Functional nanoparticle premix, process for obtaining same, process for modifying material properties and material with modified properties

Abstract

The present invention pertains to the field of materials engineering and nanotechnology. More specifically, the invention discloses: a functional premix comprising nanoparticles and a vehicle or compatibiliser, a process for obtaining same, a process for modifying material properties, and modified materials provided with improved properties. The premix of the invention, surprisingly, is useful for modifying the properties of materials of different kinds, such as polymers, metals, ceramic materials and / or composites of different materials. The premix of the invention provides various advantages in the transport, use and incorporation of nanoparticles into different materials. In one embodiment, the invention provides remarkable modifications to the properties of polymers and represents a practical departure from previous concepts in this technical field. In another embodiment, the invention provides advantages in the modification of the properties of metallic and / or ceramic materials.

Description

Descriptive Report of Invention Patent FUNCTIONAL PREMIX OF NANOPARTICLES, PROCESS FOR OBTAINING IT, PROCESS FOR MODIFYING MATERIAL PROPERTIES AND MATERIAL WITH MODIFIED PROPERTIES Field of Invention

[0001] The present invention is in the field of Materials Engineering and Nanotechnology. More specifically, the invention discloses: a functional premix comprising nanoparticles and a carrier or compatibilizer; a process for obtaining them; a process for modifying material properties; and modified materials with improved properties. The premix of the invention, surprisingly, is useful for modifying the properties of materials of various natures, such as polymers, metals, ceramic materials, and / or composites of different materials. The premix of the invention provides several advantages in the transport, use, and incorporation of nanoparticles into different materials. In one embodiment, the invention provides notable modifications in the properties of polymers, effectively breaking with previous concepts in this technical field. In another embodiment, the invention provides advantages in modifying the properties of metallic and / or ceramic materials. Background of the Invention

[0002] The use of nanoparticles to modify the properties of various materials has been the subject of intense research and development. On the one hand, large-scale use still faces multiple limitations, beginning with the lack of availability of nanoparticle preparations with high concentrations, purity, and precise particle size profiles. On the other hand, even when such nanoparticles are available, multiple technical challenges must be overcome, including quantity, purity, dispersibility, stability, and compatibility with the material to be modified.

[0003] In the field of polymers, the use of nanoparticles is not typically the subject of studies or technologies, partly due to the limitations mentioned above and partly due to their molecular structure. The present invention provides an approach to modifying polymer properties that was previously unknown, both in terms of the different modified properties and their magnitude. Furthermore, some polymers are not physically or chemically compatible with certain nanoparticles, particularly due to polarity. The present invention also provides a solution to this problem.

[0004] These and other reasons contribute to the lack of industrial-scale availability of polymers doped with nanoparticles with a variety of particle size distributions, all within the nanometer range. The present invention solves these problems.

[0005] In the field of metals and ceramic materials, the use of nanoparticles is the subject of some studies and technologies. However, a recurring challenge in using nanoparticles in these materials is the problems of dispersion and / or homogenization. The present invention provides a solution to these problems.

[0006] In the search for the state of the art in scientific and patent literature, the following documents related to the topic were found:

[0007] Patent application WO2022036427, with common inventors and the present invention, discloses a niobium nanoparticle preparation obtained by a top-down approach. This preparation also includes the following technical characteristics: particles entirely in the nanometer particle size range; high purity; and industrial-scale production, with a cost-effective approach. This nanometric powder preparation has very high purity, since the process does not add impurities or lead to the formation of reaction products, as is the case with state-of-the-art bottom-up (or synthesis) processes. On the other hand, WO2022036427 does not mention the modulation of material properties resulting from the use of a nanoparticle premix as disclosed in the present patent application.

[0008] Patent document US200701 16976A1 addresses how to provide a composition that combines improved impact resistance with effective corona resistance. As a solution, US200701 16976A1 discloses a nanocomposite comprising a polymer composition and nanoparticles with an average largest dimension less than or equal to approximately 500 nanometers. However, US200701 16976A1 does not mention the modulation of material properties resulting from the use of a nanoparticle premix such as that disclosed in this patent application.

[0009] Patent document CN 1 10229412 addresses the issue of solving nanomaterial compatibility issues with polymers so that mechanical properties such as hardness are not affected. Thus, CN1 10229412 discloses a nanocomposite with increased strength and hardness obtained by melt blending a premix. The premix comprises: a) a nanomaterial that may be metal oxides, transition metals, and rare earths; b) a liquid medium that may be water or other solvents; c) polypropylene; and, preferably, to increase the amount of liquid medium to which the nanomaterial is bound, an auxiliary agent may also be added. Despite this, CN1 10229412 does not mention the modulation of material properties resulting from the use of a nanoparticle premix such as that disclosed in this patent application.

[0010] The article by Hajduk et al. (2021) (Thermal and optical properties of PMMA firns reinforced with Nb20s nanoparticles) reveals the effect of niobium pentoxide nanoparticles in altering the thermal and physical properties of polymethyl methacrylate (PMMA). On the other hand, Hajduk et al. (2021) does not mention the modulation of material properties resulting from the use of a nanoparticle premix such as that disclosed in the present patent application.

[0011] Patent document US2009226711 A1 discloses a biaxially oriented nanocomposite film formed by a process comprising mixing a nanofiller and a polymer composition to forming a nanocomposite; extruding the nanocomposite as a melt to form a molten tube; expanding the tube biaxially by means of mechanical force and air pressure to form a bubble; and collapsing the bubble to form at least one sheet of a biaxially oriented nanocomposite film, wherein the biaxially oriented nanocomposite film has a breakdown strength (dielectric strength) of at least 300 V / micrometer. On the other hand, US200922671 1 A1 does not mention the modulation of material properties resulting from the use of a nanoparticle premix such as that disclosed in the present patent application.

[0012] Patent document JP2003073558 proposes a method for producing a composition of ultrafine metal oxide particles and a polymer containing electron-donating groups, in which the surface of the particles is modified with acidic and basic groups. More specifically, the method comprises: 1) hydrolysis of a compound to obtain ultrafine metal oxide particles and surface modification with an aliphatic carboxylic acid and an aliphatic amine; 2) dispersing / dissolving the particles in a desired solvent and combining with a polymer solution to form a mixed solution; 3) optionally heating and stirring to promote the formation of the composite of the ultrafine metal oxide particles and the polymer. On the other hand, JP2003073558 does not mention the modulation of material properties resulting from the use of a nanoparticle premix such as that disclosed in this patent application.

[0013] From what can be inferred from the literature researched, no documents were found anticipating or suggesting the teachings of the present invention. Summary of the Invention

[0014] The present invention solves several problems of the prior art through a functional premix comprising a nanoparticle load and at least one carrier. The premix (or premix) of the invention is surprisingly useful for modifying one or more properties of materials. very different materials, such as polymers, metals, ceramics, and / or composites of different materials, is surprisingly useful for modifying the properties of very different materials, such as polymers, metals, ceramics, and / or composites of different materials. A process for obtaining said premix is ​​also disclosed.

[0015] The premix of the invention is particularly useful for solving problems of stability, dispersibility, and / or adequate incorporation of nanoparticles into various materials. The premix of the invention also solves the technical problem of suspending nanoparticles during handling, preventing dispersion into the environment.

[0016] Modifying polymers or other materials, such as metals and / or ceramics, with the incorporation of micrometer-sized particles leads to catastrophic failures such as cracks, deformations, irregularities in geometry, and other problems. Furthermore, for certain expensive materials, the mass percentage resulting from the use of micrometer-sized particles can make the final product cost unviable. Finally, because micrometer-sized particles are used, the so-called "mean free path" and surface energy are incapable of interacting with the medium to the point of generating new structures. The invention solves this problem and provides premixes containing nanoparticles in high concentrations.Since the nanoparticle concentrations of the premixes of the invention are orders of magnitude higher than those required to obtain improvements in the properties of the final materials containing such nanoparticles, the premixes of the invention are particularly useful for the subsequent preparation of materials with lower nanoparticle concentrations, using said premixes as premixes or compatibilizers. If one wishes to prepare a material with 50 ppm of any of the nanoparticles described in this patent application, simply use a 1:10 mixture of the respective premix with the one to be modified and homogenize until the product with the aforementioned concentration is obtained. Other final concentrations can be obtained through adjustment. of premix concentrations in the desired material.

[0017] The invention also provides a process for modifying materials, as well as the modified materials obtained.

[0018] It is, therefore, one of the objects of the invention to provide a functional premix comprising: a solid, semi-solid, pasty or liquid vehicle or compatibilizer; and a load of 0.0001 to 50% by weight of nanoparticles of defined particle size and chemically defined composition.

[0019] In one embodiment, said vehicle or compatibilizer is selected from: a polymeric, ceramic, metallic material, or combinations thereof. In one embodiment, said polymeric material (the term “polymer” being used broadly) is selected from: diols, polyols, adhesives / plasticizers such as mesamoll, elastomers, rubbers, thermoplastic polymers, thermosetting polymers, resins, waxes, epoxy resins, phenolic resins, polymethyl methacrylate (acrylic), polystyrene, polyvinyl chloride (PVC), polyethylene, polypropylene, natural polymers selected from rubber, silk, wool, cellulose, or combinations thereof. In one embodiment, said diol or polyol is selected from: alkyl glycol, alkylene glycol, polyalkylene glycol, ethylene glycol, propylene glycol, butyl glycol, polyethylene glycol, polypropylene glycol, or combinations thereof.

[0020] . In one embodiment, said nanoparticles have a size of less than 750nm and a degree of amortization of at least 19%.

[0021] Another object of the invention is to provide a process for obtaining a functional premix comprising at least one step of incorporating a nanoparticle load into a solid, semi-solid or pasty vehicle into a metallic, ceramic and / or polymeric matrix material during a processing step of said material.

[0022] It is another object of the invention to provide a process for modifying the properties of a material, said process comprising one or more steps of incorporating the functional premix of the invention into a metallic, ceramic, polymeric, composite material, or combinations thereof. same, during a processing step of said material. In one embodiment, in which the premix of the invention is used to incorporate nanoparticles into a polymeric material, the carrier is a compatibilizer that integrates into the final polymeric matrix provided with nanoparticles. In one embodiment, in which the premix of the invention is used to incorporate nanoparticles into a metallic or ceramic material, the carrier usually does not integrate into the final metallic or ceramic matrix, due to the high processing temperature and volatilization of the carrier, with the nanoparticles remaining in said modified product.

[0023] It is another object of the invention to provide a material with modified properties due to the incorporation of the premix of the invention, said modified material being metallic, ceramic, polymeric, a composite, or combinations thereof.

