Functional nanoparticle premix, method of obtaining the premix, method of altering properties of a material, and material having altered properties

Abstract

The present invention is in the field of materials engineering and nanotechnology. More specifically, the present invention discloses: a functional premix comprising nanoparticles and a carrier or compatibilizer; a method of obtaining the premix; a method of altering the properties of a material; and a modified material formed with improved properties. Unexpectedly, the premix of the present invention can be used to alter the properties of different kinds of materials, such as polymers, metals, ceramic materials, and / or composites of different materials. The premix of the present invention has numerous advantages in terms of transportation, use, and incorporation of nanoparticles into different materials. In one embodiment, the present invention provides significant modification of the properties of polymers and, in fact, breaks the existing concepts in this technical field. In another embodiment, the present invention provides advantages in altering the properties of metals and / or ceramic materials.

Description

Technical Field

[0001] This invention belongs to the fields of materials engineering and nanotechnology. More specifically, this invention discloses: a functional premix comprising nanoparticles and a carrier or compatibilizer; a method for obtaining the premix; a method for modifying material properties; and the resulting modified material with improved properties. Unexpectedly, the premix of this invention can be used to modify the properties of different kinds of materials (e.g., polymers, metals, ceramic materials, and / or composites of different materials). The premix of this invention offers numerous advantages in terms of transport, use, and incorporation of nanoparticles into different materials. In one embodiment, this invention provides significant modification to the properties of polymers, breaking through existing concepts in practice. In another embodiment, this invention provides advantages in modifying the properties of metallic and / or ceramic materials. Background Technology

[0002] The application of nanoparticles to modify the properties of various materials has become a hot research and development topic. On the one hand, large-scale application still faces many limitations, primarily the inability to obtain nanoparticle formulations with high concentrations, high purity, and precise particle size characteristics. On the other hand, even if such nanoparticles could be obtained, several technical challenges need to be overcome, including dosage, purity, dispersibility, stability, and compatibility with the materials to be modified.

[0003] In the field of polymers, the application of nanoparticles is generally not a research or technical topic, partly due to the aforementioned limitations and partly due to their molecular structure. This invention provides a method for modifying polymer properties in a way that is unknown in the prior art, in terms of the different modified properties and the degree of modification. Furthermore, some polymers are physically and chemically incompatible with certain nanoparticles, particularly due to polarity issues. This invention also provides a solution to this problem.

[0004] These and other reasons have led to the fact that industrial-scale polymers with selective particle size distributions and entirely nanoparticle-doped polymers are not yet available. This invention solves these problems.

[0005] In the field of metallic or ceramic materials, the application of nanoparticles is a subject of several research and technological studies. However, a common challenge when using nanoparticles in these materials is the problem of dispersibility and / or uniformity. This invention provides a solution to such problems.

[0006] After searching existing technologies in scientific and patent literature, the following documents related to this topic were found: Patent application WO2022036427, co-invented with this invention, discloses a niobium nanoparticle formulation obtained by a top-down method. This formulation possesses the following technical features: particles entirely within the nanoparticle size range; high purity; industrial-scale production; and an economically feasible and suitable cost. Because this method does not introduce impurities or lead to the formation of reaction products as in prior art bottom-up (or synthetic) methods, the nanoparticle formulation exhibits very high purity. However, WO2022036427 does not mention the regulation of the properties of polymers obtained from the specific nanoparticle formulation disclosed in this patent application.

[0007] Patent document US20070116976A1 relates to a method of providing a composition combining improved impact resistance and effective corona resistance. As a solution, US20070116976A1 discloses a nanocomposite material comprising a polymer composition and nanoparticles with an average maximum size less than or equal to about 500 nanometers. However, US20070116976A1 does not mention the modulation of the properties of the polymer obtained from the specific nanoparticle formulation disclosed in this patent application.

[0008] Patent document CN110229412 relates to solving the compatibility problem between nanomaterials and polymers, ensuring that mechanical properties such as hardness are not affected. Therefore, CN110229412 discloses a nanocomposite material with improved strength and hardness prepared by melt blending a premix. This premix comprises: a) nanomaterials, which may be metal oxides, transition metals, and rare earth elements; b) a liquid medium, which may be water or other solvents; c) polypropylene; and preferably, an additive may be added to increase the amount of liquid medium bound to the nanomaterials. However, CN110229412 does not mention the regulation of the properties of polymers obtained from the specific nanoparticle formulation disclosed in this patent application.

[0009] The article by Hajduk et al. (2021) (Thermal and optical properties of PMMA films reinforced with Nb₂O₅ nanoparticles) reveals the effect of niobium pentoxide nanoparticles on altering the thermal and physical properties of polymethyl methacrylate (PMMA). On the other hand, Hajduk et al. (2021) do not mention the modulation of the properties of polymers obtained from the specific nanoparticle formulations disclosed in this patent application.

[0010] Patent document US2009226711A1 discloses a biaxially oriented nanocomposite film prepared by a method comprising the following steps: mixing a nanofiller with a polymer composition to form a nanocomposite material; melt-extruding the nanocomposite material to form a melt tube; biaxially expanding the tube by mechanical force and gas pressure to form a bubble; and collapsing the bubble to form at least one layer of biaxially oriented nanocomposite film, wherein the tensile strength (dielectric strength) of the biaxially oriented nanocomposite film is at least 300 V / μm. However, US2009226711A1 does not mention the regulation of the properties of the polymer obtained from the specific nanoparticle formulation disclosed in this patent application.

[0011] Patent document JP2003073558 discloses a method for preparing a composition of ultrafine metal oxide particles and a polymer containing electron-donating groups, wherein the particle surface is modified with acidic and basic groups. More specifically, the method includes: 1) hydrolyzing a compound to obtain ultrafine metal oxide particles and surface-modifying them with aliphatic carboxylic acids and aliphatic amines; 2) dispersing / dissolving the particles in a desired solvent and mixing them with a polymer solution to form a mixed solution; 3) optionally heating and stirring to promote the formation of the ultrafine metal oxide particles and polymer composite material. On the other hand, JP2003073558 does not mention the regulation of the properties of the polymer obtained from the specific nanoparticle formulation disclosed in this patent application.

[0012] It can be inferred from the literature reviewed that no literature was found that anticipated or implied the teachings of the present invention. Summary of the Invention

[0013] This invention addresses several problems in the prior art through a functional premix comprising nanoparticle fillers and at least one carrier. The premix (or pre-mixture) of this invention is unexpectedly used to modify one or more properties of very different materials (e.g., polymers, metals, ceramics, and / or composites of different materials). Unexpectedly, it can be used to modify the properties of very different materials (e.g., polymers, metals, ceramics, and / or composites of different materials). A method for obtaining said premix is ​​also disclosed.

[0014] The premixes of this invention are specifically designed to address the issues of stability, dispersibility, and / or adequate incorporation of nanoparticles into various materials. The premixes of this invention also solve the technical problem of suspending nanoparticles during processing, thereby preventing their diffusion into the environment.

[0015] Modifying polymers or other materials (e.g., metals and / or ceramics) by incorporating particles in the micrometer size range can lead to catastrophic failures, such as cracking, deformation, geometric irregularities, and other problems. Furthermore, for some high-cost materials, the mass percentage resulting from using micrometer-sized particles can make the final product prohibitively expensive. Finally, due to the use of micrometer-sized particles, the so-called "mean free path" and surface energy cannot interact with the medium, thus preventing the formation of new structures. This invention addresses this problem and provides premixes containing high concentrations of nanoparticles. Because the nanoparticle concentration in the premixes of this invention is several orders of magnitude higher than the nanoparticle concentration required to achieve performance improvements in the final material containing such nanoparticles, the premixes of this invention are particularly suitable for subsequent preparation of materials with lower nanoparticle concentrations, using the premixes as premixes or compatibilizers. If it is desired 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 corresponding premix and the material to be modified, and homogenize until a product with a specific concentration is obtained. Other final concentrations can be obtained by adjusting the concentration of the premix in the desired material.

[0016] The present invention also provides a method for modifying materials, and the modified materials obtained therefrom.

[0017] Therefore, one object of the present invention is to provide a functional premix comprising: a solid, semi-solid, paste or liquid carrier or compatibilizer; and 0.0001 to 50% by weight of nanoparticle filler having a defined particle size and chemical composition.

[0018] In one embodiment, the carrier or compatibilizer is selected from polymers, ceramics, metallic materials, or combinations thereof. In one embodiment, the polymer material (wherein "polymer" is used in a broad sense) is selected from: diols, polyols, adhesives / plasticizers (e.g., mesamoll), elastomers, rubber, 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, the diol or polyol is selected from: alkyl glycols, alkylene glycols, polyalkylene glycols, ethylene glycol, propylene glycol, butylethylene glycol, polyethylene glycol, polypropylene glycol, or combinations thereof.

[0019] In one embodiment, these nanoparticles are smaller than 750 nm and have an amorphization degree of at least 19%.

[0020] Another object of the present invention is to provide a method for obtaining a functional premix, the method comprising at least one step of incorporating nanoparticle fillers into a solid, semi-solid or paste-like carrier for incorporation into said material during a processing step of a metal, ceramic and / or polymer matrix material.

[0021] Another object of the present invention is to provide a method for modifying the properties of a material, the method comprising one or more steps of incorporating the functional premix of the present invention into the material during processing steps of a metal, ceramic, polymer, composite material, or combination thereof. In embodiments where nanoparticles are incorporated into a polymer material using the premix of the present invention, the carrier is a compatibilizer integrated into the final polymer matrix containing the nanoparticles. In embodiments where nanoparticles are incorporated into a metal or ceramic material using the premix of the present invention, the carrier typically does not integrate into the final metal or ceramic matrix due to high processing temperatures and carrier volatilization, and the nanoparticles remain in the modified product.

