Method of manufacturing powdered materials by controlled spraying of atoms of a target material and subsequent deposition on a powdered base material

Abstract

The present invention discloses a method of manufacturing novel powdered materials by controlled spraying of atoms. In this method, the material to be deposited (target) can be chosen from among any of the elements in the periodic table or a combination of at least two of said elements. The material that will receive the deposit, called the base material or substrate, can be chosen from among the following materials: polymeric, metallic, semiconducting, ceramic, molecular sieves, perovskites, MOFs, carbonaceous materials or any type / class of powdered material with a vapour pressure of less than 10-1mBar. The method taught by the present invention describes means of planning and achieving different coating structures for the base material (substrate) by defining and controlling production processes. This makes it possible to derive a plurality of novel materials with novel properties as well as predefined properties.

Description

PROCESS OF MANUFACTURING POWDERED MATERIALS, THROUGH CONTROLLED SPRAYING OF ATOMS OF A TARGET MATERIAL AND SUBSEQUENT DEPOSITION ON POWDERED BASE MATERIAL Field of Invention Patent

[0001] The present invention is in the field of materials engineering. More specifically, it relates to a standardized and precise process for manufacturing powdered materials, where the deposition layer structure can be planned and precisely achieved through the definition and control of production parameters. The present invention allows for the planning and execution of a variety of new structures and materials. Background of the Invention Patent

[0002] Climate change is one of the factors driving researchers to develop new, cleaner technologies—those that use less energy, emit fewer pollutants, or require smaller quantities of raw materials for manufacturing. To this end, the study of new materials is gaining increasing traction.

[0003] The methodology of coating base materials (substrates) with others (target), in order to confer new properties, is quite old and has brought many alternatives to the various sectors of industry, such as the automotive, aviation, structures, jewelry, catalytic processes, among others.

[0004] New materials are commonly developed through the appropriate combination of natural elements. This combination can occur through chemical or physical means. Generally, chemical methods have some disadvantages, such as greater waste generation, low stability, and greater difficulty in process control. Within physical methods, technologies are also already known, including: atom ejection by momentum transfer (sputtering), thermal deposition, electron beam sublimation ejection (e-beam deposition), and laser ablation (laser ablation), known as PVD (Physical Vapor Deposition).

[0005] Traditionally, PVD processes are used in various industrial sectors, such as microelectronics, data storage, medical equipment and devices, energy, metalworking (especially on solid parts requiring advanced properties), decorative coatings such as glass facades between buildings, jewelry, etc. It is important to note that in traditional industry, the process is commonly applied to solid, flat parts of any shape and size.

[0006] However, traditional surface coating processes present gaps in the development of new materials, primarily due to the limited use typically found in already massive and solid parts. However, they require large concentrations of target elements for adhesion to the surface of the base material (substrate), and they lack precise control over the formation of various structural possibilities on the surfaces of base materials (flat substrates).

[0007] In a search of the state of the art, in national and international databases, some documents were located that deal with particulate material deposition processes, through physical vapor deposition (PVD).

[0008] Patent application BRPI0823165A2 refers to particulate ceramic materials coated with a layer of nanoparticles with multiple crystalline structures and the process for obtaining them. These coatings are obtained by introducing precursors into a water-in-oil emulsion, which, when decomposed during detonation, form nanoparticles that adhere to the surface of the ceramic powder. The characteristics of the resulting coating, such as thickness, adhesion, porosity, and coverage percentage, can be adjusted by controlling process variables. The thickness of the layer to be coated varies between 5 and 150 nm. Ceramic powders can be coated with multiple crystalline structures, including binary, ternary, or higher. However, although the document describes a process where specific manufacturing characteristics are defined through control of production processes, such as layer structure, for example, this objective is achieved through a “water-in-oil emulsion detonation” process, which differs from the present invention, where the applied process is PVD.

[0009] Document WO2016175552A1 describes a method for preparing a conductive composite resin, which includes the step of forming inorganic nanoparticles on the surface of a carbon base, with particle sizes between 0.01 and 100 micrometers, by PVD. The document in question describes a powdered base material (substrate) and a target with nanometric particles to be added to the surface of the base material, through PVD. The powdered base material is subjected to agitation at a rate of 0.1 to 400 rpm. The vaporized particles are deposited on the base powder at a thickness of 1 to 10 micrometers per unit area per minute, thus controlling the parameters can provide different structures in the layer. The process described here does not teach or demonstrate means of controlling the final structure to be formed, with precise control of the dispersion, concentration, and dimension of the final structure.

[0010] Document WO0028969A2 describes a physical vapor deposition (PVD) process for pharmaceutical particles. The number of coating particles and the structure of the coating layer vary according to the target objective and are achieved by controlling the physical parameters of the deposition process, such as vapor pressure and exposure time of the target particles. The document also teaches that the material to be coated can be of organic or inorganic origin, and the coating thickness can vary from 1 nm to 1000 nm or more. However, this document does not disclose a process for obtaining new materials with single-atom, cluster, or sub-nanometric structures, nor does it reveal precise control of the dispersion of atoms on the substrate surface.

[0011] Document US2013011440A1, presented here, describes a method for thin layer deposition, specifically for the production of multilayer coatings comprising nanolayers, nanostructures, and nanocomposites. The deposition process is demonstrated through the following steps: a) selecting the substrate material; b) selecting the target material, which comprises at least two with distinct physicochemical properties; c) delivering a laser beam of non-uniform intensity and width; d) aiming the laser at the target, with at least two target segments exposed to different laser intensities; and e) coordinating the parameters so that each target material absorbs an adequate amount of energy to enable evaporation or desorption of the material.

[0012] The target materials can be organic or inorganic. The parameters to be controlled are: wavelength, laser beam pulse duration, pulse repetition rate, distance from the target material to the substrate, and the substrate's orientation relative to the target. In addition to not disclosing a process that teaches the formation of single-atom, cluster, or sub-nanometer structures, the process required by this document does not include powdered substrates, which differs from the present invention.

