stream comprising a stream of projected molten metal surrounded by a sheath of air plasma such that molten metal surfaces of the molten metal are plasma treated would be indicated as discussed for claim 1 above. The directing the metallic arc-spray coating stream at the metal oxide region is indicated as discussed for claim 1 above. The application of inert gas auxiliary gas onto the metal surface of the article would be suggested as discussed for claim 1 above. The molten metal bonding with the metal oxide region to bond the arc spray coating to the surface would be suggested by Watchko at 0028 which has a bonded coating which can be chemical bonding, for example, and following the same process as claimed which would give the same results, where the Watchko materials are such that would also be indicated to get oxides on the surface as indicated by Hanson when providing suggested plasma cleaning etc, and Watchko allows surface modification with the plasma and substrate material that can have oxides in ambient, such that it would be understood that the oxides would be acceptably provided on the surface before the arc spray coating.
Claim 29: Watchko describes a method to adhere an arc spray coating to a surface of an article (note 0027-0028, 0023), where the article can be metal and the surface would be metal as the surface of a simply metal material (0012, 0025-0027), where the method can include an initial plasma treatment of surface 18 providing a cleaning and/or etching or otherwise modifying the surface 18 with a plasma generated from the ionization of oxygen, for example (0029), where since the surface 18 of the article is to be treated with the plasma it would have been at least suggested to position the plasma and the surface of the article to receive the plasma for treatment so that actual treatment occurs, noting how in figure 4 and 0034-0036 the surface of the article would be positioned for treatment with the arc spraying, for example. Watchko further describes generating an arc spray coating stream and directing the arc spray coating stream at what would be the plasma treated surface region, where the arc spray coating stream forms an arc spray coating surface associated with what would be the plasma treated surface region of the article (note 0034-0036 and figure 4, where it is noted that it is desired to cover substantially the entire surface of 18, and thus the plasma treated areas of 18, note 0027). Watchko further describes that the arc spray coating stream would spray molten metal to the surface of the article to be coated to deposit the molten metal on the plasma treated surface to provide coating (0027, 0032, 0035-0036, figure 4).
(A) As to using the plasma to create an energized surface region comprising a plasma treated surface of the article with a non-thermal plasma stream at atmospheric pressure, and as to the treatment of the energized surface region of a metal surface with the non-thermal plasma stream for a time such that the energized surface region comprises a metal oxide region/species having a higher surface energy than the metal surface of the article and being grown from a base metal of the article being treated (claim 29), and forming by the non-thermal plasma stream chemical bonding sites on the energized surface region, the chemical bonding sites promoting chemical bonding with the energized surface region,
Watchko notes that the article treated can be metal such as aluminum, steel, etc. (0025, 0012) and that it is desired for surface 18 to be at ambient temperature to avoid heat distortion, etc. (0030). Hanson describes how it is known to provide metal substrates (including aluminum, steel, etc.) that form oxides on exposure to ambient conditions (column 2, line 55 through column 5, line 20), where the substrate is treated with plasma by placing (so positioning) in a plasma atmosphere, where reactive species of the plasma (electrons, cations radicals) believed to react with contaminants, such as cutting oils, lubricants, corrosion inhibitors, adhesive products, etc and remove them as gaseous reaction products (e.g. CO2) while leaving the inorganic component, i.e. metal, metal oxide groups relatively unscathed, which would at least clean the surface, and any plasma source can be used, but atmospheric pressure generated plasmas preferred, where the plasma can be provided as a plasma jet and be derived from a feed gas that can include oxygen or air (column 3, lines 15-65), where it is further indicated that plasma conditions, including power density, feed gas flow rates, dwell time, and temperature can be controlled and selected to provide controlled removal of contaminant, and can maintain or increase the oxide content on the substrate surface (column 4, lines 10-32) and preferably the plasma has oxygen containing gas that is believed to generate metal oxide groups on the metal substrate (column 3, lines 55-60). Since the article/substrate is placed in the plasma atmosphere to treat, it is understood that the surface of the article would be positioned to receive the plasma stream/jet for the reaction treatment.
Furthermore, Yancey further describes an atmospheric pressure plasma can be provided as a plasma stream or plume or jet that would be directed towards a substrate and coating to remove a coating on a substrate by having components of the coating react with energetic species of the plasma (figures 2, 3, column 2, lines 10-25, where as shown the substrate would be positioned to receive the plasma stream that would be generated), where the substrate can be metallic and there is no limit on the coating type or composition that can be removed (column 6, lines 30-35), and the plasma plume etches the coating (column 7, lines 20-25), where the plasma can be a cold, or non-thermal, plasma and have reactive oxygen species in the plasma to react with the coating (column 7,lines 30-65), and where operating parameters can be controlled and there would be a time of treatment (column 8, lines 1-40), and where oxygen or air can be supplied to the plasma to give oxygen species (column 5, lines 1-10) and where removal described as etching and can remove with forming CO2 for example (column 7, lines 10-65).