[0024] In one embodiment, the modified polymeric material is selected from polyesters and similar resins, epoxy resins, phenolic resins and similar resins, polyamides and similar resins, thermoplastic polymers, thermosetting polymers, or combinations thereof. Among other properties and characteristics improved in polymeric materials, special mention is made of improved resistance to mechanical stress, modified glass transition temperature, among others. In one embodiment, the modified metallic and / or ceramic material has improved properties, notably improved resistance to mechanical stress and / or corrosion, among others.

[0025] These and other objects of the invention will be immediately appreciated by those skilled in the art and will be described in detail below. Brief Description of the Figures

[0026] The following figures are presented:

[0027] Figure 1 shows the FTIR spectra of the samples.

[0028] Figure 1 A shows, respectively, the spectra of epoxy resin - Sample 1, epoxy resin - Sample 2 and epoxy resin - Sample 3.

[0029] Figure 1 B shows the superposition of these spectra (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0030] Figure 2 shows the FTIR spectra of the samples.

[0031] Figure 2A shows, respectively, the spectra of epoxy resin - Sample 4, epoxy resin - Sample 5 and epoxy resin - Sample 6.

[0032] Figure 2B shows the superposition of these spectra (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0033] Figure 3 shows the FTIR spectra of the samples.

[0034] Figure 3A shows, respectively, the spectra of epoxy resin - Sample 7, epoxy resin - Sample 8 and epoxy resin - Sample 9.

[0035] Figure 3B shows the superposition of these spectra (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0036] Figure 4 shows the FTIR spectra of the samples.

[0037] Figure 4A shows, respectively, the spectra of epoxy resin - Sample 10, epoxy resin - Sample 11 and epoxy resin - Sample 12.

[0038] Figure 4B shows the superposition of these spectra (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0039] Figure 5 shows the FTIR spectrum of the Lacktherm 1314 resin sample (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0040] Figure 6 presents a thermogravimetric analysis: the mass loss profile as a function of temperature and first derivative of the resin sample Sample 1 (on the Y axis, on the left, the & of the TG; on the Y axis on the right the DTF (% / min); and temperature in degrees Celsius on the X axis).

[0041] Figure 7 presents a thermogravimetric analysis: the mass loss profile as a function of temperature and first derivative of the resin sample Sample 2 (on the Y axis, on the left, the & of the TG; on the Y axis on the right the DTF (% / min); and temperature in degrees Celsius on the X axis).

[0042] Figure 8 presents a thermogravimetric analysis: the mass loss profile as a function of temperature and first derivative of the resin sample Sample 3 (on the Y axis, on the left, the & of the TG; on the Y axis on the right the DTF (% / min); and temperature in degrees Celsius on the X-axis).

[0043] Figure 9 presents a thermogravimetric analysis: the mass loss profile as a function of temperature and first derivative of the resin sample Sample 4 (on the Y axis, on the left, the & of the TG; on the Y axis on the right, the DTF (% / min); and temperature in degrees Celsius on the X axis).

[0044] Figure 10 presents a thermogravimetric analysis: the mass loss profile as a function of temperature and first derivative of the resin sample Sample 5 (on the Y axis, on the left, the & of the TG; on the Y axis on the right, the DTF (% / min); and temperature in degrees Celsius on the X axis).

[0045] Figure 1 1 presents a thermogravimetric analysis: the mass loss profile as a function of temperature and first derivative of the resin sample Sample 6 (on the Y axis, on the left, the & of the TG; on the Y axis on the right, the DTF (% / min); and temperature in degrees Celsius on the X axis).

[0046] Figure 12 presents a thermogravimetric analysis: the mass loss profile as a function of temperature and first derivative of the resin sample Sample 7 (on the Y axis, on the left, the & of the TG; on the Y axis on the right, the DTF (% / min); and temperature in degrees Celsius on the X axis).

[0047] Figure 13 presents a thermogravimetric analysis: the mass loss profile as a function of temperature and first derivative of the resin sample Sample 8 (on the Y axis, on the left, the & of the TG; on the Y axis on the right, the DTF (% / min); and temperature in degrees Celsius on the X axis).

[0048] Figure 14 presents a thermogravimetric analysis: the mass loss profile as a function of temperature and first derivative of the resin sample Sample 9 (on the Y axis, on the left, the & of the TG; on the Y axis on the right, the DTF (% / min); and temperature in degrees Celsius on the X axis).

[0049] Figure 15 presents a thermogravimetric analysis: the mass loss profile as a function of temperature and first derivative of the resin sample Sample 10 (on the Y axis, on the left, the & of the TG; on the Y axis on the right, the DTF (% / min); and temperature in degrees Celsius on the X axis).

[0050] Figure 16 presents a thermogravimetric analysis: the loss profile mass as a function of temperature and first derivative of the resin sample Sample 11 (on the Y axis, on the left, the & of the TG; on the Y axis on the right the DTF (% / min); and temperature in degrees Celsius on the X axis).

[0051] Figure 17 presents a thermogravimetric analysis: the mass loss profile as a function of temperature and first derivative of the resin sample Sample 11 (on the Y axis, on the left, the & of the TG; on the Y axis on the right, the DTF (% / min); and temperature in degrees Celsius on the X axis).

[0052] Figure 18 presents a thermogravimetric analysis: the mass loss profile as a function of temperature and first derivative of the resin sample Sample 12 (on the Y axis, on the left, the & of the TG; on the Y axis on the right, the DTF (% / min); and temperature in degrees Celsius on the X axis).

[0053] Figure 19 presents a thermogravimetric analysis: the mass loss profile as a function of temperature and first derivative of the Lacktherm 1314-1 resin sample (on the Y axis, on the left, the & of the TG; on the Y axis on the right, the DTF (% / min); and temperature in degrees Celsius on the X axis).

[0054] Figure 20 presents SEM images and EDS results for resin sample 1. In A) and B) scanning electron microscopy images are shown; in C) the EDS analysis image is shown.

[0055] Figure 21 shows SEM images and EDS results for resin sample 2. In A) a scanning electron microscopy image is shown; in B) the EDS analysis image is shown.

[0056] Figure 22 presents SEM images and EDS results for resin sample 3. In A) and B) scanning electron microscopy images are shown; in C) the EDS analysis image is shown.

[0057] Figure 23 presents SEM images and EDS results for resin sample 4. In A) and B) scanning electron microscopy images are shown; in C) the EDS analysis image is shown.

[0058] Figure 24 presents SEM images and EDS results for resin sample 5. In A) and B) scanning electron microscopy images are shown; in C) the EDS analysis image is shown.

[0059] Figure 25 shows SEM images and EDS results for resin sample 6. In A) and B) scanning electron microscopy images are shown; in C) the EDS analysis image is shown.

[0060] Figure 26 presents SEM images and EDS results for resin sample 7. In A) and B) scanning electron microscopy images are shown; in C) the EDS analysis image is shown.

[0061] Figure 27 shows SEM images and EDS results for resin sample 8. In A) and B) scanning electron microscopy images are shown; in C) the EDS analysis image is shown.

[0062] Figure 28 shows SEM images and EDS results for resin sample 9. In A) and B) scanning electron microscopy images are shown; in C) the EDS analysis image is shown.

[0063] Figure 29 presents SEM images and EDS results for resin sample 10. In A) and B) scanning electron microscopy images are shown; in C) the EDS analysis image is shown.

[0064] Figure 30 presents SEM images and EDS results for resin sample 1 1 . In A) and B) scanning electron microscopy images are shown; in C) the EDS analysis image is shown.

[0065] Figure 31 presents SEM images and EDS results for resin sample 12. In A) and B) scanning electron microscopy images are shown; in C) the EDS analysis image is shown.

[0066] Figure 32 shows a graph of the modification of the storage modulus (damping effect) of the 1020 / 1 resin with increasing temperature. In A) the storage modulus is shown in E'(1,000 Hz) / Mpa on the Y axis and the temperature in degrees Celsius on the X axis. In B) a graph with the Tangent Delta is shown for the same material, with the Tangent Delta values ​​shown on the y axis and the temperature in degrees Celsius on the X axis.

[0067] Figure 33 presents a graph of the modification of the storage modulus (damping effect) of the 1010 / 1 resin with increasing temperature. In A) the storage modulus in E'(1,000 Hz) / Mpa is shown on the Y axis and the temperature in degrees Celsius on the X axis. In B) a graph with the Tangent Delta is shown for the same material, with the Tangent Delta values ​​shown on the y axis and the temperature in degrees Celsius on the X axis.

[0068] Figure 34 shows a graph of the modification of the storage modulus (damping effect) of the 1000 / 0 resin with increasing temperature. In A) the storage modulus is shown in E'(1,000 Hz) / Mpa on the Y-axis and the temperature in degrees Celsius on the X-axis. In B) a graph with the Tangent Delta is shown for the same material, with the Tangent Delta values ​​shown on the y-axis and the temperature in degrees Celsius on the X-axis. Figure 35 shows a comparative graph of the storage moduli of the 1020 / 1, 1010 / 1 and 1000 / 0 resins, as shown in the graphs in figures 32A, 33A and 34A.

[0069] Figure 36 shows a comparative graph of the Tangent Delta data for resins 1020 / 1, 1010 / 1 and 1000 / 0, with graphs from figures 32B, 33B and 34B.

[0070] Figure 37 illustrates comparative curves of the storage modulus (E') by temperature for each sample described in example 8.

[0071] Figure 38 illustrates comparative curves of tangent delta (tan d) by temperature for each sample described in example 8.

[0072] Figure 39 shows a bar graph for the average activation energy (AE) for each sample described in Example 8.

[0073] Figure 40 shows a bar graph for the average storage modulus (E') of each sample described in Example 8.

[0074] Figure 41 shows a bar graph for the average tangent delta (tan d) of each sample described in Example 8.

[0075] Figure 42 shows a line graph comparing the variation in storage modulus (E') by concentration and nanoparticle type.

[0076] Figure 43 shows a line graph comparing the variation in tangent delta (tan d) by concentration and type of nanoparticle.