[0022] Another object of the present invention is to provide a material with altered properties due to the incorporation of the premix of the present invention, wherein the modified material is a metal, ceramic, polymer, composite material or a combination thereof.

[0023] In one embodiment, the modified polymer material is selected from polyesters, epoxy resins, phenolic resins, polyamides, thermoplastic polymers, thermosetting polymers, or combinations thereof. Among other improved polymer material properties and characteristics, particularly improved resistance to mechanical stress and glass transition temperature are mentioned. In one embodiment, the modified metallic and / or ceramic material has improved properties, with significantly improved resistance to mechanical stress and / or corrosion resistance.

[0024] These and other objects of the present invention will be readily understood by those skilled in the art and will be described in detail below. Attached Figure Description

[0025] Please refer to the following attached diagram: Figure 1 depicts the FTIR spectrum of the sample.

[0026] exist Figure 1A The spectra of epoxy resin sample 1, epoxy resin sample 2 and epoxy resin sample 3 are shown in the figure.

[0027] exist Figure 1B The superposition of the spectra is shown in the figure (Y-axis represents transmittance in % and X-axis represents transmittance in cm). -1 (The wave number is calculated).

[0028] Figure 2 shows the FTIR spectrum of the sample.

[0029] exist Figure 2AThe spectra of epoxy resin sample 4, epoxy resin sample 5 and epoxy resin sample 6 are shown in the figure.

[0030] exist Figure 2B The superposition of the spectra is shown in the figure (Y-axis represents transmittance in % and X-axis represents transmittance in cm). -1 (The wave number is calculated).

[0031] Figure 3 depicts the FTIR spectrum of the sample.

[0032] exist Figure 3A The spectra of epoxy resin sample 7, epoxy resin sample 8 and epoxy resin sample 9 are shown in the figure.

[0033] exist Figure 3B The superposition of the spectra is shown in the figure (Y-axis represents transmittance in % and X-axis represents transmittance in cm). -1 (The wave number is calculated).

[0034] Figure 4 depicts the FTIR spectrum of the sample.

[0035] exist Figure 4A The spectra of epoxy resin sample 10, epoxy resin sample 11 and epoxy resin sample 12 are shown in the figure.

[0036] exist Figure 4B The superposition of the spectra is shown in the figure (Y-axis represents transmittance in % and X-axis represents transmittance in cm). -1 (The wave number is calculated).

[0037] Figure 5 The FTIR spectra of Lacktherm 1314 resin samples were depicted (Y-axis represents transmittance in % and X-axis represents transmittance in cm⁻¹). -1 (The wave number is calculated).

[0038] Figure 6 Thermogravimetric analysis (TGA) was used to depict the mass loss curve and first derivative of resin sample 1 as a function of temperature (the left Y-axis represents TG; the right Y-axis represents DTF (% / min); and the X-axis represents temperature in degrees Celsius).

[0039] Figure 7 Thermogravimetric analysis (TGA) was used to depict the mass loss curve and first derivative of resin sample 2 as a function of temperature (the left Y-axis represents TG; the right Y-axis represents DTF (% / min); and the X-axis represents temperature in degrees Celsius).

[0040] Figure 8 Thermogravimetric analysis (TGA) was performed on the mass loss curve and first derivative of resin sample 3 as a function of temperature (the left Y-axis represents TG; the right Y-axis represents DTF (% / min); and the X-axis represents temperature in degrees Celsius).

[0041] Figure 9 Thermogravimetric analysis (TGA) was performed on the mass loss curve and first derivative of resin sample 4 as a function of temperature. The left Y-axis represents TG; the right Y-axis represents DTF (% / min); and the X-axis represents temperature in degrees Celsius.

[0042] Figure 10 Thermogravimetric analysis (TGA) was used to depict the mass loss curve and first derivative of resin sample 5 as a function of temperature (the left Y-axis represents TG; the right Y-axis represents DTF (% / min); and the X-axis represents temperature in degrees Celsius).

[0043] Figure 11 Thermogravimetric analysis (TGA) was performed on the mass loss curve and first derivative of resin sample 6 as a function of temperature (the left Y-axis represents TG; the right Y-axis represents DTF (% / min); and the X-axis represents temperature in degrees Celsius).

[0044] Figure 12 Thermogravimetric analysis (TGA) was performed on the mass loss curve and first derivative of resin sample 7 as a function of temperature (the left Y-axis represents TG; the right Y-axis represents DTF (% / min); and the X-axis represents temperature in degrees Celsius).

[0045] Figure 13 Thermogravimetric analysis (TGA) was performed on the mass loss curve and first derivative of resin sample 8 as a function of temperature (the left Y-axis represents TG; the right Y-axis represents DTF (% / min); and the X-axis represents temperature in degrees Celsius).

[0046] Figure 14 Thermogravimetric analysis (TGA) was performed on the mass loss curve and first derivative of resin sample 9 as a function of temperature (the left Y-axis represents TG; the right Y-axis represents DTF (% / min); and the X-axis represents temperature in degrees Celsius).

[0047] Figure 15 Thermogravimetric analysis (TGA) was performed on the mass loss curve and first derivative of resin sample 10 as a function of temperature. The left Y-axis represents TG; the right Y-axis represents DTF (% / min); and the X-axis represents temperature in degrees Celsius.

[0048] Figure 16 Thermogravimetric analysis (TGA) was performed on the mass loss curve and first derivative of resin sample 11 as a function of temperature. The left side of the Y-axis represents TG; the right side of the Y-axis represents DTF (% / min); and the X-axis represents temperature in degrees Celsius.

[0049] Figure 17Thermogravimetric analysis (TGA) was performed on the mass loss curve and first derivative of resin sample 11 as a function of temperature. The left Y-axis represents TG; the right Y-axis represents DTF (% / min); and the X-axis represents temperature in degrees Celsius.

[0050] Figure 18 Thermogravimetric analysis (TGA) was performed on the mass loss curve and first derivative of resin sample 12 as a function of temperature. The left Y-axis represents TG; the right Y-axis represents DTF (% / min); and the X-axis represents temperature in degrees Celsius.

[0051] Figure 19 Thermogravimetric analysis (TGA) was used to depict the mass loss curves and first derivatives of Lacktherm 1314-1 resin samples as a function of temperature (the left Y-axis represents TG; the right Y-axis represents DTF (% / min); and the X-axis represents temperature in degrees Celsius).

[0052] Figure 20 The MEV image and EDS results for resin sample 1 are depicted. Scanning electron microscope images are shown in A) and B); the EDS analysis image is shown in C).

[0053] Figure 21 The MEV image and EDS results for resin sample 2 are depicted. Scanning electron microscope image is shown in A); EDS analysis image is shown in B).

[0054] Figure 22 The MEV images and EDS results for resin sample 3 are depicted. Scanning electron microscope images are shown in A) and B); the EDS analysis image is shown in C).

[0055] Figure 23 The MEV images and EDS results for resin sample 4 are depicted. Scanning electron microscope images are shown in A) and B); the EDS analysis image is shown in C).

[0056] Figure 24 The MEV images and EDS results for resin sample 5 are depicted. Scanning electron microscope images are shown in A) and B); the EDS analysis image is shown in C).

[0057] Figure 25 MEV images and EDS results for resin sample 6 are depicted. Scanning electron microscope images are shown in A) and B); EDS analysis images are shown in C).

[0058] Figure 26 The MEV images and EDS results for resin sample 7 are depicted. Scanning electron microscope images are shown in A) and B); the EDS analysis image is shown in C).

[0059] Figure 27 MEV images and EDS results for resin sample 8 are depicted. Scanning electron microscope images are shown in A) and B); EDS analysis images are shown in C).

[0060] Figure 28 MEV images and EDS results for resin sample 9 are depicted. Scanning electron microscope images are shown in A) and B); EDS analysis images are shown in C).

[0061] Figure 29 MEV images and EDS results for resin sample 10 are depicted. Scanning electron microscope images are shown in A) and B); EDS analysis images are shown in C).

[0062] Figure 30 MEV images and EDS results for resin sample 11 are depicted. Scanning electron microscope images are shown in A) and B); EDS analysis images are shown in C).

[0063] Figure 31 MEV images and EDS results for resin sample 12 are depicted. Scanning electron microscope images are shown in A) and B); EDS analysis images are shown in C).

[0064] Figure 32 The storage modulus (damping effect) of 1020 / 1 resin as a function of increasing temperature is plotted. In A), the Y-axis represents the storage modulus in E' (1.000 Hz) / MPa, and the X-axis represents the temperature in degrees Celsius. In B), the loss tangent curve of the same material is shown, with the Y-axis representing the loss tangent value and the X-axis representing the temperature in degrees Celsius.

[0065] Figure 33 A graph depicting the storage modulus (damping effect) of 1010 / 1 resin as a function of increasing temperature is presented. In A), the Y-axis represents the storage modulus in E' (1.000 Hz) / MPa, and the X-axis represents the temperature in degrees Celsius. In B), a graph showing the loss tangent of the same material is presented, with the Y-axis representing the loss tangent value and the X-axis representing the temperature in degrees Celsius.