[0013] Document KR102478642B1 teaches a process for producing niacinamide powder containing gold particles and, more specifically, teaches a method for producing niacinamide powder containing gold particles capable of maintaining a colloidal state in a solvent, uniformly distributing gold nanoparticles. However, this document does not disclose a controlled deposition process according to the desired structure, which distances it from the present invention.

[0014] Thus, the object of this patent is to solve the limitations related to the development of new materials with control and precision in the formation of different structures on the surface of the substrate. Summary of the Invention Patent

[0015] The object of this invention patent is a standardized and precise process for manufacturing powdered materials, through the controlled pulverization of atoms of a target material and its subsequent deposition on a base material (substrate), in powder form, which comprises the steps of: a) Selecting the substrate material in powder form, with a vapor pressure lower than 10°mBar; b) Carrying out, if necessary, the degassing step of the substrate material; c) Inserting the substrate material into the main vacuum chamber; d) Evacuating the chamber to the lowest possible pressure, preferably a maximum of 5x10' 6mBar; e) Select at least one element from the periodic table or its combinations, which is solid, with vapor pressure less than 10'°mBar as target material; f) Define the type of coating structure to be formed on the surface of the substrate material, which can be single atom, cluster, sub-nanoparticle or nanoparticle; g) Define the values ​​of the parameters: power density and deposition rate; h) Insert the target materials into the equipment cannons; i) Insert a controlled flow of at least one gas into the vacuum chamber, between 0.1 sccm and 10 sccm; j) Maintain the working pressure between 5x10' 3 mBar and 5x10' 1 mBar; k) Activate the voltage source and stabilize the plasma at a power density between 0.1W / cm 2 and 25W / cm 2. l) Start the process of deposition of the target material atoms on the surface of the substrate material; m) Wait for a period of 0.3 min / g to 500 min / g, for the deposition of the target material atoms on the surface of the substrate material; n) Maintain the atomic concentration not exceeding 10 at%; o) Turn off the voltage source; p) Pot the coated substrate material.

[0016] It is an object of the present invention that the substrate chosen is any powdered material with a vapor pressure of less than 10 01 mBar, preferably, polymeric, metallic, semiconductor, ceramic materials, molecular sieves, perovskites, MOFs (metalorganic networks), carbonaceous materials.

[0017] It is also an object of the present invention that the target material preferably has a vapor pressure of 10°mbar.

[0018] It is also an object of the present invention to perform degassing if the substrate material presents moisture;

[0019] Another object of the present invention, where the degassing of the substrate material comprises the steps of: a) inserting the substrate material into a pre-vacuum chamber; b) evacuating the chamber until it reaches a pressure of 2x10' 2 mBar; c) keep the substrate material in the pre-vacuum chamber for a period between 1 h and 8 h;

[0020] It is also an object of the present invention that the optional step of degassing the substrate material occurs preferably within 3 hours;

[0021] It is also an object of this invention to define the operating parameter data: power density and deposition rate, comprising the steps: a) Establish an initial power density of the equipment, which can be 0.1 to 25 W / cm 2; b) Calibrate the deposition rate of the target material; c) Check whether the deposition rate of the target material is adequate to reach the atomic concentration of the planned structure; if not, d) Adjust the power density until the deposition rate is sufficient to reach the atomic concentration specified for each structure.

[0022] It is also the object of the invention that the gases used in the flow are preferably argon, nitrogen, oxygen, methane or hydrogen;

[0023] Another object of the present invention comprises the alternative of performing heat treatment on the deposited material at the end of the process;

[0024] It is also an object of the invention that the control of the gas flow occurs through the mass-flow-controller system;

[0025] The object of the present invention is the single atom structure where the process parameters comprise: • Vacuum pressure between 5x10' 5mBar and 5x10' 6 mBar, preferably in 5x10' 6 mBar; • Plasma power density between 0.1 to 25W / cm 2 , preferably between 0.32 and 1.93 W / cm 2 . • Gas flow between 0.1sccm and 3sccm, preferably less than 1scm; • Working pressure between 2x10' 3 mBar and 5x10' 1 mBar, preferably 10' 3 mBar; • Deposition time between 0.3 min / g and 10 min / g, preferably less than 5 min / g. • Atomic concentration not exceeding 0.15 at%, preferably less than 0.1 at.

[0026] The present invention also includes the cluster structure where the process parameters comprise: • Vacuum pressure preferably between 5x10' 5 mBar; and 5x10' 6 mbar, preferably in 5x10' 6 mBar • Plasma power density between 0.1 to 25W / cm 2, preferably between 0.32 and 1.93 W / cm 2 .; • Gas flow between 0.1sccm and 3sccm, preferably less than 1sccm • Working pressure between 2x10' 3 mbar and 5x10' 1 mBar, preferably 10' 3 amber; • Deposition time between 0.5 min / g and 15 min / g, preferably less than 10 minutes / g; • Atomic concentration up to 0.20 at%, preferably less than 0.15 at%

[0027] Another object of the present invention is the structure of sub-nanoparticles where the process parameters comprise: Vacuum pressure between 5x10' 5 mBar and 5x10' 6 mBar, preferably 5x10' 6 mBar; • Plasma power density between 0.1 and 25W / cm 2 preferably between 0.32 and 1.93 cm2.; • Gas flow between 1sccm and 5sccm, preferably less than 2sccm; • Working pressure between 2x10' 3mBar and 5x10' 1 mBar, preferably 10' 3 amber; • Deposition time between 0.5 min / g and 15 min / g, preferably less than 10 minutes / g; • Atomic concentration between 0.2 at% and 0.25 at%.

[0028] The invention also includes the nanoparticle structure, where the process parameters include: • Vacuum pressure between 5x10' 5 mBar and 5x10' 6 mBar preferably smaller than 5x10' 6 amber; • Plasma power density between 0.1 and 25 W / cm 2 ' preferably between 0.32 to 1.93W / cm 2 ; • Gas flow between 1sccm and 10sccm, preferably less than 5sccm; • Working pressure between 2x10' 3 mBar and 5x10' 1 mBar, preferably 10' 3 mBar; • Deposition time between 5 min / g and 500 min / g, preferably less than 30 min / g; • Atomic concentration of up to 10 at%, preferably less than 1 at%.

