# US 2018/0023185 A1 · Plasma Process and Reactor for the Thermochemical Treatment of the Surface of Metallic Pieces > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 2018/0023185 A1 - Document ID: US20180023185A1 - Status: Published application - Kind: A1 - Application number: 15/520,154 - Filed: 2015-10-19 - Published: 2018-01-25 - Earliest claimed: 2014-10-20 - Assignees: Universidade Federal De Santa Catarina - Applicants: Universidade Federal De Santa Catarina - Inventors: Cristiano BINDER; Euclides Alexandre BERNARDELLI; Gisele HAMMES; Aloisio Nelmo KLEIN; Thiago De Souza LAMIM; Roberto BINDER - Web page: https://patentgrep.com/patent/US20180023185A1 ## CPC - C23C 14/22: characterised by the process of coating - C23C 16/26: Deposition of carbon only - C23C 16/50: using electric discharges {(generation and control of plasma in discharge tubes for surface treatment H01J37/32, H01J37/34)} - H01J 37/32027: {DC powered} - H01J 37/32532: {Electrodes} - H01J 37/3423: {Shape} - 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) - H01J: ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS (spark-gaps H01T; electric arc lamps H05B31/00; particle accelerators H05H) ## Abstract The reactor (R) has a reaction chamber (RC) provided with a support (S) for metallic pieces and with a system of an anode, connected to a ground, and of a cathode system connected to the support (S) and to a pulsating DC power supply. In the reaction chamber (RC), heated and supplied with a gas load, is formed, by means of an electric discharge in the cathode, a gas plasma. A liquid or gas precursor is admitted in at least one tubular cracking chamber associated with a high voltage energy source. It may be provided at least one tubular sputtering chamber associated with an electric power supply receiving a solid precursor. A potential difference is applied between the anode and one and/or other of said tubular chambers, to release the alloy elements to be ionically bombarded against the metallic pieces, either simultaneously or individually and in any order. ## Claims ### Claim 1 A process for the thermochemical treatment of the surface of metallic pieces, in a plasma reactor (R) having a reaction chamber (RC) provided with: a support (S) carrying the metallic pieces; a system of anode and cathode having one of its electrodes associated with a pulsating DC power supply; an inlet of ionizable gas load; an inlet of liquid or gas precursor; and an outlet for exhaustion of gas load, characterized in that it comprises the steps of: a) connecting the anode to a first electrode and to a ground and connecting the cathode to the support (S), operating as the other electrode of the system of anode and cathode, and to a negative potential of the pulsating DC power supply; b) statically positioning the metallic pieces on the support (S) associated with the cathode in the interior of the reaction chamber (RC); c) surrounding the support (S) and the metallic pieces with an ionizable gas load supplied to the reaction chamber (RC) through the inlet; d) heating the interior of the reaction chamber (RC) to a working temperature; e) applying to the cathode, associated with the support (S) and with the metallic pieces, an electric discharge in order to cause the formation of a gas plasma of ions having a high kinetic energy surrounding the metallic pieces and the support (S); f) admitting a flow of liquid or gas precursor in at least one tubular cracking chamber having at least one end open to the interior of the reaction chamber (RC) and being associated with a high voltage energy source; g) applying a potential difference between the at least one tubular cracking chamber and the anode of the system of anode and cathode for dissociating the molecules of the precursor admitted into said tubular cracking chamber, releasing, to the interior of the reaction chamber (RC), the atoms of the alloy elements to be ionically bombarded against the surfaces of the metallic pieces (1) negatively polarized by the pulsating DC power supply; and h) providing the exhaustion of the gas load from the interior of the reaction chamber (RC). ### Claim 2 (depends on 1) The process, as set forth in claim 1, characterized in that the tubular cracking chamber is subjected to the working temperature in the interior of the reaction chamber (RC). ### Claim 3 (depends on 1) The process, as set forth in claim 1, characterized in that the tubular cracking chamber defines a hollow cathode in association with the anode the system of anode and cathode of the reaction chamber (RC) of the reactor (R). ### Claim 4 (depends on 1) The process, as set forth in claim 1, characterized in that the liquid precursor is selected between a hexamethyldisiloxane (C6Hi8OSi2) and a silane. ### Claim 5 (depends on 1) The process, as set forth in claim 1, characterized in that the ionizable gas load further comprises adding a gas selected from oxygen, hydrogen, nitrogen and argon to react with the atoms or molecules obtained by cracking of the liquid precursor, thus forming compounds directed to the metallic pieces with a kinetic energy resulting from the acceleration caused by the potential difference applied to the system of anode and cathode. ### Claim 6 (depends on 1) The process, as set forth in claim 1, characterized in that the ionization of the gas load and of the liquid precursor is carried out by a DC electric discharge under a low pressure atmosphere, generating plasma and producing the alloy elements for the surface treatment of the metallic pieces. ### Claim 7 (depends on 1) The process, as set forth in claim 1, characterized in that the cracked precursor, released from the tubular cracking chamber and to have the desirable atoms of the alloy elements ionically bombarded against the surface of the metallic pieces, has eventual undesirable atoms retained in a filtering device located immediately downstream from said open end of the tubular cracking chamber. ### Claim 8 (depends on 7) The process, as set forth in claim 7, characterized in that the retention of undesirable atoms of the cracked precursor is obtained by chemical reaction between said atoms and the filtering device. ### Claim 9 (depends on 1) The process, as set forth in claim 1, characterized in that it further comprises, before, during or after the steps of surface thermochemical treatment by cracking of the liquid or gas precursor, the steps of: a) if not already previously carried out, connecting the anode to a first electrode and to a ground and connecting the cathode to the support (S), operating as the other electrode of the system of anode and cathode, and to a negative potential of the pulsating DC power supply; b) if not already previously carried out, statically positioning the metallic pieces on the support S associated with the cathode inside the reaction chamber RC; c) if not already previously carried out, surrounding the support (S) and the metallic pieces with an ionizable gas load fed to the reaction chamber (RC) through the inlet; d) if not already previously carried out, heating the interior of the reaction chamber (RC) to a working temperature; e) applying to the cathode, associated with the support (S) and to the metallic pieces, an electric discharge in order to cause the formation of a ion gas plasma, having high kinetic energy, surrounding the metallic pieces and the support (S); f) providing a solid precursor defining the interior of at least one tubular sputtering chamber, having one end open to the interior of the reaction chamber (RC) and being associated with an electric power supply; g) applying a potential difference between the at least one tubular sputtering chamber and the anode of the system of anode and cathode in order to provide the sputtering of the solid precursor, releasing from the latter and into the interior of the reaction chamber (RC), the alloy elements to be ionically bombarded against the surfaces of the metallic pieces negatively polarized by the pulsating DC power supply; and h) providing the exhaustion of the gas load from the interior of the reaction chamber RC. ### Claim 10 (depends on 9) The process, as set forth in claim 9, characterized in that the at least one tubular sputtering chamber is subjected to the working temperature in the interior of the reaction chamber (RC). ### Claim 11 (depends on 9) The process, as set forth in claim 9, characterized in that the at least one tubular sputtering chamber defines a hollow cathode associated with the anode of the system of anode and cathode of the reaction chamber (RC) of the reactor (R). ### Claim 12 (depends on 9) The process, as set forth in claim 9, characterized in that the ionization of the gas load and of the solid precursor is carried out by a DC electric discharge under a low pressure atmosphere, generating plasma and producing the alloy elements for the surface treatment of the metallic pieces. ### Claim 13 A process for the thermochemical treatment of the surface of metallic pieces, in a plasma reactor (R) having a reaction chamber (RC) provided with: a support (S) carrying the metallic pieces; a system of anode and cathode having one of its electrodes associated with a high voltage pulsating DC power supply; an inlet of ionizable gas load; and an outlet, for exhaustion of gas load, characterized in that it comprises the steps of: a) connecting the anode to a first electrode and to a ground and connecting the cathode to the support (S), operating as the other electrode of the system of anode and cathode, and to a negative potential