[0066] Figure 34 A graph depicting the storage modulus (damping effect) of 1000 / 0 resin as a function of increasing temperature is presented. In A), the Y-axis represents the storage modulus in E' (1.000 Hz) / MPa, and the X-axis represents the temperature in degrees Celsius. In B), a graph showing the loss tangent of the same material is presented, with the Y-axis representing the loss tangent value and the X-axis representing the temperature in degrees Celsius. Figure 35 The following are examples of resins 1020 / 1, 1010 / 1, and 1000 / 0: Figure 32The graphs in A, 33A and 34A show a comparison of the energy storage modulus.

[0067] Figure 36 The basis for resins 1020 / 1, 1010 / 1, and 1000 / 0 is shown. Figure 32 Comparison of loss tangent curves in curves B, 33B, and 34B.

[0068] Figure 37 The figure shows a comparison curve of the storage modulus (E') of each sample described in Example 8 as a function of temperature.

[0069] Figure 38 The figure shows a comparison curve of the loss tangent (tan d) of each sample described in Example 8 as a function of temperature.

[0070] Figure 39 A bar chart showing the average activation energy (AE) of each sample described in Example 8 is shown.

[0071] Figure 40 A bar chart showing the average storage modulus (E') of each sample described in Example 8 is shown.

[0072] Figure 41 A bar chart showing the average loss tangent (tan d) for each sample described in Example 8 is shown.

[0073] Figure 42 A line graph is shown, which compares the storage modulus (E') with changes in concentration and nanoparticle type.

[0074] Figure 43 A line graph is shown, which compares the loss tangent (tan d) with concentration and nanoparticle type.

[0075] Figure 44 The FTIR spectrum of sample 1000 / 0 described in Example 8 is depicted (Y-axis is transmittance in % and X-axis is transmittance in cm). -1 (The wave number is calculated).

[0076] Figure 45 The FTIR spectrum of sample 1010 / 1 described in Example 8 is depicted (Y-axis is transmittance in % and X-axis is transmittance in cm). -1 (The wave number is calculated).

[0077] Figure 46 The FTIR spectrum of sample 1010 / 2 described in Example 8 is depicted (Y-axis is transmittance in % and X-axis is transmittance in cm). -1 (The wave number is calculated).

[0078] Figure 47The FTIR spectrum of sample 1010 / 3 described in Example 8 is depicted (Y-axis is transmittance in % and X-axis is transmittance in cm). -1 (The wave number is calculated).

[0079] Figure 48 The FTIR spectrum of sample 1010 / 4 described in Example 8 is depicted (Y-axis is transmittance in % and X-axis is transmittance in cm). -1 (The wave number is calculated).

[0080] Figure 49 The FTIR spectrum of sample 1020 / 1 described in Example 8 is depicted (Y-axis is transmittance in % and X-axis is transmittance in cm). -1 (The wave number is calculated).

[0081] Figure 50 The FTIR spectrum of sample 1020 / 2 described in Example 8 is depicted (Y-axis is transmittance in % and X-axis is transmittance in cm). -1 (The wave number is calculated).

[0082] Figure 51 The FTIR spectrum of sample 1020 / 3 described in Example 8 is depicted (Y-axis is transmittance in % and X-axis is transmittance in cm). -1 (The wave number is calculated).

[0083] Figure 52 The FTIR spectrum of sample 1020 / 4 described in Example 8 is depicted (Y-axis is transmittance in % and X-axis is transmittance in cm). -1 (The wave number is calculated).

[0084] Figure 53 The FTIR spectrum of sample 1030 / 4 described in Example 8 is depicted (Y-axis is transmittance in % and X-axis is transmittance in cm). -1 (The wave number is calculated).

[0085] Figure 54 The FTIR spectrum of sample 1040 / 4 described in Example 8 is depicted (Y-axis is transmittance in % and X-axis is transmittance in cm). -1 (The wave number is calculated).

[0086] Figure 55 A comparison of the FTIR spectra of the samples described in Example 8 is presented (Y-axis is transmittance in % and X-axis is transmittance in cm⁻¹). -1 (The wave number is calculated).

[0087] Figure 56 The storage modulus (E') of sample 1010 / 1 as a function of temperature was plotted.

[0088] Figure 57The curve of the loss tangent (tan d) of sample 1010 / 1 as a function of temperature was plotted.

[0089] Figure 58 The curve of loss modulus (E'') of sample 1010 / 1 as a function of temperature was plotted.

[0090] Figure 59 The storage modulus (E') of sample 1010 / 2 as a function of temperature was plotted.

[0091] Figure 60 The curve of the loss tangent (tan d) of sample 1010 / 2 as a function of temperature was plotted.

[0092] Figure 61 The curve of loss modulus (E'') of sample 1010 / 2 as a function of temperature was plotted.

[0093] Figure 62 The storage modulus (E') of sample 1010 / 3 as a function of temperature was plotted.

[0094] Figure 63 The curve of the loss tangent (tan d) of sample 1010 / 3 as a function of temperature was plotted.

[0095] Figure 64 The curve of loss modulus (E'') of sample 1010 / 3 as a function of temperature was plotted.

[0096] Figure 65 A bar chart showing the average storage modulus (E') of each sample described in Example 15 is shown.

[0097] Figure 66 A bar chart showing the average loss modulus (E'') of each specimen described in Example 15 is shown.

[0098] Figure 67 The average glass transition temperature (T) of each sample described in Example 15 is shown. g (a bar chart of )

[0099] Figure 68 The figure shows the size histogram obtained by transmission microscopy analysis of a niobium pentoxide particle sample (referred to as AR) as is.

[0100] Figure 69 The figure shows the size histogram obtained by transmission microscopy analysis of a niobium pentoxide particle sample that has been ground for 1 hour.

[0101] Figure 70 The figure shows the size histogram obtained by transmission microscopy analysis of a niobium pentoxide particle sample that has been ground for 3 hours.

[0102] Figure 71 The figure shows the size histogram obtained by transmission microscopy analysis of a niobium pentoxide particle sample that has been ground for 6 hours.

[0103] Figure 72 The figure shows the size histogram obtained by transmission microscopy analysis of a niobium pentoxide particle sample that has been ground for 12 hours.

[0104] Figure 73 The illustration shows a comparison of X-ray diffraction patterns, which indicate that the crystal phase of niobium pentoxide particle samples treated for different grinding times (i.e., 1 hour, 3 hours, 6 hours, and 12 hours) changed significantly.

[0105] Figure 74 The graphs show crystallinity (%), grain size (nm), and grinding time (h).

[0106] Figure 75 Niobium pentoxide particles are highlighted in an ultrathin section of a 50 ppm sample.

[0107] Figure 76 Niobium pentoxide particles are highlighted in an ultrathin section of a 100 ppm sample.

[0108] Figure 77 Niobium pentoxide particles are highlighted in an ultrathin section of a 250 ppm sample.

[0109] Figure 78 Niobium pentoxide particles are highlighted in an ultrathin section of a 500 ppm sample.

[0110] Figure 79 A graph showing the surface temperature of the brake pads at the end of each braking cycle for each test specimen is presented.

[0111] Figure 80 Photographs of samples V1, V6, and V8 after three accelerated corrosion test cycles are shown.

[0112] Figure 81 The graph shows the Gogan C hardness and cold compressibility (5 MPa, whole pad) of the phenolic resin friction material containing niobium pentoxide nanoparticles. Detailed Implementation

[0113] In the context of this invention, the term "niobium substance or niobium-containing material" should be understood in its broadest sense as any substance containing the element niobium. The term "niobium substance or niobium-containing material" encompasses a variety of niobium-containing chemical substances, including metallic niobium, niobium oxide, oxalate, hydrate, hydride, carbide or nitride, ferroniobium, or niobium alloyed with other metals or transition metals, or combinations thereof. It also includes niobium pentoxide (Nb₂O₅), NbO₂, NbO, niobium oxalate, niobic acid, and FeNb.

[0114] In the context of this invention, the term "titanium substance or titanium-containing material" should be understood in its broadest sense as any substance containing the element titanium. The term "titanium substance or titanium-containing material" covers a variety of titanium-containing chemical substances, 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.

[0115] In the context of this invention, the term "tantalum substance or tantalum-containing material" should be understood in its broadest sense as any substance containing the element tantalum. The term "tantalum substance or tantalum-containing material" covers a variety of tantalum-containing chemical substances, including metallic tantalum, tantalum oxide, oxalate, hydrate, hydride, carbide or nitride, ferrotantalum, or tantalum alloyed with other metals or transition metals, or combinations thereof. It also includes tantalum pentoxide.

[0116] In the context of this invention, the term "polymer" is used in a broad sense and is selected from: diols, polyols, adhesives / plasticizers (e.g., alkyl sulfonates), elastomers, rubber, 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, the diol or polyol is selected from: alkyl glycols, alkylene glycols, polyalkylene glycols, ethylene glycol, propylene glycol, butylethylene glycol, polyethylene glycol, polypropylene glycol, or combinations thereof.

[0117] A polymer should be understood in its broadest sense as a macromolecule composed of at least two monomers, which may have the same or different chemical compositions.

[0118] The premixes of this invention, when using a polymer carrier or compatibilizer, can be used to obtain modified polymers or modified metals or ceramics. If a modified polymer is obtained, the carrier or compatibilizer is ideally a thermoplastic material (due to its better processability). If a modified metal or ceramic is obtained, the carrier can be a thermosetting polymer, or preferably a low molecular weight and / or more fluid polymer, preferably a sacrificial carrier that is volatile during the processing of the material to be modified.

[0119] The present invention can also be defined by the following items.

[0120] Functional premixes include: solid, semi-solid, paste, or liquid carriers or compatibilizers; and 0.0001 to 50% by weight of nanoparticle fillers having defined particle size and chemical composition.