[0029] Another object of the invention alternatively comprises a process for forming cluster-type structures, sub-nanometric or nanometric, with at least two target elements fused before deposition;

[0030] It is still an object, alternatively a process with at least at least two independent target elements, deposited at the same time (concomitantly), on the substrate material;

[0031] Another object of the present invention also comprises two independent target elements, deposited at different times (in sequence), on the substrate material;

[0032] For the purposes of this invention patent, the term “single atom” will be referred to as “single atom”, the term “some atoms” will be referred to as “cluster”, the term “metal-organic networks” will be referred to as “MOFs”, the term “shield” will be referred to as “shutter system”, the term “Physical Vapor Deposition” will be referred to as PVD, the term “data storage” will be referred to as “data storage”. Brief Description of the Figures

[0033] FIGURE 1 illustrates a microscopy image of silver nanoparticles deposited on carbon black powder.

[0034] FIGURE 2 illustrates a microscopy image of palladium nanoparticles deposited on ceria powder (CeO2).

[0035] FIGURE 3 illustrates a microscopy image of palladium nanoparticles deposited on alumina powder (AI2O3).

[0036] FIGURE 4 illustrates a microscopy image of palladium subnanoparticles deposited on silica powder (SiO2) - SBA-15.

[0037] FIGURE 5 illustrates a microscopy image of palladium clusters deposited on silica (SiO2) - SBA-15.

[0038] FIGURE 6 illustrates a mass calibration curve for the elements silver, ruthenium and niobium.

[0039] FIGURE 7(A) illustrates a single gun (2), with a single metal alloy target being deposited and the formation of the coated substrate (3);

[0040] FIGURE 7(B) illustrates two cannons (2) and (3), each with a different element, being deposited concomitantly on the substrate (4);

[0041] FIGURE 7 (C1 and C2) illustrates two cannons (2) and (3), each one with a different element, being deposited at different times (one after the other); Detailed Description of the Invention

[0042] The present invention is related to the physical process of enrichment of powder materials, which is part of the family of processes known as Physical Vapor Deposition (PVD).

[0043] In short, PVD can be explained as the ejection of atoms or clusters of atoms from at least one target material (elements from the periodic table) and subsequent deposition on a specific base material (substrate). From a technical point of view, the ejection of atoms from the target material can occur in different ways, including ejection by momentum transfer (sputtering), ejection by sublimation via heat (thermal deposition), ejection by sublimation via an electron beam (e-beam deposition), and ejection via a laser (laser ablation).

[0044] The present invention comprises the possibility of the substrate being powdered material (as long as it has low vapor pressure, preferably in the order of 10°mBar). In this way, the atoms ejected from the target material will adhere to the powder particles, giving these particles new properties, or forming new materials with pre-defined structures.

[0045] The key advantage of physical enrichment technology is the precise control of the deposition of the target material onto powder particles within a vacuum environment, allowing for the formation of different structures on their surfaces. In this way, atoms ejected from the material of one or more targets of different compositions achieve partial coating (single atoms, clusters, sub-nanometer particles, and even dispersed nanoparticles).

[0046] The ultimate goal of the process is to optimize the characteristics of the substrate material that received the atoms, adding properties that the material did not previously possess. For example, a plastic material that receives a The gold coating now has characteristics such as electrical conductivity on its surface, maintaining the polymer's lightness and geometric shape in its original state. The ability to pre-define the structure that will be created in the new material is crucial for its future application. It is known that, in different applications, the type of structure of the supported material directly influences the final characteristics of the newly formed material.

[0047] The process described here can be performed in known PVD equipment, which includes the possibility of agitating the substrate, preferably the equipment described in document BR102019008353.

[0048] Thus, the first step is to select the base material (powder substrate), which can come from any class, such as polymeric, metallic, semiconductor, ceramic, molecular sieves, zeolites, perovskites, MOFs, carbonaceous materials, and any other material with a vapor pressure below 10°mBar. After this step, the base material undergoes an optional treatment called degassing, which involves storing the substrate material in a pre-vacuum chamber that is evacuated to a pressure of 2x10' 2 mBar, for a period that can range from 1 h to 8 h (typically, it occurs in at least 3 h). Degassing must occur when the substrate material presents moisture.

[0049] Next, a fraction of the stored base material is transferred to the main vacuum chamber, where it is positioned inside the chamber. The chamber is then evacuated to a maximum base pressure of 5 x 10'. 6 mBar.

[0050] The next step is to choose at least one element from the periodic table, or combinations thereof, to be the target material. The element must be solid and have a vapor pressure less than 10°mBar.

[0051] When the process occurs with more than one target element, it can be deposited in at least three different ways, namely: a) Two or more elements melted and added as a target in the same cannon; b) Two or more individual elements, inserted into different barrels and with a concomitant deposition process; c) Two or more individual elements inserted into different barrels and with a sequential deposition process.

[0052] Next, the type of coating structure to be formed on the surface of the substrate material must be defined, which can be a single atom, cluster, sub-nanoparticle or nanoparticle.

[0053] After selecting the structure, the power density and deposition rate parameters must be adjusted. These parameters must be adjusted to match the maximum atomic concentration established for each structure. Atomic concentration is determined by the ratio of the target's atomic density to the substrate's atomic density. The atomic concentration of each structure is defined in TABLE 1: TABLE 1

[0054] In this way, the power density and deposition rate parameters are defined through trial and error, according to the steps described: a) Establish an initial power density for the equipment, which can be between 0.1 and 25 W / cm 2 ; b) Perform calibration of the deposition rate of the selected target material; c) Check whether the deposition rate is adequate to achieve the mass concentration of the planned structure; if not, d) Adjust the power density until the deposition rate is sufficient to achieve the mass concentration specified for each structure.