of the pulsating DC power supply; b) statically positioning the metallic pieces in the support (S) associated with the cathode in the interior of the reaction chamber (RC); c) surrounding the support (S) and the metallic pieces with an ionizable gas load supplied to the reaction chamber (RC) through the inlet; d) heating the interior of the reaction chamber (RC) to a working temperature; e) applying to the cathode, associated with the support (S) and with the metallic pieces, an electric discharge in order to cause the formation of a gas plasma of ions having a high kinetic energy surrounding the metallic pieces and the support (S); f) providing a solid precursor defined inside a tubular sputtering chamber having one end open to the interior of the reaction chamber (RC) and being associated with an electric power supply; g) applying a potential difference between at least one tubular sputtering chamber and the anode of the system of anode and cathode in order to provide the sputtering of the solid precursor, releasing from the latter and into the reaction chamber (RC), the alloy elements to be ionically bombarded against the surfaces of the metallic pieces negatively polarized by the pulsating DC power supply; and h) providing the exhaustion of the gas load from the interior of the reaction chamber (RC). ### Claim 14 (depends on 13) The process, as set forth in claim 13, characterized in that the at least one tubular sputtering chamber is subjected to the working temperature of the interior of the reaction chamber (RC). ### Claim 15 (depends on 13) The process, as set forth in claim 13, characterized in that the at least one tubular sputtering chamber defines a hollow cathode in association with the anode of the anode-cathode system of the reaction chamber (RC) of the reactor. ### Claim 16 (depends on 13) The process, as set forth in claim 13, characterized in that the ionization of the gas load and of the solid precursor is carried out by a DC electric discharge under a low pressure atmosphere, generating plasma and producing the alloy elements for the surface treatment of the metallic pieces. ### Claim 17 (depends on 1) The process, as set forth in claim 1, characterized in that the ionizable gas load is admitted in the interior of the reaction chamber (RC) by the upper part of the reactor (R) and according to a vertical symmetry axis of the reaction chamber (RC) and of the arrangement of the metallic pieces on the support (S). ### Claim 18 A reactor for the thermochemical treatment of the surface of metallic pieces, said plasma reactor (R) having a metallic housing defining, internally, a reaction chamber (RC) provided with: a support (S) carrying the metallic pieces; a system of anode and cathode associated with a pulsating DC power supply; an inlet of ionizable gas load; an inlet of liquid or gas precursor; an outlet of exhaustion of gas load, connected to a vacuum system; and a heating means mounted to the metallic housing in order to heat the interior of the reaction chamber (RC) to a working temperature, characterized in that it comprises: the anode connected to a first electrode and to a ground, and the cathode connected to the support (S), operating as the other electrode of the system of anode and cathode, and to a respective negative potential of the pulsating DC power supply; the support (S) carrying, statically, the metallic pieces and being associated with the cathode in the interior of the reaction chamber (RC); at least one tubular cracking chamber of a respective flow of liquid or gas precursor to be admitted therein, having at least one end open to the interior of the reaction chamber (RC) and being associated with a high voltage energy source for dissociating the molecules of the precursor and their release to the interior of the reaction chamber (RC). ### Claim 19 (depends on 18) The reactor, as set forth in claim 18, characterized in that the at least one tubular cracking chamber is positioned in the interior of the reaction chamber (RC), above the support (S) and is subjected to the working temperature of the interior of the reaction chamber (RC) and receives the flow of liquid or gas precursor by means of a supply tube coming from a source of liquid or gas precursor, external to the reactor. ### Claim 20 (depends on 19) The reactor, as set forth in claim 19, characterized in that the at least one tubular cracking chamber defines a hollow cathode in association with the anode of the system of anode and cathode of the reaction chamber (RC) of the reactor (R). ### Claim 21 (depends on 19) The reactor, as set forth in claim 19, characterized in that the energization of the at least one tubular cracking chamber is carried out by the supply tube itself of liquid or gas precursor. ### Claim 22 (depends on 18) The reactor, as set forth in claim 18, characterized in that it further comprises a filtering device located immediately downstream from the respective at least one open end of the tubular cracking chamber and which is able to chemically react with eventual undesirable atoms released by the tubular cracking chamber together with the desirable atoms of the alloy elements to be ionically bombarded against the surface of the metallic pieces, said eventual undesirable atoms being retained in the filtering device. ### Claim 23 (depends on 22) The reactor, as set forth in claim 22, characterized in that the filtering device is defined by a tube built or internally lined with a material that may react with said undesirable atoms, and is positioned and affixed adjacent to and axially aligned with said open end of the tubular cracking chamber. ### Claim 24 (depends on 23) The reactor, as set forth in claim 23, characterized in that the filtering device is defined by a tubular extension of the tubular cracking chamber itself. ### Claim 25 (depends on 18) The reactor, as set forth in claim 18, characterized in that it further comprises: at least one tubular sputtering chamber carrying the solid precursor, having one end open to the interior of the reaction chamber (RC) and being associated with an electric power supply, in order to provide the sputtering of the solid precursor and the release of its alloy elements ionically bombarded against the metallic pieces negatively polarized by the pulsating DC power supply. ### Claim 26 (depends on 25) The reactor, as set forth in claim 25, characterized in that the at least one tubular sputtering chamber is positioned in the interior of the reaction chamber (RC), above the support (S) and is subjected to the working temperature of the interior of the reaction chamber (RC). ### Claim 27 (depends on 26) The reactor, as set forth in claim 26, characterized in that the at least one tubular sputtering chamber defines a hollow cathode in association with the anode of the system of anode and cathode of the reaction chamber (RC) of the reactor (R). ### Claim 28 (depends on 27) The reactor, as set forth in claim 27, characterized in that the solid precursor is defined by the respective tubular sputtering chamber. ### Claim 29 A reactor for the thermochemical treatment of the surface of metallic pieces, said plasma reactor (R) having a metallic housing defining, internally, a reaction chamber (RC) provided with: a support (S) carrying the metallic pieces; a system of anode and cathode associated with a high voltage pulsating DC power supply; an inlet of ionizable gas load; a solid precursor operatively associated with the interior of the reaction chamber (RC); an outlet, of exhaustion of gas load, connected to a vacuum system; and a heating means mounted to the metallic housing, in order to heat the interior of the reaction chamber (RC) to a working temperature, characterized in that it comprises: the anode connected to a first electrode and to a ground, and the cathode connected to the support (S), operating as the other electrode of the system of anode and cathode, and to a negative potential of the pulsating DC power supply; the support (S) carrying, statically, the metallic pieces and being associated with the cathode in the interior of the reaction chamber (RC); at least one tubular sputtering chamber carrying the solid precursor, having one end open to the interior of the reaction chamber (RC) and being associated with an electric power supply, in order to provide the sputtering of the solid precursor and the release of its alloy elements ionically bombarded against the metallic pieces negatively polarized by the pulsating DC power supply. ### Claim 30 (depends on 29) The reactor, as set forth in claim 29, characterized in that the at least one tubular sputtering chamber is positioned in the interior of the reaction chamber (RC), above the support (S) and is subjected to the working temperature of the interior of the reaction chamber (RC). ### Claim 31 (depends on 30) The reactor, as set forth in claim 30, characterized in that the at least one tubular sputtering chamber defines a hollow cathode in association with the anode of the system of anode and cathode of the reaction chamber (RC) of the reactor (R). ### Claim 32 (depends on 31) The reactor, as set forth in claim 31, characterized in that the solid precursor is defined by the respective tubular sputtering chamber. ### Claim 33 (depends on 18) The reactor, as set forth in claim 18, characterized in that inlet of ionizable gas load is provided in the upper part of the reactor (R) and according to a symmetry vertical axis of the reaction chamber (RC) and of the arrangement of the metallic pieces on the support (S).