[0077] Figure 44 presents the FTIR spectra of the 1000 / 0 sample described in example 8 (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0078] Figure 45 shows the FTIR spectra of sample 1010 / 1 described in example 8 (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0079] Figure 46 shows the FTIR spectra of the 1010 / 2 sample described in example 8 (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0080] Figure 47 shows the FTIR spectra of the 1010 / 3 sample described in example 8 (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0081] Figure 48 presents the FTIR spectra of the 1010 / 4 sample described in example 8 (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0082] Figure 49 presents the FTIR spectra of sample 1020 / 1 described in example 8 (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0083] Figure 50 shows the FTIR spectra of the 1020 / 2 sample described in example 8 (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0084] Figure 51 shows the FTIR spectra of the 1020 / 3 sample described in example 8 (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0085] Figure 52 presents the FTIR spectra of the 1020 / 4 sample described in example 8 (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0086] Figure 53 presents the FTIR spectra of the 1030 / 4 sample described in example 8 (transmittance in % on the Y axis and wavenumber in cm -1 on the axis X).

[0087] Figure 54 presents the FTIR spectra of the 1040 / 4 sample described in example 8 (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0088] Figure 55 shows a comparison of the FTIR spectra of the samples described in example 8 (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0089] Figure 56 shows the storage modulus (E') curve of sample 1010 / 1 as a function of temperature.

[0090] Figure 57 shows the tangent delta (tan d) curve of sample 1010 / 1 as a function of temperature.

[0091] Figure 58 shows the loss modulus (E”) curve of sample 1010 / 1 as a function of temperature.

[0092] Figure 59 shows the storage modulus (E') curve of sample 1010 / 2 as a function of temperature.

[0093] Figure 60 shows the tangent delta (tan d) curve of sample 1010 / 2 as a function of temperature.

[0094] Figure 61 shows the loss modulus (E”) curve of sample 1010 / 2 as a function of temperature.

[0095] Figure 62 shows the storage modulus (E') curve of sample 1010 / 3 as a function of temperature.

[0096] Figure 63 shows the tangent delta (tan d) curve of sample 1010 / 3 as a function of temperature.

[0097] Figure 64 shows the loss modulus (E”) curve of sample 1010 / 3 as a function of temperature.

[0098] Figure 65 shows a bar graph of the average storage modulus (E') for each sample described in Example 15.

[0099] Figure 66 shows a bar graph of the average loss modulus (E”) for each sample described in Example 15.

[0100] Figure 67 shows a bar graph of the average temperature of glass transition (T g ) for each sample described in example 15.

[0101] Figure 68 illustrates the size histogram obtained from the transmission microscopy analysis of the as-received Niobium pentoxide particle sample (denoted AR).

[0102] Figure 69 illustrates the size histogram obtained from the transmission microscopy analysis of the sample of Niobium pentoxide particles subjected to milling for 1 h.

[0103] Figure 70 illustrates the size histogram obtained from the transmission microscopy analysis of the sample of Niobium pentoxide particles subjected to milling for 3h.

[0104] Figure 71 illustrates the size histogram obtained from the transmission microscopy analysis of the sample of Niobium pentoxide particles subjected to milling for 6h.

[0105] Figure 72 illustrates the size histogram obtained from the transmission microscopy analysis of the sample of Niobium pentoxide particles subjected to milling for 12 hours.

[0106] Figure 73 illustrates a comparison of X-ray diffractograms that demonstrate significant changes in the crystalline phase for samples of Niobium pentoxide particles subjected to different milling times (i.e., 1 h, 3h, 6h and 12h).

[0107] Figure 74 shows a graph of crystallinity (%) and crystallite size (nm) versus milling time (h).

[0108] Figure 75 shows particles of Niobium pentoxide highlighted in an ultrathin section of the sample at 50 ppm.

[0109] Figure 76 shows particles of Niobium pentoxide highlighted in an ultrathin section of the sample at 100 ppm.

[0110] Figure 77 shows particles of Niobium pentoxide highlighted in an ultrathin section of the sample at 250 ppm.

[0111] Figure 78 shows particles of Niobium pentoxide highlighted in an ultrathin section of the sample at 500 ppm.

[0112] Figure 79 shows a graph of the brake pad surface temperature at the end of each braking cycle for each of the samples tested.

[0113] Figure 80 shows photos of samples V1, V6 and V8 after 3 cycles of the accelerated corrosion test.

[0114] Figure 81 shows a graph of the Gogan C hardness and cold compressibility (5 MPa, whole pad) test for the friction materials containing niobium pentoxide nanoparticles in phenolic resin. Detailed Description of the Invention

[0115] In the context of the present invention, the term "niobium species or niobium-containing material" should be understood in its broadest sense as any species containing the element niobium. The term "niobium species or niobium-containing material" encompasses various chemical entities containing niobium, including metallic niobium, niobium oxides, oxalates, hydrates, hydrides, carbides, or nitrides, niobium iron or niobium alloyed with other metals or transition metals, or combinations thereof. It also includes niobium pentoxide (Nb206), NbO2, NbO, niobium oxalate, niobic acid, and FeNb.

[0116] In the context of the present invention, the term "titanium species or titanium-containing material" should be understood in its broadest sense as any species containing the element titanium. The term "titanium species or titanium-containing material" encompasses various chemical entities containing titanium, including metallic titanium, titanium oxides, oxalates, hydrates, hydrides, carbides, or nitrides, or titanium alloyed with other metals or transition metals, or combinations thereof. It also includes titanium dioxide.

[0117] In the context of the present invention, the term “Tantalum species or Tantalum-containing material” should be understood in its broadest sense as any species containing the element Tantalum. The term “Tantalum species or Tantalum-containing material” encompasses various chemical entities containing tantalum, including metallic tantalum, oxides, oxalates, hydrates, hydrides, carbides, or nitrides of tantalum, iron tantalum, or tantalum alloyed with other metals or metals. transition metals, or combinations thereof. Also includes tantalum pentoxide.

[0118] In the context of the present invention, the term "polymer or polymeric compound" is used in a broad sense, being selected from: diols, polyols, adhesives / plasticizers such as mesamoll, elastomers, rubbers, thermoplastic polymers, thermosetting polymers, resins, waxes, epoxy resins, phenolic resins, polymethyl methacrylate (acrylic), polystyrene, polyvinyl chloride (PVC), polyethylene, polypropylene, natural polymers selected from rubber, silk, wool, cellulose, or combinations thereof. In one embodiment, said diol or polyol is selected from: alkyl glycol, alkylene glycol, polyalkylene glycol, ethylene glycol, propylene glycol, butyl glycol, polyethylene glycol, polypropylene glycol, or combinations thereof.

[0119] It should be understood in its broadest sense as a macromolecule formed by the combination of at least two monomers, in which said monomers may comprise the same or different chemical composition.

[0120] The premix of the invention, when using a polymeric carrier or compatibilizer, can be useful for both producing modified polymers and modified metals or ceramics. For producing modified polymers, the carrier or compatibilizer is ideally a thermoplastic due to its improved processability. For producing modified metals or ceramics, the carrier may be a thermosetting polymer or, preferably, a low molecular weight and / or more fluid polymer, preferably a sacrificial carrier that evaporates during the processing of the material to be modified.

[0121] The invention may also be defined by the following clauses.

[0122] Functional premix comprising: a solid, semi-solid, pasty or liquid vehicle or compatibilizer; and a load of 0.0001 to 50% by weight of nanoparticles of defined particle size and chemically defined composition.

[0123] Premix as defined above, in which said vehicle or compatibilizer is selected from: a polymeric, ceramic, metallic material, or combinations thereof.

[0124] Premix as defined above, in which said polymeric material is selected from: diols, polyols, adhesives / plasticizers such as mesamoll, elastomers, rubbers, thermoplastic polymers, thermosetting polymers, resins, waxes, epoxy resins, phenolic resins, polymethyl methacrylate (acrylic), polystyrene, polyvinyl chloride (PVC), polyethylene, polypropylene, natural polymers selected from rubber, silk, wool, cellulose, or combinations thereof.

[0125] Premix as defined above, wherein said diol or polyol is selected from: alkyl glycol, alkylene glycol, polyalkylene glycol, ethylene glycol, propylene glycol, butyl glycol, polyethylene glycol, polypropylene glycol or combinations thereof.

[0126] Premix as defined above, wherein said nanoparticles are nanoparticles of metals, transition metals, non-metals, oxides, ceramic oxides, rare earths, or combinations thereof.

[0127] Premix as defined above, wherein said nanoparticles are of a material containing niobium, titanium, tantalum, their oxides, hydrates, carbides, oxalates, graphene, graphene oxide, or combinations thereof.

[0128] Premix as defined above, wherein said nanoparticles are niobium pentoxide, niobium oxalate, niobic acid, FeNb, titanium dioxide, tantalum pentoxide, or combinations thereof.

[0129] Premix as defined above, wherein said nanoparticles are smaller than 750nm, preferably smaller than 500nm.

[0130] Premix as defined above, wherein said nanoparticle charge comprises a degree of crystallinity below 81% or a degree of amortization of at least 19%.

[0131] Premix as defined above, wherein said nanoparticle charge comprises: (i) a degree of crystallinity below 61%, preferably a degree of crystallinity below 45% and more preferably a degree of crystallinity below 30%; or (ii) a degree of amortization of at least 39%, preferably a degree of amortization of at least 55% and more preferably a degree of amortization of at least 70%.

[0132] Process of obtaining the functional premix as defined above, comprising the steps of: - incorporate from 0.0001 to 50% by weight of nanoparticles of metals, transition metals, non-metals, oxides, ceramic oxides, rare earths, or combinations thereof into a vehicle or compatibilizer selected from a polymeric, ceramic, metallic material, or combinations thereof; and - homogenize and until a solid, semi-solid or pasty premix is ​​obtained.

[0133] Process for modifying materials, comprising one or more steps of adding the functional premix defined above to a processing step of metallic, ceramic, polymeric material or combinations thereof.

[0134] Material with modified properties obtained by the process defined above.

[0135] Material as defined above, comprising a concentration of nanoparticles in the range of 1 to 500 ppm.

[0136] In the present invention, the degree of crystallinity or amortization of the nanoparticles is relevant for some applications. In one embodiment of the functional premix, said nanoparticle charge comprises (i) a degree of crystallinity below 61%, preferably a degree of crystallinity below 45%, and even more preferably a degree of crystallinity below 30%; or (ii) a degree of amortization of at least 39%, preferably a degree of amortization of at least 55%, and even more preferably a degree of amortization of at least 70%.

[0137] In one embodiment of the functional premix, said nanoparticle load comprises a degree of amortization of at least 19%.

[0138] In one embodiment of the functional premix, said nanoparticle charge preferably comprises a degree of crystallinity below 80%, more preferably below 75%, more preferably below 70%, more preferably below 65%, more preferably below 61%, more preferably below 60%, more preferably below 55%, more preferably below 50%, more preferably a degree of crystallinity below 45%, more preferably below 40%, more preferably below 35% and even more preferably a degree of crystallinity below 30%. In one embodiment, the degree of crystallinity is below 29%, more preferably below 28%, more preferably below 27%. In a non-limiting embodiment, the degree of crystallinity is 26%.