[0055] The next step is to insert the target materials into the equipment's respective cannons. Next, a controlled flow of at least one gas (argon, nitrogen, oxygen, methane, or hydrogen) is introduced into the vacuum chamber. Flow control is achieved using a commercial system known as a mass-flow controller and varies between 0.1 sccm and 10 sccm, depending on the desired structure.

[0056] The choice of gases to be inserted into the chamber, as well as the flow rate of each gas when more than one is inserted, is related to the desired material in the structure. This methodology is known; however, some examples are illustrated as follows: For metallic structures, argon is used; for metal oxides, argon and oxygen; for metal nitrides, argon and nitrogen; for metal carbides, argon and methane with hydrogen; and for metal oxynitrides, argon, nitrogen, and oxygen. The methodology for selecting gases is known in the state of the art and can be found in the documents: FEIL, AF: COSTA, Marlla Vallerius da ; KRELING, Afonso ; JACOBSEN, Saulo Davila ; VARGAS, André Luís Marin ; FERNANDES, Jesum Alves ; BLANDO, Eduardo ; HÜBLER, Roberto . Influence of Deposition Parameters on Corrosion Protection of TiN Deposited by Biased Magnetron Sputtering. Brazilian Journal of Vacuum Applications, forthcoming, v. 25, p.135-140, 2006 and Feil, Adriano F.; PAPLEO, RM ; HUBLER, R. Tuning the Crystalline Structure and Properties of TiO Thin Films Deposited by DC Reactive Magnetron Sputtering by Adjusting the Ar / O Ratio. JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY, v. 17, p. 8967-8974, 2017.

[0057] As a controlled flow of gas enters the vacuum chamber, the vacuum system valves are partially closed to achieve a balance between the gas entering the chamber and the gas evacuated by the chamber's vacuum system. To achieve this, the main valves are closed and a secondary vacuum circuit is activated, where a fine-throttle valve is fitted, capable of maintaining chamber pressure between 5 and 10 -3 mBar and 5x10' 1 mBar.

[0058] With pressure stabilization, the voltage source is activated and the plasma is stabilized with a power density between 01 W / cm 2 and 25W / cm 2After plasma stabilization, the shutter system is opened, initiating the process of deposition of target atoms onto the powder material. The process occurs for a period that can vary between 0.3 min / g and 500 min / g, depending on the structure to be formed and / or the desired material concentration. The process is then completed by turning off the source. The operation time must be sufficient to maintain a low total atom concentration, preferably less than 10% of the substrate mass. The material is then filled into a container while still under vacuum.

[0059] To complete the process of forming structures in the base material, the powder produced can be heat-treated (by placing the material in a furnace with or without a controlled atmosphere, at a temperature between 300°C and 700°C, depending on the material's composition) to force the insertion of atoms (such as Au, Pt, Ir, Rh, Ni, and Co) into the base material. This subsequent heat treatment step is not mandatory and can be performed in situ or ex situ after the deposition process. Preferential Realization

[0060] The single atom structure was obtained using as base material, alumina (AI2O3), ceria (Ce2Os), zirconia (ZrC ), titania (TiO2), silica (SiO2), sodium titanate nanotubes, graphene, carbon black, carbon nanotubes (CNTs), PTFE, PEEK, among others. Initially, the selected material was stored in a pre-vacuum chamber and evacuated to a pressure of 2x10 _ 2mBar, for a period of at least 3 hours. This step is performed to remove moisture and oxygen from the surface of the silica.

[0061] In a second step, a fraction of the stored silica (1 g) was transferred to the main vacuum chamber and positioned in the stirring vessel inside the chamber.

[0062] To define the single atom structure, the power density of 0.32W / cm was initially established. 2 , then, the deposition rate of the target material was calibrated in the equipment. It was found that this was adequate to achieve the atomic concentration of the planned structure.

[0063] The chamber was then evacuated to a base pressure of 5x10' 6 mBar. For this purpose, processes were carried out with palladium metal.

[0064]

[0065] Next, a controlled flow of argon gas was inserted into the vacuum chamber. The flow is controlled by a commercial system known as a mass-flow controller; it should not exceed 1 sccm.

[0066] As a controlled flow of argon enters the vacuum chamber, the vacuum system valves are partially closed to achieve equilibrium between the gas entering the chamber and the gas being evacuated. To achieve this, the main valves were closed and a secondary vacuum circuit was activated, which includes a fine-throttle valve capable of maintaining chamber pressure at 5x10'. 3 mBar.

[0067] With the pressure stabilized, the voltage source was turned on and the closed-system plasma was stabilized, with a power density not exceeding 0.32 W / cm 2. After plasma stabilization, the shutter system was opened and the process of deposition of target atoms onto the powder material under agitation was initiated.

[0068] The palladium deposition process occurred between 1.1 min / g and 11.2 min / g, and was completed by turning off the source.

[0069] It is essential that the process be stopped quickly so that the total atom concentration is less than 0.15 at%, relative to the mass of the substrate (SBA-15). The material was then filled into a container still under vacuum.

[0070] To complete the single-atom structure formation process, the powder produced was heat-treated to force the insertion of Pd atoms into the SBA-15 silica crystal lattice. This subsequent heat treatment step is optional and can be performed in situ or ex situ after the deposition process.

[0071] At the end of the palladium deposition process on the surface of SBA-15 silica, high-resolution microscopy and spectroscopy analyses were performed, which indicated that atoms of the deposited metal were dispersed on the surface of SBA-15.

[0072] These isolated atoms were preferentially trapped in oxygen vacancies or defect points in the silica crystal lattice.

[0073] With heat treatment, these atoms can migrate to the structure, creating more intense chemical bonds with the silica.