[0121] As described above, the carrier or compatibilizer is selected from polymers, ceramics, metals, or combinations thereof.

[0122] As described above, the polymer material is selected from: diols, polyols, binders / plasticizers (such as alkyl sulfonates), elastomers, rubber, 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.

[0123] As described above, the diol or polyol is selected from: alkyl glycols, alkylene glycols, polyalkylene glycols, ethylene glycol, propylene glycol, butyl ethylene glycol, polyethylene glycol, polypropylene glycol, or combinations thereof.

[0124] As described above, the nanoparticles are nanoparticles of metals, transition metals, nonmetals, oxides, ceramic oxides, rare earth elements, or combinations thereof.

[0125] As described above, the premixes contain niobium, titanium, tantalum, their oxides, hydrates, carbides, oxalates, graphene, graphene oxide, or combinations thereof.

[0126] As described above, the nanoparticles are niobium pentoxide, niobium oxalate, niobic acid, FeNb, titanium dioxide, tantalum pentoxide, or a combination thereof.

[0127] As described above, the nanoparticles are less than 750 nm, preferably less than 500 nm.

[0128] As described above, the premix contains nanoparticle fillers with a crystallinity of less than 81% or an amorphization of at least 19%.

[0129] As described above, the premix comprises: (i) a crystallinity of less than 61%, preferably less than 45%, and more preferably less than 30%; or (ii) an amorphization of at least 39%, preferably at least 55%, and more preferably at least 70%.

[0130] A method for obtaining the functional premix as described above includes the following steps: - Incorporating 0.0001 to 50% by weight of nanoparticles of metals, transition metals, nonmetals, oxides, ceramic oxides, rare earth elements, or combinations thereof into a carrier or compatibilizer selected from polymers, ceramics, metallic materials, or combinations thereof; and - Homogenize until a solid, semi-solid, or paste-like premix is ​​obtained.

[0131] A method for modifying materials, comprising one or more steps of adding a functional premix as defined above to a processing step of a metal, ceramic, polymer material or a combination thereof.

[0132] Materials with altered properties obtained through the methods defined above.

[0133] The material described above contains nanoparticles at a concentration of 1 to 500 ppm.

[0134] In this invention, the crystallinity or amorphization of the nanoparticles is relevant to certain applications. In one embodiment of the functional premix, the nanoparticle filler comprises: (i) a crystallinity of less than 61%, preferably less than 45%, and more preferably less than 30%; or (ii) an amorphization of at least 39%, preferably at least 55%, and even more preferably at least 70%.

[0135] In one embodiment of the functional premix, the degree of amorphization of the nanoparticle filler is at least 19%.

[0136] In one embodiment of the functional premix, the crystallinity of the nanoparticle filler is preferably less than 80%, more preferably less than 75%, more preferably less than 70%, more preferably less than 65%, more preferably less than 61%, more preferably less than 60%, more preferably less than 55%, more preferably less than 50%, more preferably less than 45%, more preferably less than 40%, more preferably less than 35%, and even more preferably less than 30%. In one embodiment, the crystallinity is less than 29%, more preferably less than 28%, and more preferably less than 27%. In a non-limiting embodiment, the crystallinity is 26%.

[0137] In one embodiment of the functional premix, the nanoparticle filler preferably comprises a crystallinity of less than 61%, more preferably less than 45%, and even more preferably less than 30%.

[0138] In one embodiment of the functional premix, the nanoparticle filler preferably comprises an amorphous degree 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 at least 55%, more preferably at least 60%, more preferably at least 65%, and even more preferably a crystallinity of at least 70%. In one embodiment, the amorphous degree is at least 71%, more preferably at least 72%, more preferably at least 73%. In a non-limiting embodiment, the amorphous degree is 74%.

[0139] In one embodiment of the functional premix, the nanoparticle filler preferably has an amorphization degree of at least 39%, more preferably at least 55%, and even more preferably at least 70%.

[0140] In one embodiment of the functional premix, the nanoparticles are composed of nonmetals, metals, transition metals, rare earth elements, substances containing these elements, or combinations thereof.

[0141] In one embodiment of the functional premix, the niobium pentoxide nanoparticles have the following particle size distribution characteristics: d10: 14 to 110 nm; d50: 29 to 243 nm; d90: 89 to 747 nm.

[0142] In one embodiment of the functional premix, the titanium dioxide nanoparticles have the following particle size distribution characteristics: d10 is 148 to 189 nm; d50 is 239 to 485 nm; and d90 is 402 to 970 nm.

[0143] In one embodiment, the concentration of nanoparticles of the material with altered properties is tens to hundreds of ppm relative to the material with altered properties.

[0144] In one embodiment, the concentration of nanoparticles in the modified material is from 1 to 500 ppm.

[0145] In one embodiment, the concentration of the nanoparticles is low relative to the material, for example, in the range of single digits, tens to hundreds of ppm, such as (but not limited to): 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, the very low concentration of nanoparticles produces unexpected technical effects in modulating the properties of the polymer to which they are applied.

[0146] In one embodiment, the concentration of the nanoparticles relative to the material is from 1 to 500 ppm.

[0147] In one embodiment, the concentration of the nanoparticles relative to the material is 50, 100, 250, or 500 ppm.

[0148] In one embodiment, the resulting material with altered properties exhibits improved chemical, mechanical, electrical, and / or optical properties. In one embodiment of the method, the concentration of nanoparticles in the modified material is from tens to hundreds of ppm.

[0149] 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 properties are the polymer's storage modulus (E'), loss modulus (E''), loss factor (tan δ), and / or glass transition temperature (T). g ).

[0150] The inventors of this invention have discovered that when nanoparticles are incorporated into a polymer matrix, they can unexpectedly improve chemical and mechanical properties (such as storage modulus (E'), loss modulus (E''), and glass transition temperature (T). g And tan δ), and unexpectedly found that the higher amorphization of nanoparticles caused even more significant changes in the properties of the polymer matrix.

[0151] In one embodiment, the functional premix of the present invention serves as a dosage modifier for nanoparticles, which are packed together with a carrier for doping with metals, ceramics, polymer materials, or combinations thereof.

[0152] In one embodiment, the functional premix of the present invention serves as a sacrificial carrier or compatibilizer.

[0153] In one embodiment, the functional premix of the present invention serves as a sacrificial carrier for incorporating nanoparticles into a metal and / or ceramic matrix.

[0154] In one embodiment, the functional premix of the present invention serves as a compatibilizer, wherein both the compatibilizer and the nanoparticles are incorporated into the polymer matrix.

[0155] The following examples illustrate non-limiting embodiments of various polymers and a range of particle types, different compositions, grinding times, masses, particle size distributions, etc., which enable this specification to fully support the scope of the claims herein.

[0156] Example The embodiments shown herein are intended only to illustrate some different methods of implementing the invention, and are not intended to limit the scope of the invention.

[0157] Modifying polymers or other materials (e.g., metals and / or ceramics) by incorporating particles in the micrometer size range can lead to catastrophic failures such as cracking, deformation, geometric irregularities, and other problems. This invention addresses this problem and provides premixes containing a high concentration of nanoparticles. Because the nanoparticle concentration in the premixes of this invention is several orders of magnitude higher than the concentration required in the final material containing these nanoparticles to achieve performance improvements, the premixes of this invention are particularly advantageous for subsequent use as premixes or compatibilizers to prepare materials with lower nanoparticle concentrations. To prepare the material described in this patent application containing 5 ppm or 50 ppm of any nanoparticles, simply use a 1:100 or 1:10 mixture of the respective premix with the material to be modified, and homogenize until a specific concentration of product is obtained. Other final concentrations can be obtained by adjusting the concentration of the premix in the desired material.

[0158] To analyze the modified materials obtained using the premix of the present invention, several tests were conducted, as described below.

[0159] Dynamic mechanical thermal analysis (DMTA) has been widely used for polymer characterization by detecting relaxation processes at the macroscopic and molecular levels. In other words, it can provide information on the viscoelastic behavior of a system and decompose the modulus into two components: elastic and viscous components.

[0160] The modulus of the E* system is mathematically represented as a complex number consisting of two components: Where E' is the storage modulus (a measure of a material's elasticity—its ability to store energy), and E'' is the loss modulus (a measure of a material's ability to dissipate energy—energy lost as heat).

[0161] DMTA analysis can also obtain the loss tangent or damping tangent (tan delta), which is the ratio of energy dissipated during the cycle to the maximum stored potential energy. Materials with high loss tangents dissipate most of the energy used to deform them, while materials with low loss tangents are more elastic and have greater energy storage capacity.

[0162] Example 1—Epoxy Resin Containing Graphene Oxide Nanoparticles One embodiment of the premix of the present invention is an epoxy resin containing up to 500 ppm of graphene oxide nanoparticles. The epoxy resin used in the experiment was commercially available liquid epoxy resin DER 331 from Dow Chemical Company. TM It is a liquid reaction product of epichlorohydrin and bisphenol A.

[0163] The concentrations of graphene oxide nanoparticles incorporated into the resin are listed in Table 1. These concentrations correspond to the samples named in the tests discussed below and the samples shown in Figures 1-31. Table 1—Description of Samples 1-4 Example 2—Epoxy Resin Containing Nb2O5 Nanoparticles Another embodiment of the premix of the present invention is an epoxy resin containing up to 500 ppm of niobium pentoxide nanoparticles. The epoxy resin used in the experiment was commercially available liquid epoxy resin DER 331 from Dow Chemical Company. TM It is a liquid reaction product of epichlorohydrin and bisphenol A.