[0139] In one embodiment of the functional premix, said nanoparticle charge preferably comprises a degree of crystallinity below 61%, preferably a degree of crystallinity below 45% and even more preferably a degree of crystallinity below 30%.

[0140] In one embodiment of the functional premix, said nanoparticle filler preferably comprises a degree of amortization of at least 20%, more preferably at least 25%, more preferably at least 30%, more preferably at least 35%, more preferably at least 39%, more preferably at least 40%, more preferably at least 45%, more preferably at least 50%, more preferably a degree of amortization of at least 55%, more preferably at least 60%, more preferably at least 65%, and even more preferably a degree of crystallinity of at least 70%. In one embodiment, the degree of amortization is at least 71%, more preferably at least 72%, more preferably at least 73%. In a non-limiting embodiment, the degree of amortization is 74%.

[0141] In an embodiment of the functional premix, said nanoparticle charge preferably comprises a degree of amortization of at least 39%, preferably a degree of amortization of at least 55% and even more preferably a degree of amortization of at least 70%.

[0142] In one embodiment of the functional premix, said nanoparticles are composed of non-metals, metals, transition metals, rare earths, species containing the same or combinations thereof.

[0143] In one embodiment of the functional premix, said niobium pentoxide nanoparticles comprise a particle size distribution profile as follows: d10: between 14 and 110 nm; d50: between 29 and 243 nm; and d90: between 89 and 747 nm.

[0144] In one embodiment of the functional premix, said titanium dioxide nanoparticles comprise a particle size distribution profile of: d10 from 148 to 189nm; d50 from 239 to 485m; d90 from 402 to 970nm.

[0145] In one embodiment, the material with modified properties comprises a concentration of nanoparticles in the range of tens to hundreds of ppm relative to the material with modified properties.

[0146] In one embodiment, the modified material comprises a concentration of nanoparticles in the range of 1 to 500 ppm.

[0147] In one embodiment, the concentration of said nanoparticles relative to the material is low, e.g., in the range between units, tens and hundreds of ppm, such as (non-limiting): 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 25, 50, 75, 100, 200, 250, 300, 400, 500, 600, 700, 800, 900 or 999 ppm. In one embodiment, a very low concentration of nanoparticles generated a surprising technical effect in modulating the properties of the polymers to which they were applied.

[0148] In one embodiment, the concentration of said nanoparticles relative to the material is 1 to 500 ppm.

[0149] In one embodiment, the concentration of said nanoparticles relative to the material is 50, 100, 250 or 500 ppm.

[0150] In one embodiment, the material with modified properties obtained has improved chemical, mechanical, electrical, and / or optical properties. In one embodiment of the method, the concentration of nanoparticles in the modified material is in the range of tens to hundreds of ppm.

[0151] In one embodiment, the modified material is a polymer with a modified crystal structure. In one embodiment, the modified polymer has modified mechanical properties. In one embodiment, said property is the storage modulus (E'), loss modulus (E”), loss factor (tan õ) and / or glass transition temperature (T g ) of a polymer.

[0152] The inventors of the present invention not only found that nanoparticles, when incorporated into polymer matrices, are capable of surprisingly improving chemical and mechanical properties (such as storage modulus (E'), loss modulus (E”), glass transition temperature (T g ) and tan delta), but still surprisingly, a higher degree of damping of the nanoparticles promotes an even more significant change in the properties of the polymer matrix.

[0153] In one embodiment, the functional premix of the present invention acts as a dosage adjuster for the nanoparticles that are loaded together with the vehicle for doping metallic, ceramic, polymeric material or combinations thereof.

[0154] In one embodiment, the functional premix of the present invention acts as a sacrificial carrier or a compatibilizer.

[0155] In one embodiment, the functional premix of the present invention acts as a sacrificial carrier for the incorporation of nanoparticles into a metallic and / or ceramic matrix.

[0156] In one embodiment, the functional premix of the present invention acts as a compatibilizer, with both the compatibilizer and the nanoparticles being incorporated into the polymer matrix.

[0157] The examples below show non-limiting examples of embodiments for more than one type of polymer and for a series of particle types, varying composition, grinding times, mass, particle size distribution, etc. Therefore, the scope of the claims presented is duly supported by this descriptive report.

[0158] Examples

[0159] The examples shown here are intended only to illustrate some of the various ways in which the invention can be carried out, without however limiting the scope thereof.

[0160] Modifying polymers or other materials, such as metals and / or ceramics, with the incorporation of particles in the micrometer range can lead to catastrophic failures such as cracks, deformations, irregularities in geometry, and other problems. The invention solves this problem and provides premixes containing nanoparticles in high concentrations. Because the nanoparticle concentrations of the inventive premixes are orders of magnitude higher than those required to obtain improvements in the properties of the final materials containing such nanoparticles, the inventive premixes are particularly useful for the subsequent preparation of materials with lower nanoparticle concentrations, using these premixes as premixes or compatibilizers.If one wishes to prepare a material with 5 or 50 ppm of any of the nanoparticles described in this patent application, it is sufficient to use a 1:100 or 1:10 mixture, respectively, of the corresponding premix with the material to be modified, and homogenize until the product with the aforementioned concentration is obtained. Other final concentrations can be obtained by adjusting the premix concentrations in the desired material.

[0161] To analyze the modified materials obtained using the premix of the invention, some tests are performed, such as those described below.

[0162] Thermodynamic-mechanical analysis (DMTA) has been widely used in the characterization of polymers by detecting their relaxation processes, both at the macroscopic and molecular levels. In other words, it provides information on the viscoelastic behavior of a system by dividing the modulus into two components: an elastic contribution and a viscous contribution.

[0163] The module of the system E* is represented mathematically as a complex number composed of two components: E* = E' + iE”

[0164] Where E' is the storage modulus (measure of the elasticity of the material - the material's ability to store energy) and E” is the loss modulus (the material's ability to dissipate energy - energy lost in the form of heat).

[0165] DMTA analysis also allows obtaining the loss or damping tangent (tan delta), which is the ratio between the dissipated energy and the maximum potential energy stored during the cycle: Tan delta = E” / E'

[0166] Materials with high tan delta dissipate much of the energy used to deform them, while materials with low tan delta are more elastic and have a greater capacity to store energy.

[0167] Example 1 - Epoxy resin premix containing graphene oxide nanoparticles

[0168] A premix embodiment of the invention is an epoxy resin with up to 500 ppm of graphene oxide nanoparticles. The epoxy resin used in the experiments is the commercially available DER 331™ liquid epoxy resin from Dow Chemical Company, which is a liquid reaction product of epichlorohydrin and bisphenol A.

[0169] The concentrations of graphene oxide nanoparticles that are incorporated into the resin are described in Table 1, for the samples named in the tests discussed below and illustrated in Figures 1-31:

[0170] Table 1 - Description of samples 1-4

[0171] Example 2 - Epoxy resin containing Nb20s nanoparticles

[0172] Another premix embodiment of the invention is an epoxy resin with up to 500 ppm of niobium pentoxide nanoparticles. The epoxy resin used in the experiments is the commercially available DER 331™ liquid epoxy resin from Dow Chemical Company which is a liquid reaction product of epichlorohydrin and bisphenol A.

[0173] The concentrations of niobium pentoxide nanoparticles that are incorporated into the resin are described in the table below for the samples named in the tests discussed below and illustrated in Figures 1-31:

[0174] Table 2 - Description of samples 5-8

[0175] The granulometric profile of the niobium nanoparticles used is described in detail in patent application WO2022036427, from the same holder, for a sample subjected to 12 hours of milling.

[0176] Example 3 - Epoxy resin containing TiO2 nanoparticles

[0177] One premix embodiment of the invention is an epoxy resin with up to 500 ppm of titanium dioxide nanoparticles. The epoxy resin used in the experiments is the commercially available DER 331™ liquid epoxy resin from Dow Chemical Company, which is a liquid reaction product of epichlorohydrin and bisphenol A.

[0178] The concentrations of titanium dioxide nanoparticles that are incorporated into the resin are described in the table below for the samples named in the tests discussed below and illustrated in Figures 1-31:

[0179] Table 3 - Description of samples 9-12

[0180] The granulometric profile of the titanium nanoparticles used is described in detail in patent application BR102022010931 (still confidential) by the same holder for a sample subjected to 12 hours of milling.

[0181] Example 4 - Fourier Transform Infrared Spectroscopy (FTIR) Analysis.

[0182] The nanoparticle resin premixes prepared according to examples 1, 2, and 3 were cured and subsequently subjected to various types of tests. In a first series of tests, they were subjected to infrared spectroscopy. This technique is certainly one of the most important analytical techniques currently available. One of the great advantages of this technique is that a large number of samples, in virtually any physical state, can be studied. Liquids, solutions, pastes, powders, films, fibers, gases, and surfaces can be analyzed with a careful choice of sampling technique and preparation. The introduction of Fourier transform infrared (FTIR) spectrometers has dramatically improved the quality of infrared spectra and minimized the time required to obtain data. The constant improvement of computers has enabled the development of a variety of techniques for testing / examining previously intractable samples.Infrared radiation (IR) corresponds approximately to the part of the electromagnetic spectrum located between the visible and microwave regions. The most useful portion for material analysis and identification is located between 4000 cm². 1 and 400 cm' 1 (2.5 pm and 25 pm), the so-called mid-infrared. Infrared spectroscopy is based on the vibrations of atoms in a molecule. An infrared spectrum is commonly obtained by passing infrared radiation through a sample and determining the fraction of the incident radiation that is absorbed at each frequency (energy) or wavelength. By absorbing infrared radiation, molecules are excited to energy states. larger. This process is quantized, meaning only certain frequencies (energies) are absorbed, and this absorption corresponds to energy variations on the order of 8 to 40 kJ / mol. Although the infrared absorption process is quantized, the spectrum usually appears as a series of bands rather than lines because each change in vibrational energy level corresponds to a series of changes in rotational levels. The lines overlap, giving rise to the observed bands, vibration-rotation bands. The absorption frequency or wavelength of a radiation depends on the relative masses of the atoms, the bond strength constants, and the geometry of the atoms in the compound's structure. Each absorption frequency present in an infrared spectrum corresponds to a vibrational frequency of a portion of a molecule in the sample. The positions of the bands in infrared spectra can be expressed in wavelength (pm) or wavenumber (cm). -1), and the intensities of the bands in percentage of transmittance (%T) or absorbance (A). Transmittance is the ratio of the radiant energy transmitted by a sample to the radiant energy incident on it. Absorbance is the decimal logarithm of the inverse of transmittance, that is, A = Iog10(1 / T).