[0074] The cluster-type structure was obtained using a base material (substrate) of alumina (AI2O3), ceria (Ce2Os), zirconia (ZrC), titania (TiO2), silica (SiO2), sodium titanate nanotubes, graphene, carbon black, carbon nanotubes (CNTs), PTFE, PEEK, among others. Initially, the selected powder was stored in a pre-vacuum chamber and was evacuated to a pressure of 2x10' 2mBar, for a period of at least 3 hours. This step aims to remove moisture and oxygen from the surface of the alumina.

[0075] In a second step, a fraction of the stored alumina (1 g) was transferred to the main vacuum chamber and positioned in the stirring vessel inside the chamber.

[0076] To define the cluster structure, the following was established: power density of 0.32W / cm 2 ' afterward, the deposition rate of the target material was calibrated on the equipment. It was found that it was adequate to achieve the atomic concentration of the planned structure.

[0077] The chamber was then evacuated to a base pressure of 5x10' 6 mBar. Individual processes were carried out with palladium.

[0078]

[0079] Next, a controlled flow of argon gas was introduced into the vacuum chamber. The flow was controlled using a commercially known mass-flow controller and should not exceed 2sccm.

[0080] As a controlled flow of argon enters the vacuum chamber, the vacuum system valves are partially closed to achieve equilibrium between the gas entering the chamber and the gas being evacuated. To achieve this, the main valves were closed and a secondary vacuum circuit was activated, which includes a fine-throttle valve capable of maintaining chamber pressure at 5x10'. 3 amber.

[0081] With the pressure stabilized, the voltage source was turned on and the plasma stabilized at a power density of no more than 0.6 W / cm2. After the plasma stabilized, the shutter system was opened and the process of deposition of the target atoms onto the powder material began.

[0082] The process occurs between 2.3 min / g and 22.4 min / g and was completed by turning off the source.

[0083] It's crucial that the process be stopped quickly so that the total concentration of metal atoms is very low, less than 0.20% relative to the substrate's mass. The material is then filled into a container while still under vacuum.

[0084] At the end of the Pd metal deposition process on the gamma alumina surface, high-resolution microscopy and spectroscopy techniques were performed, which indicated that clusters of agglomerates of 3 to 5 atoms were deposited in a dispersed manner on the alumina surface.

[0085] These clusters form because the (hot) metal atoms thermalize and migrate across the surface of the alumina (which is at room temperature), forming clusters and / or agglomerates of atoms. The low metal concentration deposited on the surface of the powder results in the final structure formed being composed of few atoms.

[0086] The sub-nanoparticle type structure was obtained using different powder substrates, such as: alumina (AI2O3), ceria (Ce2Os), zirconia (ZrÜ2), titania (TIO2), silica (SIO2), sodium titanate nanotubes, graphene, carbon black, carbon nanotubes (CNTs), PTFE, PEEK, among others.

[0087] Initially, the selected powder was stored (1g) in a pre-vacuum chamber, which was evacuated to a pressure of 2x10' 2 mBar under magnetic stirring for at least 3 hours. This step aims to remove moisture and oxygen from the surface of the powder.

[0088] In a second step, a fraction of the stored powder was transferred to the main vacuum chamber and positioned inside the chamber.

[0089] To define the sub-nanoparticle structure, a power density of 0.60W / cm was established. 2 ' afterward, the deposition rate of the target material was calibrated on the equipment. It was found that it was adequate to achieve the atomic concentration of the planned structure.

[0090] The chamber was then evacuated to a base pressure of at least 5x10' 6 mBar. Individual processes were carried out with Pd metal.

[0091]

[0092] Next, a controlled flow of argon gas was introduced into the vacuum chamber. The flow was controlled by a commercially available mass-flow controller and should not exceed 5sccm.

[0093] With the entry of the controlled flow of argon into the vacuum chamber, the vacuum system valves are partially closed so that the equilibrium between the gas entering the chamber and the gas being evacuated from the chamber is achieved. To this end, the main valves were closed and a secondary vacuum circuit was activated, which contains a fine-throttle valve capable of maintaining the chamber pressure at exactly 5x10' 3 amber.

[0094] With the pressure stabilized, the voltage source was turned on, and we stabilized the plasma with a power density of no more than 1.26 W / cm2. After the plasma stabilized, the shutter system was opened, and the process of deposition of the target atoms onto the powder material began.

[0095] The process occurred between 3.4 min / g and 33.6 min / g, depending on the target material, and was completed by turning off the source.

[0096] It's crucial that the process be stopped quickly so that the total concentration of atoms is very low, less than 0.30% of the substrate's mass. The material is then filled into a container still under vacuum.

[0097] At the end of the Pd metal deposition process, on the surface of alumina (AI2O3), ceria (Ce2Os), zirconia (ZrC), titania (TiO2), silica (SiO2), sodium titanate nanotubes, graphene, carbon black, carbon nanotubes (CNTs), PTFE, PEEK, among others, high-resolution microscopy and spectroscopy techniques were performed, which showed the formation of sub-nanometric particles with an average diameter of less than 1 nm deposited with high dispersion on the surface of the powder materials.

[0098] The nanoparticle-type structure was obtained using different powder substrates, such as: alumina (AI2O3), ceria (Ce2Os), zirconia (ZrÜ2), titania (TIO2), silica (SIO2), sodium titanate nanotubes, graphene, carbon black, carbon nanotubes (CNTs), PTFE, PEEK, among others.