Therefore it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Watchko to use a non-thermal plasma stream that is generated and at atmospheric pressure and to position the surface of the article to receive this non-thermal plasma stream and treating the surface of the article with this stream as suggested by Hanson and Yancey to provide a desirable surface cleaning/etching treatment and modification before the arc spraying, since Watchko teaches treating a metal surface such as aluminum or steel with plasma generated from oxygen gas, for example, to clean/etch/modify the surface before the arc spraying, and also teaches that it is desired to avoid heat distortion, etc. of the surface, and Hanson teaches that an atmospheric pressure plasma that generates plasma using oxygen gas for example, can be used to clean (remove contaminants) a metal surface such as aluminum or steel that forms oxides by placing it in the plasma atmosphere which can be a jet of plasma to react with the contaminants and remove them and can also increase the oxide content of the metal surfaces, and Yancey teaches that a form of atmospheric plasma using oxygen radicals that can also be used to similarly clean/etch/ remove coating on a surface that can be metal by reacting can be a non-thermal atmospheric plasma, where articles would be provided and placed for Hanson and Yancey so that the surface can be treated with the plasma. As to the treatment providing an energized surface region comprising a plasma treated surface of the article, it would be understood that this would be indicated to occur by Hanson and Yancey since the surface would be exposed to an energized reacting plasma as described by applicant, and so the area exposed would be energized, and as well, Hanson indicates that further oxidation can occur, and noting original claims 5, 14, for example it is indicated as energized region a metal oxide region, so it is understood that the oxidation at least would give an energized surface region to the extent claimed where occurs, and that would occur over time, noting the dwell time control indicted by Hanson and time of treatment indicated as used by Yancey, such that the energized surface region is treated over time, where the Watchko materials are such that would also be indicated to get oxides on the surface as indicated by Hanson as materials that form oxides in ambient, and also when providing suggested plasma cleaning etc, and Watchko allows surface modification with the plasma, so it would be understood that the oxides would be acceptably provided on the surface before the arc spray coating, and as well does not prevent exposure to ambient and so would not prevent oxides from being present as well, and this oxide formation would meet the requirement of the energized surface region comprises a metal oxide region/species. Furthermore, as to the oxide surface region being grown from a base metal of the surface, since the reaction is with the surface to increase oxide content on the substrate surface, the oxide content would be understood to be grown from a base metal of the substrate article, and would have an outer oxide surface on the top. With reaction and growth, it would be further understood there would be a time of growth, to allow the reaction. Furthermore, it would be suggested to provide such oxide formation and growth, since Hanson indicates how this is a process that desirably occurs with the plasma treatment (note column 3, lines 55-60) that includes the cleaning process (note column 3, lines 15-30). As to the oxide content having a higher surface energy than the metal surface, since the surface is energized by the treatment, it is understood to provide the higher surface energy claimed. Furthermore, since the process is the same described by applicant for the higher surface energy, the same results as claimed would be expected.
Furthermore, as to the non-thermal plasma stream forming chemical bonding sites on the energized surface region, the chemical bonding sites promoting chemical bonding with the energized surface region as claimed, the process as discussed above would indicate forming oxides on the surface, and this is understood to form a chemical bonding sites that would promote chemical bonding with the energized surface region as claimed since applicant indicates providing the oxide formation to enhance bonding and the process giving chemical bonding in the specification as filed, and Where the claimed and prior art products are identical or substantially identical in structure or composition, or are produced by identical or substantially identical processes, a prima facie case of either anticipation or obviousness has been established. In re Best, 562 F.2d 1252, 1255, 195 USPQ 430, 433 (CCPA 1977). Watchko also allows chemical bonding (oo28).
Optionally, further using EITHER von Niessen OR Nagayama, von Niessen further describes a process for applying a thermally sprayed coating using a plasma spraying (abstract) where the substrate is typically metallic (0018), and where a pretreatment cleaning is performed on the substrate with a plasma treatment, and an oxide layer is generated on the substrate (note for example, 0020, 0028, 0038), and where this oxide layer gives a better adhesion of the coating structure on the substrate (note 0028). Nagayama further describes a substrate can be provided of a metal such as an aluminum alloy (note 0031), where the substrate is provided with a pretreatment using plasma to form an oxidation of the surface (note 0029, 0034-0035) and then the surface is thermally sprayed by a process such as plasma spraying (note 0036, 0042), where the oxidation pre-treatment helps improve the adhesion of the thermally sprayed coating (0029).