[0164] The concentrations of niobium pentoxide nanoparticles incorporated into the resin are listed in the table below. These concentrations correspond to the samples named in the tests discussed below and the samples shown in Figures 1-31: Table 2 – Description of Samples 5-8 The particle size distribution characteristics of the niobium nanoparticles used are described in detail in the same applicant's patent application WO2022036427, which pertains to a sample that has been ground for 12 hours.

[0165] Example 3 – Epoxy Resin Containing TiO2 Nanoparticles One embodiment of the premix of the present invention is an epoxy resin containing up to 500 ppm titanium dioxide nanoparticles. The epoxy resin used in the experiment was commercially available liquid epoxy resin DER 331 from Dow Chemical Company. TM It is a liquid reaction product of epichlorohydrin and bisphenol A.

[0166] The concentrations of titanium dioxide nanoparticles incorporated into the resin are listed in the table below. These concentrations correspond to the samples named in the tests discussed below and the samples shown in Figures 1-31: Table 3 – Description of Samples 9-12 The particle size distribution characteristics of the titanium nanoparticles used are described in detail in the same applicant's patent application BR102022010931 (still confidential), which pertains to a sample that has been ground for 12 hours.

[0167] Example 4 – Fourier Transform Infrared Spectroscopy (FTIR) Analysis The nanoparticle-containing resin premixes prepared according to Examples 1, 2, and 3 were cured and subsequently subjected to several types of tests. In the first set of tests, they were subjected to infrared spectroscopy analysis. This technique is undoubtedly one of the most important analytical techniques currently available. One of its significant advantages is its ability to study most samples in virtually any physical state. By carefully selecting sampling techniques and preparation methods, liquids, solutions, pastes, powders, films, fibers, gases, and surfaces can be analyzed. The introduction of Fourier transform infrared spectroscopy (FTIR) has significantly improved the quality of infrared spectra and minimized the time required to acquire data. The continuous advancement of computer technology has made it possible to develop various techniques for testing / detecting previously difficult-to-handle samples. Infrared (IR) radiation roughly corresponds to the portion of the electromagnetic spectrum located between the visible and microwave regions. In materials analysis and identification, the most useful portion lies at 4000 cm⁻¹. -1 Up to 400 cm -1(2.5 μm to 25 μm), also known as the mid-infrared region. Infrared spectroscopy is based on the vibrations of atoms in molecules. Infrared spectra are typically obtained by passing infrared radiation through a sample and measuring the fraction of incident radiation absorbed at each frequency (energy) or wavelength. By absorbing infrared radiation, molecules are excited to higher energy levels. This process is quantized, meaning that only certain frequencies (energys) are absorbed, and this absorption corresponds to energy changes 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 spectral lines because each change in vibrational energy level corresponds to a change in a series of rotational energy levels. These spectral lines overlap to form the observed bands: vibrational-rotational bands. The absorption frequency or wavelength of the radiation depends on the relative mass of the atoms in the compound structure, the bond strength constant, and the atomic geometry. Each absorption frequency appearing in an infrared spectrum corresponds to a vibrational frequency in a portion of the sample molecule. The position of a band in an infrared spectrum can be represented by wavelength (μm) or wavenumber (cm). -1 The intensity of a spectral band can be expressed as a percentage of transmittance (%T) or absorbance (A). Transmittance is the ratio of the radiant energy transmitted through the sample to the radiant energy incident on the sample. Absorbance is the decimal logarithm of the reciprocal of transmittance, i.e., .

[0168] In this embodiment, a Bruker OPTIK GmbH HTS-XT Vertex 70 spectrometer was used, employing ATR (attenuated total reflectance) mode and equipped with a diamond crystal. The liquid sample was placed in the instrument's sample holder and incubated at 4000 cm⁻¹. -1 Up to 400 cm -1 Measurements were taken within the observation range with a resolution of 4 cm. -1 And perform 32 scans.

[0169] The results are shown in Figures 1-5.

[0170] Figure 1 depicts the FTIR spectrum of the sample. Figure 1A The spectra of samples 1, 2, and 3 are shown in the figure. Figure 1B The superposition of the spectra is shown in the figure (Y-axis represents transmittance in % and X-axis represents transmittance in cm). -1 (The wave number is calculated).

[0171] Figure 2 shows the FTIR spectrum of the sample. Figure 2A The spectra of samples 4, 5, and 6 are shown in the image. Figure 2B The superposition of the spectra is shown in the figure (Y-axis represents transmittance in % and X-axis represents transmittance in cm). -1 (The wave number is calculated).

[0172] Figure 3 depicts the FTIR spectrum of the sample. Figure 3A The spectra of samples 7, 8, and 9 are shown in the image. Figure 3B The superposition of the spectra is shown in the figure (Y-axis represents transmittance in % and X-axis represents transmittance in cm). -1 (The wave number is calculated).

[0173] Figure 4 depicts the FTIR spectrum of the sample. Figure 4A The spectra of samples 10, 11, and 12 are shown in the figure. Figure 4B The superposition of the spectra is shown in the figure (Y-axis represents transmittance in % and X-axis represents transmittance in cm). -1 (The wave number is calculated).

[0174] Figure 5 The FTIR spectra of Lacktherm 1314 resin samples were depicted (Y-axis represents transmittance in % and X-axis represents transmittance in cm⁻¹). -1 (wave number) Example 5 – Thermogravimetric Analysis The premixes prepared according to Examples 1, 2, and 3 were cured and analyzed using thermogravimetric analysis. The results are shown in... Figure 6-19 middle.

[0175] Figure 6 Thermogravimetric analysis (TGA) was performed on the mass loss curve and first derivative of sample 1 as a function of temperature (the left Y-axis represents TG; the right Y-axis represents DTF (% / min); and the X-axis represents temperature in degrees Celsius).

[0176] Figure 7 Thermogravimetric analysis: mass loss curve and first derivative of sample 2 as a function of temperature were plotted (the left Y-axis is TG; the right Y-axis is DTF (% / min); and the X-axis is temperature in degrees Celsius).

[0177] Figure 8 Thermogravimetric analysis (TGA) was performed on the mass loss curve and first derivative of sample 3 as a function of temperature (the left Y-axis represents TG; the right Y-axis represents DTF (% / min); and the X-axis represents temperature in degrees Celsius).

[0178] Figure 9 Thermogravimetric analysis (TGA) was performed on the mass loss curve and first derivative of sample 4 as a function of temperature (the left Y-axis represents TG; the right Y-axis represents DTF (% / min); and the X-axis represents temperature in degrees Celsius).

[0179] Figure 10 Thermogravimetric analysis (TGA) was performed on the mass loss curve and first derivative of sample 5 as a function of temperature (the left Y-axis represents TG; the right Y-axis represents DTF (% / min); and the X-axis represents temperature in degrees Celsius).

[0180] Figure 11 Thermogravimetric analysis: mass loss curve and first derivative of sample 6 as a function of temperature were plotted (the left Y-axis is TG; the right Y-axis is DTF (% / min); and the X-axis is temperature in degrees Celsius).

[0181] Figure 12 Thermogravimetric analysis (TGA) was performed on the mass loss curve and first derivative of sample 7 as a function of temperature (the left Y-axis represents TG; the right Y-axis represents DTF (% / min); and the X-axis represents temperature in degrees Celsius).

[0182] Figure 13 Thermogravimetric analysis (TGA) was performed on the mass loss curve and first derivative of sample 8 as a function of temperature (the left Y-axis represents TG; the right Y-axis represents DTF (% / min); and the X-axis represents temperature in degrees Celsius).

[0183] Figure 14 Thermogravimetric analysis (TGA) was performed on the mass loss curve and first derivative of sample 9 as a function of temperature (the left Y-axis represents TG; the right Y-axis represents DTF (% / min); and the X-axis represents temperature in degrees Celsius).

[0184] Figure 15 Thermogravimetric analysis (TGA) was performed on the mass loss curve and first derivative of sample 10 as a function of temperature (the left Y-axis represents TG; the right Y-axis represents DTF (% / min); and the X-axis represents temperature in degrees Celsius).

[0185] Figure 16 Thermogravimetric analysis (TGA) was performed on the mass loss curve and first derivative of sample 11 as a function of temperature. The left Y-axis represents TG; the right Y-axis represents DTF (% / min); and the X-axis represents temperature in degrees Celsius.

[0186] Figure 17 Thermogravimetric analysis (TGA) was performed on the mass loss curve and first derivative of sample 11 as a function of temperature. The left Y-axis represents TG; the right Y-axis represents DTF (% / min); and the X-axis represents temperature in degrees Celsius.

[0187] Figure 18 Thermogravimetric analysis (TGA) was performed on the mass loss curve and first derivative of sample 12 as a function of temperature. The left Y-axis represents TG; the right Y-axis represents DTF (% / min); and the X-axis represents temperature in degrees Celsius.

[0188] Figure 19 Thermogravimetric analysis (TGA) was used to depict the mass loss curves and first derivatives of Lacktherm 1314-1 resin samples as a function of temperature (the left Y-axis represents TG; the right Y-axis represents DTF (% / min); and the X-axis represents temperature in degrees Celsius).

[0189] Example 6 – Scanning Electron Microscopy Analysis The premixes prepared and cured according to Examples 1, 2, and 3 were analyzed by scanning electron microscopy (SEM) and EDS (with definitions specified). The results are shown in... Figure 24-35 middle.

[0190] Figure 20 The MEV image and EDS results for sample 1 are depicted. Scanning electron microscope images are shown in A) and B); the EDS analysis image is shown in C).

[0191] Figure 21 The MEV image and EDS results for sample 2 are depicted. Scanning electron microscope image is shown in A); EDS analysis image is shown in B).