[0099] Initially, the selected powder was stored in a pre-vacuum chamber that was evacuated to a pressure of 2x10' 2 mBar, for a period of at least 3 hours. This step aims to remove moisture and oxygen from the surface of the powder. [000100] In a second moment, a fraction of the stored powder was transferred to the main vacuum chamber and positioned in the stirring vessel inside the chamber. [000101] To define the nanoparticle structure, a power density of 1.26W / cm was established. 2, then, the deposition rate of the target material was calibrated in the equipment. It was found that this was adequate to achieve the atomic concentration of the planned structure. [000102] The chamber was then evacuated to a base pressure of at least 5x10' 6 mBar. Individual processes were carried out with silver metal. [000103] Next, a controlled flow of argon gas was inserted into the vacuum chamber. The flow was controlled with a commercial and known mass-flow-controller system and should not be greater than 5sccm. [000104] With the entry of the controlled flow of argon into the vacuum chamber, the vacuum system valves are partially closed to achieve a balance between the gas entering the chamber and the gas being evacuated from the chamber. To this end, the main valves are closed and a secondary vacuum circuit is activated where there is a fine throttling valve, capable of maintaining the chamber pressure at 5x10 -3 mBar. [000105] With the pressure stabilized, the voltage source was turned on and the plasma was stabilized with a power density ranging from 1.26 to 5 W / cm 2 . [000106] After the plasma stabilized, the shutter system was opened and the process of deposition of the target atoms in the powder material under stirring was started. [000107] The process occurs for a time proportional to the mass concentration of nanoparticles in relation to the mass of powder (FIGURE 6). The deposition time and the power used are parameters that influence the size of the nanoparticles obtained. Typically, the higher the power used in the same deposition time, the larger the average size of the nanoparticles. [000108] For the formation of homogeneous and well-dispersed nanoparticles, the maximum atomic concentration must be between 0.4 and 10%. At the end of the process, the material is filled into a container still under vacuum. [000109] At the end of the silver deposition process, on the surface of alumina (AI2O3), ceria (Ce2Os), zirconia (ZrC ), titania (TiO2), silica (SiO2), sodium titanate nanotubes, graphene, carbon black, carbon nanotubes (CNTs), PTFE, PEEK, among others, high-resolution microscopy and spectroscopy analyses were performed. The tests performed demonstrated the formation of nanometric particles with an average diameter ranging from 1 to 50nm, as a function of time and / or power used. The analyzed samples showed that the nanoparticles present high dispersion on the surface of the powder materials and that there is precise control of the average diameter with low dispersion. It was observed that the lower the deposition power density (less than 1.26W / cm2), the lower the temperature of the powder sample and the lower the metal concentration, the smaller the diameter of the nanoparticles formed. [000110] Formation of TiO2 nanoparticles from a metallic titanium target. [000111 ] The TiO2 nanoparticle-type structure was obtained using different powder substrates, such as: alumina (AI2O3), ceria (Ce2O3), zirconia (ZrO2), titania (TiO2), silica (SiO2), sodium titanate nanotubes, graphene, carbon black, carbon nanotubes (NTC), PTFE, PEEK, among others. [000112] Initially, the selected powder was stored in a pre-vacuum chamber, which was evacuated to a pressure of 2x10' 2 mBar, for a period of at least 3 hours. This step aims to remove moisture and oxygen from the surface of the powder. [000113] In a second moment, a fraction of the stored powder (1 g) was transferred to the main vacuum chamber and positioned in the container of agitation inside the chamber. [000114] To define the nanoparticle structure, a power density of 1.26W / cm was established. 2' afterward, the deposition rate of the target material was calibrated on the equipment. It was found that it was adequate to achieve the atomic concentration of the planned structure. [000115] The chamber was then evacuated to a base pressure of at least 5x10' 6 mBar. The titanium target was selected. [000116] [000117] Next, a controlled flow of argon and oxygen gas in a ratio of 5:1 was inserted into the vacuum chamber. The flow was controlled through a commercial and known system, called a mass-flow-controller and should not be greater than 5sccm. [000118] With the controlled flow of argon and oxygen entering the vacuum chamber, the vacuum system valves are partially closed so that equilibrium between the gas entering the chamber and the gas being evacuated from the chamber is achieved. To this end, the main valves were closed and a secondary vacuum circuit was activated, which has a fine throttling valve capable of maintaining the chamber pressure at exactly 5x10' 3 mBar. [000119] With the pressure stabilized, the voltage sources were switched on and the plasma was stabilized at a power density of no more than 1.93 W / cm 2 After the plasma stabilized, the shutter was opened and the process of deposition of the target atoms in the powder material under agitation was initiated. [000120] The process occurred during a period of 8 minutes and ended with the source being turned off. [000121] Formation of TiO2 nanoparticles using a TiO2 target [000122] The TiO2 nanoparticle-like structure was obtained using different powder substrates, such as: alumina (AI2O3), ceria (Ce2Os), zirconia (ZrC), titania (TiO2), silica (SiO2), sodium titanate nanotubes, graphene, carbon black, carbon nanotubes (CNTs), PTFE, PEEK among others. [000123] Initially, the selected powder was stored in a pre-vacuum chamber that was evacuated to a pressure of 2x10' 2 mBar, for a period of at least 3 hours. This step aims to remove moisture and oxygen from the surface of the powder. [000124] In a second moment, a fraction of the stored powder was transferred to the main vacuum chamber and positioned in the stirring container inside the chamber. [000125] To define the nanoparticle structure, the power density of 1.26 W / cm was established. 