Therefore, it further would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention that when providing the process of Watchko in view of Hanson and Yancey, to specifically optimize the conditions to provide the oxide formation as taught by Hanson, for example, to help with adhesion of the further sprayed coating (thermally sprayed) of Watchko as suggested by EITHER von Niessen OR Nagayama, since Hanson indicates how the plasma treatment with cleaning can also be used to provide oxide on the surface, and EITHER von Niessen OR Nagayama would indicate how it is known that providing oxide on the surface of a metal substrate can help with better adhesion of a further applied thermal sprayed coating. Additionally, both von Niessen and Nagayama notes further plasma spraying can be used to apply the coating, and section (B) below would further suggest the use of plasma in the arc spraying process.
(B) Furthermore, as to the arc spray coating stream comprising a stream of molten metal surrounded by a sheath of air plasma such that molten metal surfaces of the molten metal are plasma treated, Watchko would provide that the arc spraying would provide an arc spray stream of molten metal being propelled towards the metal surface of the article (note 0035-0036, 0027, 0032, figure 4), where the stream would have molten droplets and thus molten metal surfaces of these droplets (0035-0036, figure 4). Watchko would indicate gas 84 provides atomization giving the droplets (note 0034-0036). Watchko notes that a secondary stream gas can be provided that would provide a sheath of gas around the molten metal stream and further atomization noting the exits at 92 in figure 4 for additional gas 88 (0035).
Baughman further indicates that it is also known to provide wire arc spraying where a plasma provided with air as a creating gas (so air plasma), for example, is directed to pass to a continuously fed wire tip along with an arc to the tip where additional air is funneled around the plasma plume and also intersects the formed spray to accelerated atomize and shroud the metal droplets (column 2, lines 30-50). As shown by figure 1, the melting with the arc and plasma intersecting the wire would give stream of molten metal, where given the plasma plume would be expected to be at least acceptably surrounded by a sheath of plasma gas (at the least, before the additional air, and there would still be a stream of plasma headed to the surface as well), and as well the droplets of molten metal would also be exposed to the plasma and thus be treated by the plasma while being propelled to the surface of the article being coated (note figure 1, showing the plasma plume travelling with the droplets to the substrate surface), where an apparatus for such application is provided as shown in figure 1.
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the claimed invention to modify Watchko in view of Hanson and Yancey, EITHER alone OR further in view of EITHER von Niessen OR Nagayama to either use air plasma for atomizing gas 84 as in Watchko or use a wire arc system as in Baughman from the teachings of Baughman with an expectation of providing a predictably acceptable spraying, since Watchko provides arc spraying, and Baughman provides that arc spraying can further be conventionally provided with a central air plasma gas that forms a stream of molten metal from a wire tip and where there is a further secondary stream of gas that provides atomization, where when the plasma gas impacts the wire and forms a molten stream it would be understood to provide a sheath of plasma around the molten stream as the plasma plume would be indicated as surrounding the wire tip and metal or at least be expected to predictably and acceptably be provided to do so from the plasma plume shape shown, and as well the plasma would treat the metal surfaces of the droplets formed in the molten stream while being propelled to the surface as described above.
(C) Furthermore, as to applying an auxiliary gas onto the metal surface of the article, where the gas can comprise an inert gas, for example,
Yancey would further indicate how auxiliary gas can be provided to shape the plasma (for the non-thermal plasma stream), providing a focused stream that may increase removal rate, and also can assist in cooling the substrate during application of the plasma (note column 9, lines 1-65, and figures 5-9, where auxiliary gas can be provided on one side of the plasma flame as gas curtain or air knife 568, on the other side as gas curtain or air knife 768, or auxiliary gas can be provided with two streams, 568 and 768 at the same time, noting figure 9). The auxiliary gas can be inert gas (column 9, lines 39-40, described for 768, but understood to apply to 568 as well, since 768 is used for the same purpose as 568, note column 9,lines 45-50). It is understood that the auxiliary gas used as described in Yancey would be applied onto the surface of the article, since it follows and shapes and flows alongside the non-thermal plasma (note figures 5-9) that would be directed to the surface of the article to treat the surface, and as well, it is indicated as providing cooling to the substrate, so indicted to be directed to the surface to impact and cool the surface of the substrate, or at least be suggested to do so to give the desired tr