[0183] In this example, the Bruker OPTIK GmbH HTS-XT, model Vertex 70, operating in ATR (Attenuated Total Reflectance) mode with a diamond crystal was used. The liquid samples were deposited in the equipment's sample holder and the measurements were performed in an observation range of 4,000 cm. 1 at 400 cnr 1 with a resolution of 4 cm-1 and making 32 scans.

[0184] The results are shown in figures 1-5.

[0185] Figure 1 shows the FTIR spectra of the samples. Figure 1A shows, respectively, the spectra of Sample 1, Sample 2 and Sample 3. Figure 1B shows the superposition of these spectra (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0186] Figure 2 shows the FTIR spectra of the samples. In Figure 2A the spectra of Sample 4, Sample 5 and Sample 6 are shown, respectively. Figure 2B shows the superposition of these spectra (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0187] Figure 3 shows the FTIR spectra of the samples. Figure 3A shows, respectively, the spectra of Sample 7, Sample 8 and Sample 9. Figure 3B shows the superposition of these spectra (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0188] Figure 4 shows the FTIR spectra of the samples. Figure 4A shows, respectively, the spectra of Sample 10, Sample 11 and Sample 12. Figure 4B shows the superposition of these spectra (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0189] Figure 5 shows the FTIR spectrum of the Lacktherm 1314 resin sample (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0190] Example 5 - Thermogravimetric analysis

[0191] The premixes prepared according to Examples 1, 2, and 3 were cured and analyzed by thermogravimetry. The results are shown in Figures 6-19.

[0192] Figure 6 presents a thermogravimetric analysis: the mass loss profile as a function of temperature and first derivative of Sample 1 (on the Y axis, on the left, the & of the TG; on the Y axis on the right, the DTF (% / min); and temperature in degrees Celsius on the X axis).

[0193] Figure 7 presents a thermogravimetric analysis: the mass loss profile as a function of temperature and first derivative of Sample 2 (on the Y axis, on the left, the & of the TG; on the Y axis on the right, the DTF (% / min); and temperature in degrees Celsius on the X axis).

[0194] Figure 8 presents a thermogravimetric analysis: the mass loss profile as a function of temperature and first derivative of sample 3 (on the Y axis, on the left, the & of the TG; on the Y axis on the right, the DTF (% / min); and temperature in degrees Celsius on the X axis).

[0195] Figure 9 presents a thermogravimetric analysis: the profile of the loss of mass as a function of temperature and first derivative of Sample 4 (on the Y axis, on the left, the & of the TG; on the Y axis on the right the DTF (% / min); and temperature in degrees Celsius on the X axis).

[0196] Figure 10 presents a thermogravimetric analysis: the mass loss profile as a function of temperature and first derivative of Sample 5 (on the Y axis, on the left, the & of the TG; on the Y axis on the right, the DTF (% / min); and temperature in degrees Celsius on the X axis).

[0197] Figure 1 1 presents a thermogravimetric analysis: the mass loss profile as a function of temperature and first derivative of Sample 6 (on the Y axis, on the left, the & of the TG; on the Y axis on the right, the DTF (% / min); and temperature in degrees Celsius on the X axis).

[0198] Figure 12 presents a thermogravimetric analysis: the mass loss profile as a function of temperature and first derivative of Sample 7 (on the Y axis, on the left, the & of the TG; on the Y axis on the right, the DTF (% / min); and temperature in degrees Celsius on the X axis).

[0199] Figure 13 presents a thermogravimetric analysis: the mass loss profile as a function of temperature and first derivative of Sample 8 (on the Y axis, on the left, the & of the TG; on the Y axis on the right, the DTF (% / min); and temperature in degrees Celsius on the X axis).

[0200] Figure 14 presents a thermogravimetric analysis: the mass loss profile as a function of temperature and first derivative of Sample 9 (on the Y axis, on the left, the & of the TG; on the Y axis on the right, the DTF (% / min); and temperature in degrees Celsius on the X axis).

[0201] Figure 15 presents a thermogravimetric analysis: the mass loss profile as a function of temperature and first derivative of Sample 10 (on the Y axis, on the left, the & of the TG; on the Y axis on the right, the DTF (% / min); and temperature in degrees Celsius on the X axis).

[0202] Figure 16 presents a thermogravimetric analysis: the mass loss profile as a function of temperature and first derivative of Sample 1 1 (on the Y axis, on the left, the & of the TG; on the Y axis on the right, the DTF (% / min); and temperature in degrees Celsius on the X-axis).

[0203] Figure 17 presents a thermogravimetric analysis: the mass loss profile as a function of temperature and first derivative of Sample 1 1 (on the Y axis, on the left, the & of the TG; on the Y axis on the right, the DTF (% / min); and temperature in degrees Celsius on the X axis).

[0204] Figure 18 presents a thermogravimetric analysis: the mass loss profile as a function of temperature and first derivative of Sample 12 (on the Y axis, on the left, the & of the TG; on the Y axis on the right, the DTF (% / min); and temperature in degrees Celsius on the X axis).

[0205] Figure 19 presents a thermogravimetric analysis: the mass loss profile as a function of temperature and first derivative of the Lacktherm 1314-1 resin sample (on the Y axis, on the left, the & of the TG; on the Y axis on the right, the DTF (% / min); and temperature in degrees Celsius on the X axis).

[0206] Example 6 - Scanning Electron Microscopy Analysis

[0207] The analysis of the premixes prepared according to Examples 1, 2, and 3 and cured was performed by scanning electron microscopy (SEM) and EDS (indicate significance). The results are shown in Figures 24–35.

[0208] Figure 20 presents SEM images and EDS results for sample 1. In A) and B) scanning electron microscopy images are shown; in C) the EDS analysis image is shown.

[0209] Figure 21 presents SEM images and EDS results for sample 2. In A) a scanning electron microscopy image is shown; in B) the EDS analysis image is shown.

[0210] Figure 22 presents SEM images and EDS results for sample 3. In A) and B) scanning electron microscopy images are shown; in C) the EDS analysis image is shown.

[0211] Figure 23 presents SEM images and EDS results for sample 4. In A) and B) scanning electron microscopy images are shown; in C) the EDS analysis image is shown.

[0212] Figure 24 presents SEM images and EDS results for the sample 5. In A) and B) scanning electron microscopy images are shown; in C) the EDS analysis image is shown.

[0213] Figure 25 shows SEM images and EDS results for sample 6. In A) and B) scanning electron microscopy images are shown; in C) the EDS analysis image is shown.

[0214] Figure 26 presents SEM images and EDS results for sample 7. In A) and B) scanning electron microscopy images are shown; in C) the EDS analysis image is shown.

[0215] Figure 27 shows SEM images and EDS results for sample 8. In A) and B) scanning electron microscopy images are shown; in C) the EDS analysis image is shown.

[0216] Figure 28 presents SEM images and EDS results for sample 9. In A) and B) scanning electron microscopy images are shown; in C) the EDS analysis image is shown.

[0217] Figure 29 presents SEM images and EDS results for sample 10. In A) and B) scanning electron microscopy images are shown; in C) the EDS analysis image is shown.

[0218] Figure 30 presents SEM images and EDS results for sample 11. In A) and B) scanning electron microscopy images are shown; in C) the EDS analysis image is shown.

[0219] Figure 31 presents SEM images and EDS results for sample 12. In A) and B) scanning electron microscopy images are shown; in C) the EDS analysis image is shown.

[0220] Example 7 - Epoxy resin premix containing Nb20s nanoparticles - tangent Delta storage modulus analysis with temperature change.

[0221] For the tests, triplicates of samples 1000 / 0; 1010 / 1; 1020 / 1 were considered, since the other samples are only surplus specimens and did not present considerable variability for the tests.

[0222] Polymer samples comprising carbon dioxide microparticles titanium and niobium pentoxide were not tested because they presented catastrophic failures such as cracks, deformations, and irregularities in geometry.

[0223] In contrast, the premixes containing nanoparticles were obtained adequately, i.e., the nanoparticles were incorporated into the resin at the tested concentrations. The respective premixes, prior to curing, are particularly useful for the subsequent preparation of resins with lower nanoparticle concentrations, using these premixes as premixes. That is, if one wishes to prepare an epoxy resin with 50 ppm of any of the nanoparticles described in the examples above (graphene oxide, niobium pentoxide, titanium dioxide), a 1:10 mixture of the respective premix and the resin is used, and homogenized until the product with the specified concentration is obtained. Other final concentrations can be obtained by adjusting the concentrations.

[0224] Table 4 shows the codes of the tested samples:

[0225] Table 5 shows the results of the activation energy (average value) for the mentioned resins.

[0226] Table 6 shows the storage modulus results (average value) for the aforementioned resins.

[0227] Table 7 shows the tangent delta results (average value) for the aforementioned resins.

[0228] Table 8 shows the glass transition temperature TG results (average value) for the mentioned resins.

[0229] Table 9 shows the raw storage modulus data of 1020 / 1 resin according to temperature, indicating the damping effect.

[0230] Table 9 - Storage module data.

[0231] Table 10 shows the raw storage modulus data of 1010 / 1 resin according to temperature, indicating the damping effect.

[0232] Table 10 - Storage module data.

[0233] Table 11 shows the raw storage modulus data of the 1000 / 0 resin according to temperature, indicating the damping effect.

[0234] Table 11 - Storage module data.

[0235] Table 12 shows the data on the average storage modulus of resins 1020 / 1, 1010 / 1 and 1000 / 0 according to temperature.

[0236] Table 12 - averages of storage module measurements.

[0237] Table 13 shows the tangent delta data of 1020 / 1 resin according to temperature.

[0238] Table 13 - tangent delta data for resin 1020 / 1.

[0239] Table 14 shows the tangent delta data of 1010 / 1 resin according to temperature.

[0240] Table 14 - Tangent delta data for resin 1010 / 1

[0241] Table 15 shows the tangent delta data of 1000 / 0 resin according to temperature.

[0242] Table 15 - tangent delta data for 1000 / 0 resin.

[0243] Table 16 shows the comparative tangent delta data of the resins. 1020 / 1, 1010 / 1 and 1000 / 0, according to the temperature.

[0244] Table 16 - Comparison between tangent delta averages

[0245] The data in Tables 8-16 can be viewed in graph form, as illustrated in Figures 32-36.