2' afterward, the deposition rate of the target material was calibrated on the equipment. It was found that it was adequate to achieve the atomic concentration of the planned structure. [000126] The chamber was then evacuated to a base pressure of at least 5x10' 6 mBar. The titanium oxide (TiO2) target was selected. [000127] Next, a controlled flow of argon gas was inserted into the vacuum chamber. The flow was controlled through a commercial and known system, called a mass-flow-controller and should not be greater than 5sccm. [000128] With the entry of the controlled flow of argon into the vacuum chamber, the vacuum system valves are partially closed so that equilibrium between the gas entering the chamber and the gas being evacuated from the chamber is achieved. To this end, the main valves were closed and a secondary vacuum circuit was activated, where there is a fine throttling valve, capable of maintaining the chamber pressure at exactly 5x10' 3 amber. [000129] With the pressure stabilized, the voltage sources were turned on and the plasma was stabilized at a power density of no more than 1.93 W / cm 2 . After the plasma stabilization, the shutter was opened and the process of deposition of target atoms in the powder material under stirring, was initiated. [000130] The process occurred during a period of 8 minutes and ended with the source being turned off. [000131] Formation of TiN nanoparticles from a metallic titanium target [000132] The TiN nanoparticle-type structure was obtained using different powder substrates, such as: alumina (AI2O3), ceria (Ce2Os), zirconia (ZrC), titania (TIO2), silica (SIO2), sodium titanate nanotubes, graphene, carbon black, carbon nanotubes (CNTs), PTFE, PEEK, among others. [000133] Initially, the selected powder was stored in a pre-vacuum chamber that was evacuated to a pressure of 2x10' 2 mBar, for a period of at least 3 hours. This step aims to remove moisture and oxygen from the surface of the powder. [000134] In a second step, a fraction of the stored powder was transferred to the main vacuum chamber. [000135] To define the nanoparticle structure, a power density of 1.26W / cm was established. 2' afterward, the deposition rate of the target material was calibrated on the equipment. It was found that it was adequate to achieve the atomic concentration of the planned structure. [000136] The chamber was then evacuated to a base pressure of at least 5x10' 6 mBar. The titanium target was selected. [000137] Next, a controlled flow of argon and nitrogen gas in a ratio of 3:1 was inserted into the vacuum chamber. The flow was controlled through a commercial and known system, called a mass-flow-controller and should not be greater than 5sccm. [000138] With the entry of the controlled flow of argon and nitrogen into the vacuum chamber, the vacuum system valves are partially closed so that equilibrium between the gas entering the chamber and the gas being evacuated from the chamber is achieved. To this end, the valves were closed main and a secondary vacuum circuit was activated where there is a fine throttling valve, capable of maintaining the chamber pressure at exactly 5x10 ' 3 amber. [000139] With the pressure stabilized, the voltage sources were turned on and the plasma was stabilized at a power density of no more than 1.93 W / cm 2 . After the plasma stabilized, the shutter was opened and the process of deposition of the target atoms in the powder material began. [000140] The process occurred during a period of 8 minutes and ended with the source being turned off. [000141] Formation of AuAq bimetallic sub-nanoparticles, with AuAq target. [000142] The bimetallic sub-nanoparticle type structure was obtained using different powder substrates, such as: alumina (AI2O3), ceria (Ce2Os), zirconia (ZrC), titania (TIO2), silica (SIO2), sodium titanate nanotubes, graphene, carbon black, carbon nanotubes (CNTs), PTFE, PEEK, among others. [000143] Initially, the selected powder was stored in a pre-vacuum chamber that was evacuated to a pressure of 2x10' 2 mBar, for a period of at least 3 hours. This step aims to remove moisture and oxygen from the surface of the powder. [000144] In a second step, a fraction of the stored powder was transferred to the main vacuum chamber and positioned inside the chamber. [000145] For the definition of the sub-nanoparticle structure, the power density of 0.6W / cm was established. 2' afterward, the deposition rate of the target material was calibrated on the equipment. It was found that it was adequate to achieve the atomic concentration of the planned structure. [000146] The chamber was then evacuated to a base pressure of at least 5x10' 6 mBar. A target made of Au-Ag metal alloy was selected. [000147] Next, a controlled flow of argon gas was inserted into the vacuum chamber. The flow was controlled using a commercially known system called a mass flow controller and should not exceed 5sccm. [000148] With the entry of the controlled flow of argon into the vacuum chamber, the vacuum system valves are partially closed so that equilibrium between the gas entering the chamber and the gas being evacuated from the chamber is achieved. To this end, the main valves were closed and a secondary vacuum circuit was activated, where there is a fine throttling valve, capable of maintaining the chamber pressure at exactly 5x10' 3 amber. [000149] With the pressure stabilized, the voltage source was switched on and the plasma was stabilized with a power density of no more than 0.32 W / cm 2 . After the plasma stabilized, the shutter was opened and the process of deposition of the target atoms onto the powder material began. [000150] The process occurred during a period of 8 minutes and ended with the source being turned off. [000151] The bimetallic sub-nanoparticle type structure was obtained using different powder substrates, such as: alumina (AI2O3), ceria (Ce2Os), zirconia (ZrC), titania (TIO2), silica (SIO2), sodium titanate nanotubes, graphene, carbon black, carbon nanotubes (CNTs), PTFE, PEEK, among others. [000152] Initially, the selected powder was stored in a pre-vacuum chamber that was evacuated to a pressure of 2x10' 2 mBar, for a period of at least 3 hours. This step aims to remove moisture and oxygen from the surface of the powder. [000153] In a second moment, a fraction of the stored powder was transferred to the main vacuum chamber and positioned inside the chamber. [000154] For the definition of the sub-nanoparticle structure, the power density of 0.6W / cm was established. 2 , for silver and 0.32W / cm 2 , for gold, after, the deposition rate calibration was carried out of the target material, in the equipment. It was found that this was adequate to achieve the atomic concentration of the planned structure. [000155] The chamber was then evacuated to a base pressure of at least 5x10' 6 mBar. Silver and gold targets were selected. [000156] Next, a controlled flow of argon gas was inserted into the vacuum chamber. The flow was controlled through a commercial and known system, called a mass-flow-controller and should not be greater than 5sccm. [000157] With the entry of the controlled flow of argon into the vacuum chamber, the vacuum system valves are partially closed so that equilibrium between the gas entering the chamber and the gas being evacuated from the chamber is achieved. To this end, the main valves were closed and a secondary vacuum circuit was activated, where there is a fine throttling valve, capable of maintaining the chamber pressure at exactly 5x10' 3 amber. [000158] With the pressure stabilized, the voltage sources were switched on and the plasma was stabilized with a power density of no more than 0.6 W / cm 2 for silver and 0.32 W / cm 2 for gold. After the plasma stabilized, the shutters were opened and the process of deposition of the target atoms onto the powder material began. [000159] The process occurred during a period of 8 minutes and ended with the source being turned off. [000160] TABLE 2 describes, as an example, some elements and the data for each parameter, so that the desired structure on the substrate surface is achieved. TABLE 2