[0192] Figure 22 The MEV images and EDS results for sample 3 are depicted. Scanning electron microscope images are shown in A) and B); the EDS analysis image is shown in C).

[0193] Figure 23 The MEV images and EDS results for sample 4 are depicted. Scanning electron microscope images are shown in A) and B); the EDS analysis image is shown in C).

[0194] Figure 24 The MEV images and EDS results for sample 5 are depicted. Scanning electron microscope images are shown in A) and B); the EDS analysis image is shown in C).

[0195] Figure 25 The MEV images and EDS results for sample 6 are depicted. Scanning electron microscope images are shown in A) and B); the EDS analysis image is shown in C).

[0196] Figure 26 The MEV images and EDS results for sample 7 are depicted. Scanning electron microscope images are shown in A) and B); the EDS analysis image is shown in C).

[0197] Figure 27 The MEV images and EDS results for sample 8 are depicted. Scanning electron microscope images are shown in A) and B); the EDS analysis image is shown in C).

[0198] Figure 28 The MEV images and EDS results for sample 9 are depicted. Scanning electron microscope images are shown in A) and B); the EDS analysis image is shown in C).

[0199] Figure 29The MEV images and EDS results for sample 10 are depicted. Scanning electron microscope images are shown in A) and B); the EDS analysis image is shown in C).

[0200] Figure 30 The MEV images and EDS results for sample 11 are depicted. Scanning electron microscope images are shown in A) and B); the EDS analysis image is shown in C).

[0201] Figure 31 The MEV images and EDS results for sample 12 are depicted. Scanning electron microscope images are shown in A) and B); the EDS analysis image is shown in C).

[0202] Example 7 – Epoxy Resin Premix Containing Nb2O5 Nanoparticles – Analysis of the Change in Loss Tangent Storage Modulus with Temperature For testing purposes, three repeated tests were considered for samples 1000 / 0, 1010 / 1, and 1020 / 1, since the other samples were simply the remaining test samples and did not show significant changes in the test.

[0203] Polymer samples containing titanium dioxide and niobium pentoxide micron particles were not tested because they exhibited catastrophic failures, such as cracking, deformation, and geometric irregularities.

[0204] Conversely, a premix containing nanoparticles was actually obtained, i.e., the nanoparticles were incorporated into the resin at a test concentration. The corresponding premix is ​​particularly suitable for use as a premix for subsequent preparation of resins with lower nanoparticle concentrations before curing. That is, if it is desired to prepare an epoxy resin containing 50 ppm of any of the nanoparticles (graphene oxide, niobium pentoxide, titanium dioxide) described in the above examples, a 1:10 mixture of the corresponding premix and resin is used, and homogenization is performed until the product of the stated concentration is obtained. Other final concentrations can be obtained by adjusting the concentration.

[0205] Table 4 shows the test specimen numbers: Table 5 shows the results of the activation energy (average value) of the resin. Table 6 shows the storage modulus (average) results for the resin. Table 7 shows the loss tangent (average) results for the resin. Table 8 shows the glass transition temperature (TG) results for the resin. Table 9 shows the raw data of the storage modulus of resin 1020 / 1 as a function of temperature, indicating the damping effect.

[0206] Table 9 – Energy Storage Modulus Data. Table 10 shows the raw data of the storage modulus of resin 1010 / 1 as a function of temperature, indicating the damping effect.

[0207] Table 10 – Energy Storage Modulus Data. Table 11 shows the raw data of the storage modulus of resin 1000 / 0 as a function of temperature, indicating the damping effect.

[0208] Table 11 – Energy Storage Modulus Data. Table 12 shows the average data of the storage modulus of resins 1020 / 1, 1010 / 1, and 1000 / 0 as a function of temperature.

[0209] Table 12 – Average values ​​of energy storage modulus measurements. Table 13 shows the loss tangent data of resin 1020 / 1 as a function of temperature.

[0210] Table 13 – Loss tangent data for resin 1020 / 1. Table 14 shows the loss tangent data of resin 1010 / 1 as a function of temperature.

[0211] Table 14 – Loss Tangent Data for Resin 1010 / 1 Table 15 shows the loss tangent data of resin 1000 / 0 as a function of temperature.

[0212] Table 15 – Loss tangent data for resin 1000 / 0. Table 16 shows the comparison data of the loss tangent of resins 1020 / 1, 1010 / 1, and 1000 / 0 as a function of temperature.

[0213] Table 16 – Comparison of the average value of the loss angle tangent The data in Table 8-16 can be viewed graphically, as shown below. Figure 32-36 middle.

[0214] Figure 32 A graph depicting the storage modulus (damping effect) of 1020 / 1 resin as a function of increasing temperature is presented. In A), the Y-axis represents the storage modulus in E' (1.000 Hz) / MPa, and the X-axis represents the temperature in degrees Celsius. In B), a loss tangent graph of the same material is shown, with the Y-axis representing the loss tangent value and the X-axis representing the temperature in degrees Celsius. The graphs show the averages and deviations according to Tables 9 and 13.

[0215] Figure 33 A graph depicting the storage modulus (damping effect) of 1010 / 1 resin as a function of increasing temperature is presented. In A), the Y-axis represents the storage modulus in E' (1.000 Hz) / MPa, and the X-axis represents the temperature in degrees Celsius. In B), a loss tangent graph of the same material is shown, with the Y-axis representing the loss tangent value and the X-axis representing the temperature in degrees Celsius. The graphs show the average and deviation based on the data in Tables 10 and 14.

[0216] Figure 34A graph depicting the storage modulus (damping effect) of 1000 / 0 resin as a function of increasing temperature is presented. In A), the Y-axis represents the storage modulus in E' (1.000 Hz) / MPa, and the X-axis represents the temperature in degrees Celsius. In B), a loss tangent graph of the same material is shown, with the Y-axis representing the loss tangent value and the X-axis representing the temperature in degrees Celsius. The graphs show the averages and deviations according to Tables 11 and 15.

[0217] Figure 35 The basis for resins 1020 / 1, 1010 / 1, and 1000 / 0 is shown. Figure 36 A. Comparison curves of energy storage modulus shown in graphs A, 37A, and 38A.

[0218] Figure 36 The basis for resins 1020 / 1, 1010 / 1, and 1000 / 0 is shown. Figure 36 Comparison of loss tangent curves in B, 37B and 38B.

[0219] Taking all factors into consideration, Table 8-16 and Figure 32-36 The results shown indicate that incorporation of low concentrations (in the ppm range) of nanoparticles can significantly modify the mechanical properties of polymers, as can be seen from the loss tangent results. Tan delta can be understood as the energy dissipation capacity of a material. The higher the Tan delta, the easier the material dissipates energy. On the other hand, the lower the Tan delta, the greater the elasticity of the material when using fillers, and therefore the greater its filler storage capacity. Therefore, by changing Tan delta (increasing or decreasing it), the properties of the material can be tuned to better suit different applications; for example, a lower Tan delta is preferred for structural applications.

[0220] Example 8 – Sample Description Table 17 provides a description of the test specimens in the following examples: Polymer samples containing titanium dioxide and niobium pentoxide micron-sized particles were not tested because they exhibited catastrophic failures, such as cracking, deformation, and geometric irregularities. Similar to the foregoing embodiments, a premix containing nanoparticles was actually obtained, i.e., the nanoparticles were incorporated into the resin at the test concentration. The corresponding premix is ​​particularly advantageous for subsequent use as a premix to prepare resins with lower nanoparticle concentrations; that is, if it is necessary to prepare an epoxy resin containing 50 ppm of any of the nanoparticles (graphene oxide, niobium pentoxide, titanium dioxide) from the above embodiments, a 1:10 mixture of the corresponding premix and resin is used, homogenized until the desired concentration is obtained. Other final concentrations can be obtained by adjusting the concentration.

[0221] Example 9 – Energy Storage Modulus (E') Analysis The samples described in Example 8 were analyzed by DMTA (Dynamic Mechanical Thermal Analysis) through three repeated tests, and the results of the storage modulus (E') are shown in Tables 18-26 below: Table 18 – Results of three repeated tests on the storage modulus (E') of sample 1020 / 1 Table 19 – Results of five repeated tests on the storage modulus (E') of sample 1010 / 1 Table 20 – Results of four repeated tests of the storage modulus (E') of sample 1000 / 0. Table 21 – Results of three repeated tests on the storage modulus (E') of sample 1020 / 4 Table 22 – Results of three repeated tests on the storage modulus (E') of sample 1010 / 3 Table 23 – Results of three repeated tests on the storage modulus (E') of sample 1010 / 4 Table 24 – Results of five repeated tests on the storage modulus (E') of sample 1010 / 2 Table 25 – Results of three repeated tests on the storage modulus (E') of sample 1020 / 3 Table 26 – Results of four repeated tests on the storage modulus (E') of sample 1020 / 2 Example 10 – Loss Tangent (tan d) Analysis The samples described in Example 8 were analyzed by DMTA (Dynamic Mechanical Thermal Analysis) through three repeated tests, and the results of the storage modulus (E') are shown in Tables 27-35 below: Table 27 – Results of three repeated tests of the loss tangent (tan d) for sample 1020 / 1: Table 28 – Results of five repeated tests of the loss tangent (tand) of sample 1010 / 1: Table 29 – Results of four repeated tests of the loss tangent (tand) of sample 1000 / 0: Table 30 – Results of three repeated tests of the loss tangent (tand) of sample 1010 / 4: Table 31 – Results of three repeated tests of the loss tangent (tan d) for sample 1010 / 3: Table 32 – Results of three repeated tests of the loss tangent (tan d) for sample 1020 / 4: Table 33 – Results of five repeated tests of the loss tangent (tan d) for sample 1010 / 2: Table 34 – Results of three repeated tests of the loss tangent (tan d) for sample 1020 / 3: Table 35 – Results of four repeated tests of the loss tangent (tan d) for sample 1020 / 2: Example 11 – Comparison of Loss Tangent (tan d) Data Tables 36 and 37 below show a comparison of the average loss tangent data for each sample described in Example 8: Table 36 – Comparison of data on the average loss tangent (tan d): Table 37 – Comparison of data on the average loss tangent (tan d): Example 12 – Data Comparison of Energy Storage Modulus (E') Tables 38 and 39 below show a comparison of the average storage modulus data for each sample described in Example 8: Table 38 – Comparison of Average Energy Storage Modulus (E'): Table 39 – Comparison of data on average energy storage modulus (E'): Example 13 – Comparison of DMTA Analysis Results Tables 40, 41, and 42 below show a comparison of the activation energy (EA), storage modulus (E'), and loss tangent (tan d) for each sample described in Example 8: Table 40 – Comparison of average activation energy (EA) data for each sample: Table 41 – Comparison of average storage modulus (E') for each sample: Table 42 – Comparison of average loss tangent (tan d) data for each sample: Table 43 – Average Glass Transition Temperature (T) of Each Sample g Data comparison: Figure 37 The figure shows a comparison curve of the storage modulus (E') of each sample described in Example 8 as a function of temperature.