[0246] Figure 32 presents a graph of the modification of the storage modulus (damping effect) of the 1020 / 1 resin with increasing temperature. In A) the storage modulus is shown in E'(1,000 Hz) / Mpa on the Y axis and the temperature in degrees Celsius on the X axis. In B) and A graph of the Tangent Delta is shown for the same material, with the Tangent Delta values ​​shown on the y-axis and the temperature in degrees Celsius on the x-axis. The graphs show the means and deviations, in accordance with the data in tables 9 and 13.

[0247] Figure 33 shows a graph of the modification of the storage modulus (damping effect) of 1010 / 1 resin with increasing temperature. In A) the storage modulus is shown in E'(1,000 Hz) / Mpa on the Y-axis and the temperature in degrees Celsius on the X-axis. In B) a graph with the Tangent Delta is shown for the same material, with the Tangent Delta values ​​shown on the y-axis and the temperature in degrees Celsius on the X-axis. The graphs show the means and deviations, in accordance with the data in Tables 10 and 14.

[0248] Figure 34 presents a graph of the modification of the storage modulus (damping effect) of the 1000 / 0 resin with increasing temperature. In A) the storage modulus is shown in E'(1,000 Hz) / Mpa on the Y-axis and the temperature in degrees Celsius on the X-axis. In B) a graph with the Tangent Delta is shown for the same material, with the Tangent Delta values ​​shown on the Y-axis and the temperature in degrees Celsius on the X-axis. The graphs show the means and deviations, in accordance with the data in Tables 11 and 15.

[0249] Figure 35 shows a comparative graph of the storage moduli of resins 1020 / 1, 1010 / 1 and 1000 / 0, with graphs from figures 36A, 37A and 38A.

[0250] Figure 36 shows a comparative graph of the Tangent Delta data for resins 1020 / 1, 1010 / 1 and 1000 / 0, with graphs from figures 36B, 37B and 38B.

[0251] Together, the results shown in Tables 8-16 and Figures 32-36 indicate that the incorporation of nanoparticles at a low concentration (ppm range) was able to substantially modify the mechanical properties of the polymer, as can be seen from the tangent delta results. Whereas Tan delta can be understood as a material's energy dissipation potential. A higher tan delta indicates a more dissipative material. Conversely, a lower tan delta indicates a more elastic material when a load is applied, thus having greater potential to store load. Thus, modifying the tan delta (either increasing or decreasing it) can modulate a material to become more suitable for various applications. For example, a lower tan delta may be preferred for structural applications.

[0252] Example 8 - Description of samples

[0253] Table 17 provides a description of the samples tested in the following examples:

[0254] Polymer samples containing titanium dioxide and niobium pentoxide microparticles were not tested because they exhibited catastrophic failures such as cracks, deformations, and irregularities in geometry. Similar to what was described in the previous examples, premixes containing nanoparticles were obtained adequately, that is, the nanoparticles were incorporated into the resin at the tested concentrations. The respective premixes are particularly useful for the subsequent preparation of resins with lower nanoparticle concentrations, using these premixes as premixes. That is, if one wishes to prepare an epoxy resin with 50 ppm of any of the nanoparticles described in the examples above (graphene oxide, niobium pentoxide, titanium dioxide), a 1:10 mixture of the respective premix and the resin is used, and homogenized until the product with the specified concentration is obtained. Other final concentrations can be obtained by adjusting the concentrations.

[0255] Example 9 - Analysis of the storage modulus (E')

[0256] The samples described in example 8 were analyzed in DMTA (Mechanical Thermodynamic Analysis) in triplicate and the storage modulus (E') results are shown below in tables 18-26:

[0257] Table 18 - Storage modulus (E') results for sample 1020 / 1 in triplicate

[0258] Table 19 - Storage modulus (E') results for sample 1010 / 1 in quintuplicate

[0259] Table 20 - Storage modulus (E') results for sample 1000 / 0 in quadruplicate.

[0260] Table 21 - Storage modulus (E') results for sample 1020 / 4 in triplicate.

[0261] Table 22 - Storage modulus (E') results for sample 1010 / 3 in triplicate.

[0262] Table 23 - Storage modulus (E') results for sample 1010 / 4 in triplicate.

[0263] Table 24 - Storage modulus (E') results for sample 1010 / 2 in quintuplicate

[0264] Table 25 - Storage modulus (E') results for sample 1020 / 3 in triplicate

[0265] Table 26 - Storage modulus (E') results for sample 1020 / 2 in quadruplicate

[0266] Example 10 - Analysis of the tangent of delta (tan d)

[0267] The samples described in example 8 were analyzed in DMTA (Mechanical Thermodynamic Analysis) in triplicate and the results of the storage modulus (E') are shown below in tables 27-35:

[0268] Table 27 - Tangent delta (tan d) results for sample 1020 / 1 in triplicate:

[0269] Table 28 - Tangent delta (tan d) results for sample 1010 / 1 in quintuplicate:

[0270] Table 29 - Tangent delta (tan d) results for sample 1000 / 0 in quadruplicate:

[0271] Table 30 - Tangent delta (tan d) results for sample 1010 / 4 in triplicate:

[0272] Table 31 - Tangent delta (tan d) results for sample 1010 / 3 in triplicate:

[0273] Table 32 - Tangent delta (tan d) results for sample 1020 / 4 in triplicate:

[0274] Table 33 - Tangent delta (tan d) results for sample 1010 / 2 in quintuplicate:

[0275] Table 34 - Tangent delta (tan d) results for sample 1020 / 3 in triplicate:

[0276] Table 35 - Tangent delta (tan d) results for sample 1020 / 2 in quadruplicate:

[0277] Example 11 - Comparison of tangent delta data (tan d)

[0278] Tables 36 and 37 below show a comparison of average tangent delta data for each sample described in example 8:

[0279] Table 36 - Comparison of average tangent delta (tan d) data:

[0280] Table 37 - Comparison of average tangent delta (tan d) data:

[0281] Example 12 - Comparison of storage module data (E')

[0282] Tables 38 and 39 below show a comparison of average storage modulus data for each sample described in example 8:

[0283] Table 38 - Comparison of average storage module (E') data:

[0284] Table 39 - Comparison of average storage module (E') data:

[0285] Example 13 - Comparison of DMTA analysis results

[0286] Tables 40, 41 and 42 below show, respectively, a comparative data on activation energy (EA), storage modulus (E') and tangent delta (tan d) for each sample described in example 8:

[0287] Table 40 - Comparison of average activation energy (EA) data per sample:

[0288] Table 41 - Comparison of average storage modulus (E') data per sample:

[0289] Table 42 - Comparison of data on the average tangent delta (tan d) per sample:

[0290] Table 43 - Comparison of data on the average glass transition temperature (Tg) per sample:

[0291] Figure 37 illustrates comparative curves of the storage modulus (E') by temperature for each sample described in example 8.

[0292] Figure 38 illustrates comparative curves of tangent delta (tan d) by temperature for each sample described in example 8.

[0293] Alternatively, Figures 39, 40, and 41 illustrate bar graph comparisons for the DMTA results of the samples described in Example 8.

[0294] Figure 39 shows a bar graph for the average activation energy (AE) for each sample described in Example 8.

[0295] Figure 40 shows a bar graph for the average storage modulus (E') of each sample described in Example 8.

[0296] Figure 41 shows a bar graph for the average tangent delta (tan d) of each sample described in Example 8.

[0297] Additionally, Figure 42 shows a line graph comparing the variation of the storage modulus (E') by concentration and type of nanoparticle.

[0298] Additionally, Figure 43 shows a line graph comparing the variation of tangent delta (tan d) by concentration and nanoparticle type.

[0299] From the DMTA analysis of the samples described in Example 8, it can be concluded that the incorporation of nanoparticles at a low concentration (ppm range) was able to substantially modify the polymer's mechanical properties, as can be seen from the tan delta results. Tan delta can be understood as a material's energy dissipation potential. A higher tan delta indicates a more dissipative material. Conversely, a lower tan delta indicates a more elastic material when a load is applied, thus having greater potential to store charge. Thus, modifying the tan delta (both increasing and decreasing it) can modulate a material to become more suitable for various applications; e.g., a lower tan delta may be preferred for structural applications.

[0300] Example 14 - Fourier Transform Infrared Spectroscopy (FTIR) Analysis.

[0301] The results of Fourier Transform Infrared Spectroscopy analysis are shown in Figures 44-55 for each sample as described in Example 8.

[0302] Figure 44 presents the FTIR spectra of the 1000 / 0 sample described in example 8 (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0303] Figure 45 shows the FTIR spectra of sample 1010 / 1 described in example 8 (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0304] Figure 46 shows the FTIR spectra of the 1010 / 2 sample described in example 8 (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0305] Figure 47 shows the FTIR spectra of the 1010 / 3 sample described in example 8 (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0306] Figure 48 presents the FTIR spectra of the 1010 / 4 sample described in example 8 (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0307] Figure 49 presents the FTIR spectra of sample 1020 / 1 described in example 8 (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0308] Figure 50 shows the FTIR spectra of the 1020 / 2 sample described in example 8 (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0309] Figure 51 shows the FTIR spectra of the 1020 / 3 sample described in example 8 (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0310] Figure 52 presents the FTIR spectra of the 1020 / 4 sample described in example 8 (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0311] Figure 53 presents the FTIR spectra of the 1030 / 4 sample described in example 8 (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0312] Figure 54 presents the FTIR spectra of the 1040 / 4 sample described in example 8 (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0313] Figure 55 shows a comparison of the FTIR spectra of the samples described in example 8 (transmittance in % on the Y axis and wavenumber in cm -1 on the X-axis).

[0314] Example 15 - DMTA analysis of samples containing niobium nanoparticles

[0315] The samples described in example 8 as 1010 / 1 were analyzed in DMTA (Mechanical Thermodynamic Analysis) in quadruplicate and the results are shown below in Table 44:

[0316] Table 44 - DMTA results for sample 1010 / 1 at a frequency of 1 Hz:

[0317] Table 45 - Activation energy results for sample 1010 / 1 :

[0318] The results of sample 1010 / 1 are further illustrated in figures 56, 57 and 58.

[0319] Figure 56 shows the storage modulus (E') curve of sample 1010 / 1 as a function of temperature.

[0320] Figure 57 shows the tangent delta (tan d) curve of sample 1010 / 1 as a function of temperature.

[0321] Figure 58 shows the loss modulus (E”) curve of sample 1010 / 1 as a function of temperature.