Claims

CLAIMS 1. Process of manufacturing powdered materials, through the pulverization of atoms of a target material and subsequent deposition on powdered base material, CHARACTERIZED by comprising the steps: a) Select the powdered substrate material, with vapor pressure lower than 10°mBar; b) Optionally perform the degassing step of the substrate material; d) Evacuate the chamber to the lowest possible vacuum pressure, preferably 5x10' 6mBar; e) Select at least one element from the periodic table, with vapor pressure below 10°mBar, as target material; f) Define the type of coating structure to be formed on the surface of the substrate material, which can be single atom, cluster, sub-nanoparticle or nanoparticle; g) Define the values ​​of the power density and deposition rate parameters; h) Insert the target materials into the cannons; i) Start controlled flow with at least one gas in the vacuum chamber, between 0.1 sccm and 10 sccm; j) Maintain the working pressure between 5x10' 3 mBar and 10' 1 mBar; k) Activate the voltage source and stabilize the plasma at a power density between 0.1 W / cm 2 and 25W / cm 2. l) Start the process of deposition of the target material atoms on the surface of the substrate material; m) Wait for a period of 0.3 min / g to 500 min / g, for the deposition of the target material atoms on the surface of the substrate material; n) Keep the atomic concentration below 10 at%; o) Turn off the voltage source; p) Bottle the coated substrate material.

2. Process for manufacturing powdered materials, according to claim 1, CHARACTERIZED by the chosen substrate material being preferably polymeric, metallic, semiconductor, ceramic, molecular sieves, perovskites, MOFs (metalorganic networks) and carbonaceous materials.

3. Process for manufacturing powdered materials, according to claim 1, CHARACTERIZED by the target material preferably having a vapor pressure of 10' 1 mBar.

4. Process for manufacturing powdered materials, according to claim 1, CHARACTERIZED by the target material being inserted into the equipment in the form of an alloy or as a pure element; 5. Process for manufacturing powdered materials, according to claim 1, CHARACTERIZED by the process of forming cluster-type structures, sub-nanometric or nanometric, comprising at least 2 fused target elements; 6. Process for manufacturing powdered materials, according to claim 1, CHARACTERIZED by the process for forming cluster-type structures, sub-nanometric or nanometric, comprising at least 2 target elements inserted individually into each cannon and deposited on the substrate material concomitantly; 7. Process for manufacturing powdered materials, according to claim 1, CHARACTERIZED by the process of forming cluster-type structures, sub-nanometric or nanometric, comprising at least 2 target elements inserted individually into each cannon and deposited on the substrate material at different times, in sequence; 8. Process for manufacturing powdered materials, according to claim 1, CHARACTERIZED by the degassing step occurring when the substrate material presents moisture.

9. Process for manufacturing powdered materials, according to claim 1, CHARACTERIZED by the degassing of the substrate material comprising the steps: a) inserting the substrate material into a pre-vacuum chamber; b) evacuating the chamber until reaching a pressure of 2x10' 2 mBar; c) keep the substrate material in the pre-vacuum chamber for a period between 1h and 8h.

10. Process for manufacturing powdered materials, according to claims 1 and 3, CHARACTERIZED by the degassing period of the substrate material being preferably 3h.

11. Process for manufacturing powdered materials, according to claim 1, CHARACTERIZED by the definition of the structure of the coating of the substrate surface comprising the steps of: a) Establishing an initial power density of the equipment between 0.1 and 25 W / cm 2 b) Calibrate the deposition rate of the target material; c) Check whether the deposition rate of the target material is adequate to achieve the atomic concentration of the planned structure; if not, d) Adjust the power density until the deposition rate is sufficient to achieve the atomic concentration for each structure.

12. Process for manufacturing powdered materials, according to claim 1, CHARACTERIZED by the gases inserted into the vacuum chamber preferably comprising argon, nitrogen, oxygen, methane or hydrogen.

13. Process for manufacturing powdered materials, according to claim 1, CHARACTERIZED by alternatively, at the end of the process, performing heat treatment on the coated substrate material.

14. Process for manufacturing powdered materials, according to claim 1, CHARACTERIZED by the gas control occurring through the mass-flow-controller system.

15. Process for manufacturing powdered materials, according to claim 1, CHARACTERIZED by the single atom structure, where the process parameters comprise: a) Vacuum pressure preferably at 5x10' 6mBar; b) Plasma power density preferably between 0.32 to 1.93cm2. c) Gas flow preferably less than 1 scm; d) Working pressure preferably 10-3mBar; e) Deposition time preferably less than 5min / g. f) Atomic concentration preferably less than 0.1 at%.

16. Process for manufacturing powdered materials, according to claims 1 and 10, CHARACTERIZED by the cluster structure where the process parameters comprise: a) Vacuum pressure preferably at 5x10 -6 mbar; b) Power density preferably between 0.32 and 1.93 cm2; c) Gas flow preferably less than 1 sccm; d) Working pressure preferably 10 -3 mbar; e) Deposition time preferably less than 10 minutes / g; f) Atomic concentration preferably up to 0.20 at%.

17. Process for manufacturing powdered materials, according to claims 1 and 10, CHARACTERIZED by the sub-nanoparticle structure where the process parameters comprise: a) Vacuum pressure preferably in which 5x10 -6 mbar; b) Plasma power density preferably between 0.32 and 1.93 cm2; c) Gas flow preferably less than 2 sccm; d) Working pressure preferably at 10 -3 mbar; e) Deposition time preferably less than 10 minutes / g; f) Atomic concentration preferably between 0.2 at% and 0.25 at%.

18. Process for manufacturing powdered materials, according to claims 1 and 10, CHARACTERIZED by the nanoparticle structure where the process parameters comprise: a) Vacuum pressure preferably less than 5x10 -6 mbar; d) Power density preferably between 0.32 and 1.93 cm2; e) Gas flow preferably less than 5 sccm; f) Working pressure preferably at 10'3 mbar; g) Deposition time preferably less than 30 minutes / g; h) Atomic concentration preferably less than 1 at%

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