[0222] Figure 38 The figure shows a comparison curve of the loss tangent (tan d) of each sample described in Example 8 as a function of temperature.

[0223] or, Figure 39 , 40 Figure 41 shows a bar chart comparison of the DMTA results of the samples described in Example 8.

[0224] Figure 39 A bar chart showing the average activation energy (AE) of each sample described in Example 8 is shown.

[0225] Figure 40 A bar chart showing the average storage modulus (E') of each sample described in Example 8 is shown.

[0226] Figure 41A bar chart showing the average loss tangent (tan d) for each sample described in Example 8 is shown.

[0227] also, Figure 42 A line graph is shown, which compares the storage modulus (E') with changes in concentration and nanoparticle type.

[0228] also, Figure 43 A line graph is shown, which compares the loss tangent (tan d) with concentration and nanoparticle type.

[0229] Based on the DMTA analysis of the samples described in Example 8, it can be concluded that the incorporation of low concentrations (ppm level) of nanoparticles can significantly alter the mechanical properties of the polymer, as can be seen from the tan delta results. Tan delta can be understood as the energy dissipation capacity of a material; the higher the tan delta, the stronger the energy dissipation capacity. On the other hand, the lower the tan delta, the greater the elasticity of the material when filler is applied, and therefore the greater its capacity to store filler. Therefore, changing the tan delta (increasing or decreasing) can tailor the material to better suit different applications; for example, a lower tan delta is preferred for structural applications.

[0230] Example 14 – Fourier Transform Infrared Spectroscopy (FTIR) Analysis The Fourier transform infrared spectroscopy analysis results of each sample described in Example 8 are shown below. Figures 44-55 middle.

[0231] Figure 44 The FTIR spectrum of sample 1000 / 0 described in Example 8 is depicted (Y-axis is transmittance in % and X-axis is transmittance in cm). -1 (The wave number is calculated).

[0232] Figure 45 The FTIR spectrum of sample 1010 / 1 described in Example 8 is depicted (Y-axis is transmittance in % and X-axis is transmittance in cm). -1 (The wave number is calculated).

[0233] Figure 46 The FTIR spectrum of sample 1010 / 2 described in Example 8 is depicted (Y-axis is transmittance in % and X-axis is transmittance in cm). -1 (The wave number is calculated).

[0234] Figure 47 The FTIR spectrum of sample 1010 / 3 described in Example 8 is depicted (Y-axis is transmittance in % and X-axis is transmittance in cm). -1 (The wave number is calculated).

[0235] Figure 48 The FTIR spectrum of sample 1010 / 4 described in Example 8 is depicted (Y-axis is transmittance in % and X-axis is transmittance in cm). -1 (The wave number is calculated).

[0236] Figure 49 The FTIR spectrum of sample 1020 / 1 described in Example 8 is depicted (Y-axis is transmittance in % and X-axis is transmittance in cm). -1 (The wave number is calculated).

[0237] Figure 50 The FTIR spectrum of sample 1020 / 2 described in Example 8 is depicted (Y-axis is transmittance in % and X-axis is transmittance in cm). -1 (The wave number is calculated).

[0238] Figure 51 The FTIR spectrum of sample 1020 / 3 described in Example 8 is depicted (Y-axis is transmittance in % and X-axis is transmittance in cm). -1 (The wave number is calculated).

[0239] Figure 52 The FTIR spectrum of sample 1020 / 4 described in Example 8 is depicted (Y-axis is transmittance in % and X-axis is transmittance in cm). -1 (The wave number is calculated).

[0240] Figure 53 The FTIR spectrum of sample 1030 / 4 described in Example 8 is depicted (Y-axis is transmittance in % and X-axis is transmittance in cm). -1 (The wave number is calculated).

[0241] Figure 54 The FTIR spectrum of sample 1040 / 4 described in Example 8 is depicted (Y-axis is transmittance in % and X-axis is transmittance in cm). -1 (The wave number is calculated).

[0242] Figure 55 A comparison of the FTIR spectra of the samples described in Example 8 is presented (Y-axis is transmittance in % and X-axis is transmittance in cm⁻¹). -1 (wave number) Example 15 – DMTA Analysis of a Sample Containing Niobium Nanoparticles The sample 1010 / 1 described in Example 8 was analyzed by DMTA (Dynamic Mechanical Thermal Analysis) through four repeated tests, and the results are shown in Table 44 below: Table 44 – DMTA results of sample 1010 / 1 at 1 Hz frequency Table 45 – Activation energy results for sample 1010 / 1: The results of sample 1010 / 1 were further in Figure 56 , 57 As explained in section 58.

[0243] Figure 56 The curve of the storage modulus (E') of sample 1010 / 1 as a function of temperature was plotted.

[0244] Figure 57 The curve of the loss tangent (tan d) of sample 1010 / 1 as a function of temperature was plotted.

[0245] Figure 58 The curve of the loss modulus (E'') of sample 1010 / 1 as a function of temperature was plotted.

[0246] The sample 1010 / 2 described in Example 8 was analyzed by DMTA (Dynamic Mechanical Thermal Analysis) through four repeated tests, and the results are shown in Tables 43 and 44 below: Table 46 – DMTA results of sample 1010 / 2 at 1 Hz: Table 47 – DMTA results of sample 1010 / 2 at 5 Hz: Table 48 – Activation energy results for sample 1010 / 2: The results of sample 1010 / 2 were further in Figure 59 , 60 As explained in section 61.

[0247] Figure 59 The storage modulus (E') of sample 1010 / 2 as a function of temperature was plotted.

[0248] Figure 60 The curve of the loss tangent (tan d) of sample 1010 / 2 as a function of temperature was plotted.

[0249] Figure 61 The curve of the loss modulus (E'') of sample 1010 / 2 as a function of temperature was plotted.

[0250] The sample 1010 / 3 described in Example 8 was analyzed by DMTA (Dynamic Mechanical Thermal Analysis) through four repeated tests, and the results are shown in Table 49 below: Table 49 – DMTA results of sample 1010 / 3 at 1 Hz: Table 50 – Activation energy results for sample 1010 / 3: The results of sample 1010 / 3 were further in Figure 62 , 63 As explained in section 64.

[0251] Figure 62 The storage modulus (E') of sample 1010 / 3 as a function of temperature was plotted.

[0252] Figure 63 The curve of the loss tangent (tan d) of sample 1010 / 3 as a function of temperature was plotted.

[0253] Figure 64 The curve of loss modulus (E'') of sample 1010 / 3 as a function of temperature was plotted.

[0254] Example 16 – Comparison of DMTA analysis of samples containing niobium nanoparticles Based on the results shown in Example 15, the storage modulus (E'), loss modulus (E''), and glass transition temperature (T) of each sample were calculated. g The average value of (). The comparison data is shown in the table below: Table 51 – Storage modulus (E') values ​​for each sample: Table 52 – Loss modulus (E'') values ​​for each sample: Table 53 – Glass transition temperatures (T) of each sample g )value: Figure 65 A bar chart showing the average storage modulus (E') of each sample described in Example 15 is shown.

[0255] Figure 66 A bar chart showing the average loss modulus (E'') of each specimen described in Example 15 is shown.

[0256] Figure 67 A bar chart showing the average glass transition temperature of each sample described in Example 15 is presented.

[0257] Based on the DMTA analysis of Example 16, it can be concluded that the incorporation of low concentrations (ppm level) of nanoparticles can significantly alter the mechanical properties of the polymer, as can be seen from the tan delta results. Tan delta can be understood as the energy dissipation capacity of a material; the higher the tan delta, the stronger the energy dissipation capacity. On the other hand, the lower the tan delta, the greater the elasticity of the material when filler is applied, and therefore the greater its filler retention capacity. Therefore, changing the tan delta (increasing or decreasing) can tailor the material to better suit different applications; for example, a lower tan delta is preferred for structural applications.