[0322] The samples described in example 8 as 1010 / 2 were also analyzed in DMTA (Mechanical Thermodynamic Analysis) in quadruplicate and the results are shown below in tables 43 and 44:

[0323] Table 46 - DMTA results for sample 1010 / 2 in frequency of 1 Hz:

[0324] Table 47 - DMTA results for sample 1010 / 2 at a frequency of 5 Hz:

[0325] Table 48 - Activation energy results for sample 1010 / 2:

[0326] The results of sample 1010 / 2 are further illustrated in figures 59, 60 and 61.

[0327] Figure 59 shows the storage modulus (E') curve of sample 1010 / 2 as a function of temperature.

[0328] Figure 60 shows the tangent delta (tan d) curve of sample 1010 / 2 as a function of temperature.

[0329] Figure 61 shows the loss modulus (E”) curve of sample 1010 / 2 as a function of temperature.

[0330] The samples described in example 8 as 1010 / 3 were analyzed in DMTA (Mechanical Thermodynamic Analysis) in quadruplicate and the results are shown below in table 49:

[0331] Table 49 - DMTA results for sample 1010 / 3 at a frequency of 1 Hz:

[0332] Table 50 - Activation energy results for sample 1010 / 3:

[0333] The results of sample 1010 / 3 are further illustrated in figures 62, 63 and 64.

[0334] Figure 62 shows the storage modulus (E') curve of sample 1010 / 3 as a function of temperature.

[0335] Figure 63 shows the tangent delta (tan d) curve for sample 1010 / 3 depending on the temperature.

[0336] Figure 64 shows the loss modulus (E”) curve of sample 1010 / 3 as a function of temperature.

[0337] Example 16 - Comparison of DMTA analyses of samples containing niobium nanoparticles

[0338] Based on the results presented in example 15, the averages for the storage modulus (E'), loss modulus (E”) and glass transition temperature (T) were found. g) for each sample. The tables with the comparative data are illustrated below:

[0339] Table 51 - storage modulus (E') values ​​for each sample:

[0340] Table 52 - loss modulus (E”) values ​​for each sample:

[0341] Table 53 - values ​​of glass transition temperature (T g ) for each sample:

[0342] Figure 65 shows a bar graph of the average storage modulus (E') for each sample described in Example 15.

[0343] Figure 66 shows a bar graph of the average loss modulus (E”) for each sample described in Example 15.

[0344] Figure 67 shows a bar graph of the average temperature of glass transition (T g ) for each sample described in example 15.

[0345] From the DMTA analysis of example 16, it can be concluded that the incorporation of nanoparticles at a low concentration (ppm range) was able to substantially modify the polymer's mechanical properties, as can be seen from the tan delta results. Tan delta can be understood as a material's energy dissipation potential. A higher tan delta indicates a more dissipative material. Conversely, a lower tan delta indicates a more elastic material when a load is applied, thus having greater potential to store charge. Thus, modifying the tan delta (both increasing and decreasing it) can modulate a material to become more suitable for various applications; e.g., a lower tan delta may be preferred for structural applications.

[0346] Example 17 - Process for preparing niobium pentoxide nanoparticles

[0347] In the present example, several embodiments of niobium pentoxide nanoparticle preparations were obtained, with purity greater than 99%. Commercial niobium pentoxide, with the particle size distribution described in Table 54, was pre-comminuted in a high-energy mill containing yttria-stabilized zirconia spheres with a diameter of 400 pm, in a liquid medium and the pH adjusted to 6.6. The mill rotation speed was 3500 rpm and the particle grinding was carried out at a temperature below 40 °C. Table 4 shows the particle size distribution (PSD) of incoming niobium pentoxide (commercial product) and outgoing niobium pentoxide from a pre-comminution step.

[0348] Table 54 - Input DTP (commercial product) and output DTP after pre-comminution.

[0349] The average specific surface area S (m 2 / g) of the particles after the pre-comminution step was 0.32 m 2 / g.

[0350] In one embodiment, the pre-crushed particles were then fed to a high-energy mill, applying conditions similar to those described in Example 5, but with 200 pm Zr spheres and milling for different times, until each nanoparticle preparation was obtained. Three different nanoparticle preparations were obtained, each with a defined particle size distribution as described in Table 55.

[0351] Table 55 - Particle size distribution of three different preparations (C, D and E) of Niobium pentoxide nanoparticles.

[0352] Example 18 - Process for preparing titanium dioxide nanoparticles

[0353] In this embodiment, a batch of 1.125 kg TiO2 particles with particle size distributions of D90 1.320 pm, D50 0.6098 pm, and D10 0.153 pm was fed to a high-energy mill with 5 liters of water and containing 3.65 kJ / L 0.2-0.4 mm zeta beads. The grinding parameters were Tmax 60 °C and solids content of 18.36%. The high-energy mill was operated for several cycles, from 1 to 8 cycles of 1 hour each, at a pressure of 1.1 to 1.2 bar and a pump speed of 90 min. 1 , flow rate of 51 kgslurry / h, agitator speed of 3700 min 1 , input material temperature varying between 21.3 °C and 37.1 °C and output material temperature varying between 22.4 °C and 49.2 °C in the respective cycles, the gross energy was 2.4 kW and the grinding energy was from 1.8 to 14.4 kWh in the respective cycles. The particle size distribution profile obtained is described in table 56 below:

[0354] Table 56 - particle size distribution profile obtained after multiple comminution cycles under the conditions indicated above.

[0355] For cooling, the parameters were inlet temperature of 7.3 °C and 1 1.4 °C, respectively in the grinding chamber, mechanical seal, circulation tank and chiller, each of these stages with a flow rate of 1000 liters per hour of cooling water, totaling 4000 liters per hour.

[0356] Example 19 - Testing the degree of crystallinity of niobium pentoxide nanoparticles

[0357] The inventors studied the characteristics of the Niobium pentoxide nanoparticle preparation resulting from different milling times according to the process described in example 17.

[0358] The samples were analyzed using transmission microscopy to obtain a particle diameter histogram and X-ray diffraction to obtain structural characterization. X-ray diffraction analysis of the samples demonstrated significant changes in structural characteristics, such as degree of crystallinity (%) and crystallite size, for the samples subjected to different milling times.

[0359] Figure 68 illustrates the size histogram obtained from the transmission microscopy analysis of the as-received Niobium pentoxide particle sample (denoted AR).

[0360] Figure 69 illustrates the size histogram obtained from the transmission microscopy analysis of the sample of Niobium pentoxide particles subjected to milling for 1 h.

[0361] Figure 70 illustrates the size histogram obtained from the transmission microscopy analysis of the sample of Niobium pentoxide particles subjected to milling for 3h.

[0362] Figure 71 illustrates the size histogram obtained from the transmission microscopy analysis of the sample of Niobium pentoxide particles subjected to milling for 6h.

[0363] Figure 72 illustrates the size histogram obtained from the transmission microscopy analysis of the sample of Niobium pentoxide particles subjected to milling for 12 hours.

[0364] Figure 73 illustrates a comparison of X-ray diffractograms that demonstrate significant changes in the crystalline phase for samples of Niobium pentoxide particles subjected to different milling times (i.e., 1 h, 3h, 6h and 12h).

[0365] Figure 74 shows a graph of crystallinity (%) and crystallite size (nm) versus milling time (h).

[0366] The AR sample consisted of 81% monoclinic crystalline phase. On the other hand, Figure 74 shows that crystallinity (%) and crystallite size (nm) decrease as milling time increases. The data show an exponential decay in crystallinity (%) and crystallite size (nm), with the crystallite size (nm) apparently reaching a plateau after 6 h of milling. The reduction in crystallinity presents a similar behavior to that of the crystallite size, but still presents a significant variation after the 6 h of milling period. Regarding crystallinity, 26% monoclinic phase can be observed for the sample subjected to 12 h of milling.

[0367] The samples with more amorphous characteristics (e.g., the 12h sample) showed an even more significant improvement in the polymer properties. Significant improvements were observed as the degree of amortization increased, i.e., at least 19% amortization degree < at least 39% amortization degree < at least 55% amortization degree < at least 70% amortization degree. An even more significant modulation of the polymer properties was observed for a degree of amortization of 74%.

[0368] Example 20 - Preparation of epoxy resin samples with nanoparticles

[0369] To prepare test specimens to be characterized, niobium pentoxide nanoparticles with 12 hours of milling were weighed to reach concentrations of 50 ppm, 100 ppm, 250 ppm and 500 ppm.

[0370] The nanoparticle preparations were added to methyl ethyl ketone (MEK) and the suspension was sonicated for 15 minutes.

[0371] While the MEK + nanoparticles colloidal suspension was maintained under sonication, the epoxy resin was under constant rotational agitation under a temperature above Tg in a reactor.

[0372] The MEK + nanoparticle suspension is then deposited into the reactor containing the resin under stirring. The addition is made slowly, and after 100% dilution, the mixture remains stirred for 30 minutes, maintaining heating.

[0373] The methyl ethyl ketone was then removed under vacuum. The catalyst, a cycloaliphatic amino catalyst, was then added in a 70:30 ratio. Thus, the test specimens for the following characterizations were obtained.

[0374] Example 21 - Dispersion capacity of niobium pentoxide nanoparticles in polymer matrix

[0375] To verify the dispersion capacity of nanoparticles, polymer samples containing nanoparticles obtained by 12-hour milling using the ultramicrotomy technique were prepared. Before being sent to the ultramicrotome, the polymer matrix samples containing particles underwent cutting, trimming, and semi-fine cutting before obtaining ultrafine sections.

[0376] The ultra-thin sections have a thickness between 70-1 OOnrn, allowing the passage of the electron beam for the application of the electron transmission microscopy technique.

[0377] The ultrathin sections are placed on a copper grid before being sent to the transmission electron microscope. For these analyses, a JEOL JEM-1011 microscope with a maximum acceleration voltage of 100 kV was used. However, to maximize image contrast, the voltage used was 80 kV and, in certain situations, 60 kV.

[0378] The images obtained are brightfield, meaning that the predominant contrast mechanism is mass-thickness. In other words, the higher the atomic number of the sample or the thicker a given region of the sample, the darker it appears in the image.

[0379] Figure 75 shows particles of Niobium pentoxide highlighted in an ultrathin section of the sample at 50 ppm.

[0380] Figure 76 shows particles of Niobium pentoxide highlighted in an ultrathin section of the sample at 100 ppm.

[0381] Figure 77 shows particles of Niobium pentoxide highlighted in an ultrathin section of the sample at 250 ppm.

[0382] Figure 78 shows particles of Niobium pentoxide highlighted in an ultrathin section of the sample at 500 ppm.

[0383] Figures 75 to 78 show that there are well dispersed particles proportional to the concentration used.

[0384] Without wishing to be bound by theory, it is understood that the degree of crystallinity influences the dispersion capacity of a nanoparticle preparation within the bulk of the polymer matrix. The preparation that underwent 12-hour milling exhibits excellent dispersion capacity, as observed in transmission microscopy results on ultrathin sections obtained using the ultramicrotomy technique. Particles with a higher degree of crystallinity are expected to have a greater tendency to aggregate, consequently dispersing less uniformly within the bulk of the polymer matrix and decreasing the mean free path between particles.

[0385] Example 22 - Premix containing phenolic resin and niobium pentoxide nanoparticles and its use for the production of friction composite

[0386] In order to prove that the premix of the invention containing nanoparticles is useful for modifying properties of different materials, additional tests were performed on other polymers.

[0387] A premix containing niobium pentoxide nanoparticles obtained from 12h milling and a phenolic resin was used for the production of automotive brake pad friction composites.

[0388] Firstly, premixes with different nanoparticle contents, i.e., 0.1%, 0.7%, 1.0% and 2.0% w / w were tested, using 3 dispersion and incorporation processes of the referred nanoparticle preparation, i.e., resin dilution in alcohol + nanoparticles, suspension in alcohol + nanoparticles and dry mix + nanoparticles.

[0389] In one embodiment, 6.0 kg of the total premix mixture of this embodiment was prepared with 5.5% by weight of phenolic resin and 94.5% by weight of nanoparticles. This premix was used to prepare a friction composite with the other raw materials for this product. In an EIRICH mixer, two steps were performed: a first step with mixing of all components for 10 min and a second step that continued for 10 min, but with gradual addition in substeps (i.e., 2 min, 2 min, and 4 min).

[0390] After the mixing stage was completed, the material was pressed to form the friction material.

[0391] Table 57 illustrates each of the samples tested:

[0392] Spark and fire test was performed under the following conditions: Braking from 80 to 24 km / h, in 6s (deceleration 2.7 m / s 2 ); time between braking 90s. Repeat each braking 20 times.

[0393] During the test, it was observed that the samples incorporating the premix containing niobium pentoxide nanoparticles in diluted resin showed a delay in the onset of spark generation. Furthermore, there was a reduction in sparks during braking and a reduction in flames after braking.

[0394] Figure 79 shows a graph of the brake pad surface temperature at the end of each braking cycle for each of the tested samples. Note that sample V5 had the lowest final surface temperature, approximately 100 °C lower than sample V1 (reference).

[0395] An accelerated corrosion test was also performed on the friction material. The test conditions were as follows: 22 hours in an oven at 400°C 2h 5% NaCI saline solution (heat shock) 6 hours in the refrigerator at -5°C. Repeat each cycle 10 times.

[0396] Figure 80 shows photos of samples V1, V6 and V8 after 3 cycles of the accelerated corrosion test. It can be seen that samples V6 and V8, which have the addition of nanoparticles, presented greater corrosion resistance than the reference V1.

[0397] Finally, Figure 81 shows a graph of the Gogan C hardness test and cold compressibility (5 MPa, whole pad) for the friction materials containing Niobium pentoxide nanoparticles in phenolic resin.

[0398] Figure 81 allows us to conclude that the diluted resin (V2 and V6) increases the hardness and compressibility of the material (reduces the rigidity of the bulk), as well as increases the porosity of the material.

[0399] Without wishing to be limited to theory, it is understood that the various property improvements in composites due to a simple decrease in particle size (the so-called "scaling effect") are generally attributed to surface energy effects, since the specific surface area for a given mass of particles of the same material increases directly as size decreases. On the other hand, what has been ignored until now is that the resulting number of particles Smaller particles increase much more rapidly, and the effect of large numbers of particles can be significant in the obtained properties. In this context, someone skilled in the art would consider that a very small particle mass would have practically negligible effect, but the present results show that, surprisingly, a huge number of particles (even with a small total mass) can (i) substantially alter the material's properties; or (ii) lead to enormous processing and dispersibility difficulties, upsetting the delicate balance between optimal performance and economic viability. The importance of considering small numbers of smaller, well-dispersed particles within a polymer matrix can be highlighted in terms of the number of particles required to achieve the greatest gain in the desired property for a given particle size, a given mean free path between the closest particles.

[0400] While not wishing to be limited to theory, it is understood that the same positive relationship between the mean free path and the number of particles, as well as between the mean free path and particle size, is observed for both the ultimate tensile strength and the storage modulus, suggesting that the texturing of the matrix around the particles increases with their size. However, the dependence of stiffness on the number of particles was shown to be contrary to strength, suggesting that if the mean free path decreases (due to a greater number of particles in the polymer matrix), the expected forced orientation of the polymer chains apparently generates easier slippage, resulting in a more flexible composite but with increased strength.

[0401] Example 23 - Premix in paste or film form containing niobium pentoxide nanoparticles and its use in metal welding applications

[0402] In this example, various paste-like premixes were prepared with different polymers, including polyethylene glycols (PEGs), polypropylene glycols (PPGs) of different molecular weights, mesamoll, or butyl glycol, all using niobium pentoxide nanoparticles obtained as described in this patent application, i.e., high-energy milling.

[0403] In one embodiment, a PEG 6000 premix was prepared by mixing (weight ratios) 50% IPA (isopropyl alcohol), 30% PEG 6000, and 20% Nb20s. Preparation involved weighing the PEG and alcohol, stirring with gentle heating (>=70°C) until solubilized, and then adding the Nb20s nanoparticles, stirring with heating for 10 min. The resulting material was then heated in an oven at 100°C for 15 min until a film formed. The resulting premix is ​​in the form of a film that can be used as such, or it can be scraped and used as powder or flakes.

[0404] In another embodiment, a butyl glycol premix was prepared by mixing (weight ratios) 65% butyl glycol and 35% Nb20s. Preparation involved weighing the materials, stirring the butyl glycol, and then adding the Nb20s nanoparticles. The resulting material was then heated in an oven at 100°C until a paste formed.

[0405] In another embodiment, a mesamoll premix was prepared by mixing (weight ratios) 51% mesamoll and 49% Nb20s. Preparation involved weighing the materials, stirring the mesamoll, and then adding the Nb20s nanoparticles. In this case, dispersion was mechanical using a Cowles disperser or basic mixer. The resulting material was then heated in an oven at 100°C until a paste formed.

[0406] A premix in the form of a butyl glycol paste as described above was applied to a steel metal part, in a region that was subsequently directly subjected to a welding process over the region containing the applied premix. The premix vehicle in this embodiment of the invention is a "sacrificial" one, as it is vaporized during the welding process, while the nanoparticles are incorporated into the metal alloy formed during the welding process. The metal part obtained after welding exhibited improved properties, notably improved toughness and strength. mechanical properties, thermal dissipation (reduction in HAZ), and more consistently maintained hardness, in addition to microstructural improvements with reduced vacancies—resulting in a microstructure with fewer primary Widmanstätten ferrites and similar compounds. This new approach of incorporating nanoparticles into the welded material, simply by applying a paste to the welded area, is surprising to experts in the field and solves several technical problems, such as: enabling better welding processes without requiring changes to the other materials used; ensuring correct premix placement due to the paste form; adjusting the nanoparticle concentration in the premix according to the desired amount of nanoparticle incorporation into the weld; among other technical advantages.

[0407] Those skilled in the art will appreciate the knowledge presented herein and will be able to reproduce the invention in the presented embodiments and in other variants and alternatives, covered by the scope of the following claims.

Claims

Claims 1. Functional premix characterized by comprising: a solid, semi-solid, pasty or liquid vehicle or compatibilizer; and a load of 0.0001 to 50% by weight of nanoparticles of defined particle size and chemically defined composition.

2. Premix according to claim 1, characterized in that said vehicle or compatibilizer is selected from: a polymeric, ceramic, metallic material, or combinations thereof.

3. Premix according to claim 2, characterized in that said polymeric material is selected from: diols, polyols, adhesives / plasticizers such as mesamoll, elastomers, rubbers, thermoplastic polymers, thermosetting polymers, resins, waxes, epoxy resins, phenolic resins, polymethyl methacrylate (acrylic), polystyrene, polyvinyl chloride (PVC), polyethylene, polypropylene, natural polymers selected from rubber, silk, wool, cellulose, or combinations thereof.

4. Premix according to claim 3, characterized in that said diol or polyol is selected from: alkyl glycol, alkylene glycol, polyalkylene glycol, ethylene glycol, propylene glycol, butyl glycol, polyethylene glycol, polypropylene glycol or combinations thereof.

5. Premix according to any one of claims 1-4, characterized in that said nanoparticles are nanoparticles of metals, transition metals, non-metals, oxides, ceramic oxides, rare earths, or combinations thereof.

6. Premix according to claim 5, characterized in that said nanoparticles are of a material containing niobium, titanium, tantalum, their oxides, hydrates, carbides, oxalates, graphene, graphene oxide, or combinations thereof.

7. Premix according to claim 6, characterized in that said nanoparticles are niobium pentoxide, niobium oxalate, niobic acid, FeNb, titanium dioxide, tantalum pentoxide, or combinations thereof.

8. Premix according to any one of claims 5-7, characterized in that said nanoparticles are smaller than 750nm, preferably smaller than 500nm.

9. Premix according to claim 8, characterized in that said nanoparticle load comprises a degree of crystallinity below 81% or a degree of amortization of at least 19%.

10. Premix according to claim 9, characterized in that said nanoparticle charge comprises: (i) a degree of crystallinity below 61%, preferably a degree of crystallinity below 45% and more preferably a degree of crystallinity below 30%; or (ii) a degree of amortization of at least 39%, preferably a degree of amortization of at least 55% and more preferably a degree of amortization of at least 70%.

11. Process for obtaining the functional premix as defined in claim 1, characterized by comprising the steps of: - incorporate from 0.0001 to 50% by weight of nanoparticles of metals, transition metals, non-metals, oxides, ceramic oxides, rare earths, or combinations thereof into a vehicle or compatibilizer selected from a polymeric, ceramic, metallic material, or combinations thereof; and - homogenize and until a solid, semi-solid or pasty premix is ​​obtained.

12. Process for modifying materials characterized by comprising one or more steps of adding a functional premix as defined in claim 1 to a step of processing metallic, ceramic, polymeric material or combinations thereof.

13. Material with modified properties characterized by being obtained by the process defined in claim 12.

14. Material according to claim 13, characterized in that it comprises a concentration of nanoparticles in the range of 1 to 500 ppm.

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