[0258] Example 17 – Preparation method of niobium pentoxide nanoparticles In this embodiment, several niobium pentoxide nanoparticle formulations with purities greater than 99% were obtained. Commercially available niobium pentoxide with the particle size distribution shown in Table 54 was pre-ground in a high-energy mill containing yttrium-stabilized zirconia balls with a diameter of 400 μm in a liquid medium at a pH adjusted to 6.6. The mill speed was 3500 rpm, and particle grinding was performed at a temperature below 40°C. Table 4 shows the particle size distribution (PSD) of the feed (commercial product) and output niobium pentoxide during the pre-grinding step.

[0259] Table 54 – Feed PSD (commercial product) and pre-ground PSD. The average specific surface area S (m²) of the particles after the pre-grinding step 2 / g) is 0.32 m 2 / g.

[0260] In one embodiment, pre-ground particles are fed into a high-energy mill under conditions similar to those described in Example 5, but using 200 µm Zr balls, and milled for varying times until individual nanoparticle formulations are obtained. Three different nanoparticle formulations were obtained, each with a specific particle size distribution as described in Table 55.

[0261] Table 55 – Particle size distribution of niobium pentoxide nanoparticles in three different formulations (C, D, and E). Example 18 – Preparation method of titanium dioxide nanoparticle formulation In this embodiment, a batch of 1.125 kg of TiO2 particles with a particle size distribution of D90 1.320 µm, D50 0.6098 µm, and D10 0.153 µm was fed into a high-energy mill containing 5 liters of water and 0.2-0.4 mm zeta balls with a concentration of 3.65 kh / L. The grinding parameters were: Tmax 60°C, solid content 18.36%, and a pressure of 1.1 to 1.2 bar with a pump speed of 90 min. -1 The flow rate is 51 kg slurry / h, and the agitator speed is 3700 min. -1 Under conditions where the inlet material temperature is 21.3℃ to 37.1℃ and the outlet temperature is 22.4℃ to 49.2℃, the high-energy mill was run for 1 to 8 cycles, each cycle lasting 1 hour. The initial energy of each cycle was 2.4 kW, and the grinding energy was 1.8 to 14.4 kWh. The resulting particle size distribution characteristics are shown in Table 56 below. Table 56 – Particle size distribution characteristics obtained after multiple grinding cycles under the above conditions. For cooling, the parameters are as follows: the inlet temperatures of the grinding chamber, mechanical seal, circulating water tank and cooler are 7.3℃ and 11.4℃ respectively, the cooling water flow rate of each stage is 1000 liters per hour, and the total flow rate is 4000 liters per hour.

[0262] Example 19 – Testing the Crystallinity of Niobium Pentoxide Nanoparticles The inventors investigated the properties of niobium pentoxide nanoparticle formulations obtained at different grinding times according to the method described in Example 17.

[0263] The samples were analyzed using transmission microscopy to obtain grain size histograms, and structural characterization was obtained using X-ray diffraction. X-ray diffraction analysis showed that samples treated with different grinding times exhibited significant variations in structural characteristics such as crystallinity (%) and grain size.

[0264] Figure 68 The size histogram of a niobium pentoxide particle sample (referred to as AR) obtained by transmission microscopy analysis is shown.

[0265] Figure 69 The size histogram of a niobium pentoxide particle sample ground for 1 hour is shown.

[0266] Figure 70 The size histogram of a niobium pentoxide particle sample ground for 3 hours is shown by transmission microscopy analysis.

[0267] Figure 71The size histogram of a niobium pentoxide particle sample ground for 6 hours is shown by transmission microscopy analysis.

[0268] Figure 72 The size histogram of a niobium pentoxide particle sample ground for 12 hours is shown by transmission microscopy analysis.

[0269] Figure 73 A comparison of X-ray diffraction patterns is shown, which indicate that the crystal phase of niobium pentoxide particle samples treated for different grinding times (i.e., 1 hour, 3 hours, 6 hours, and 12 hours) changed significantly.

[0270] Figure 74 The graphs show crystallinity (%), grain size (nm), and grinding time (h).

[0271] The AR sample consisted of 81% monoclinic phase. On the other hand, Figure 74 The data shows that crystallinity (%) and grain size (nm) decrease with increasing grinding time. The data exhibit an exponential decay of crystallinity (%) and grain size (nm), with the grain size (nm) appearing to reach a distinct plateau after 6 hours of grinding. The decrease in crystallinity shows a similar characteristic to the decrease in grain size; however, significant changes in crystallinity persist after the 6-hour grinding period. Regarding crystallinity, 26% monoclinic phase was observed in the sample treated with 12 hours of grinding.

[0272] Samples with higher amorphous properties (e.g., 12-hour samples) showed even more significant improvements in enhancing polymer properties. Significant improvements were observed with increasing amorphization, i.e., at least 19% amorphization < at least 39% amorphization < at least 55% amorphization < at least 70% amorphization. For 74% amorphization, even more significant modulation of polymer properties was observed.

[0273] Example 20 – Preparation of epoxy resin samples containing nanoparticles To prepare the test samples to be characterized, niobium pentoxide nanoparticles were weighed and ground for 12 hours to achieve concentrations of 50 ppm, 100 ppm, 250 ppm and 500 ppm.

[0274] The nanoparticle formulation was added to methyl ethyl ketone (MEK), and the suspension was sonicated for 15 minutes.

[0275] While the MEK+ nanoparticle colloidal suspension is subjected to ultrasonic treatment, epoxy resin is placed in a reactor at a temperature higher than T. g The mixture is continuously rotated and stirred at a specific temperature.

[0276] Subsequently, the MEK+ nanoparticle suspension was added to the reactor containing the resin under stirring. The addition was slow, and after 100% dilution, the mixture was kept stirred under heating for 30 minutes.

[0277] Then, the methyl ethyl ketone was removed under vacuum. Subsequently, a catalyst, consisting of a 70-30 ratio of cyclic aliphatic amino catalyst, was added. This yielded the test sample for subsequent characterization.

[0278] Example 21 – Dispersion capability of niobium pentoxide nanoparticles in a polymer matrix To verify the dispersibility of nanoparticles, polymer samples containing nanoparticles were prepared using an ultrathin sectioning technique. These nanoparticles were obtained by grinding for 12 hours. Before being sent to an ultrathin sectioner, the polymer matrix samples containing particles were cut, trimmed, and semi-thin sectioned to obtain ultrathin sections.

[0279] The ultrathin sections are 70-100 nm thick, allowing electron beams to pass through, thus enabling the application of transmission electron microscopy.

[0280] Ultrathin sections were placed on a copper grid for feeding into a transmission electron microscope. These analyses were performed using a JEOL JEM-1011 microscope with a maximum accelerating voltage of 100 kV. However, to maximize image contrast, a voltage of 80 kV was used, and in some cases, 60 kV.

[0281] The obtained images are bright-field images, meaning that the primary contrast mechanism is mass-thickness. In other words, the more atoms in the sample or the thicker a given area of ​​the sample, the darker it appears in the image.

[0282] Figure 75 Niobium pentoxide particles are highlighted in an ultrathin section of a 50 ppm sample.

[0283] Figure 76 Niobium pentoxide particles are highlighted in an ultrathin section of a 100 ppm sample.

[0284] Figure 77 Niobium pentoxide particles are highlighted in an ultrathin section of a 250 ppm sample.

[0285] Figure 78 Niobium pentoxide particles are highlighted in an ultrathin section of a 500 ppm sample.

[0286] Figures 75 to 78 This indicates that the number of well-dispersed particles is directly proportional to the concentration used.

[0287] Without being bound by theory, it is understandable that crystallinity affects the dispersibility of nanoparticle formulations within a polymer matrix. Formulations milled for 12 hours exhibited excellent dispersibility, as observed in transmission microscopy results of ultrathin sections prepared using ultrathin sectioning techniques. It is expected that particles with higher crystallinity will have a greater tendency to aggregate, thus resulting in less uniform dispersion within the polymer matrix and a reduced mean free path between particles.

[0288] Example 22 – A premix containing phenolic resin and niobium pentoxide nanoparticles and its use in the preparation of friction composite materials. To demonstrate that the premix containing nanoparticles of this invention can be used to modify the properties of different materials, additional tests were conducted on other polymers.

[0289] A premix containing niobium pentoxide nanoparticles (obtained by 12 hours of milling) and phenolic resin was used to prepare a friction composite material for automotive brake pads.

[0290] First, premixes with different nanoparticle contents (i.e., 0.1%, 0.7%, 1.0%, and 2.0% m / m) were tested using three methods of dispersion and incorporation of the nanoparticle formulations: resin diluted in alcohol + nanoparticles, suspension in alcohol + nanoparticles, and dry mixing + nanoparticles.

[0291] In one embodiment, 6.0 kg of the total premix of this embodiment is prepared using 5.5 wt% phenolic resin and 94.5 wt% nanoparticles. This premix is ​​used together with other raw materials to prepare the friction composite material of this product. The process is carried out in two steps in an EIRICH mixer. The first step involves mixing all components for 10 minutes, and the second step continues mixing for 10 minutes, but with the components added gradually in several sub-steps (i.e., 2 minutes, 2 minutes, 2 minutes, and 4 minutes).

[0292] After the mixing stage is completed, the material is pressed to form a friction material.

[0293] Table 57 shows each test specimen: Spark and flame tests were conducted under the following conditions: braking from 80 km / h to 24 km / h within 6 seconds (deceleration 2.7 m / s²). 2 Braking interval is 90 seconds. Repeat each braking action 20 times.

[0294] During testing, it was observed that samples containing niobium pentoxide nanoparticles in diluted resin exhibited a delay in the time it took to generate a spark. Furthermore, the number of sparks decreased during braking, and the flame size decreased after braking.

[0295] Figure 79 A graph showing the surface temperature of the brake pads at the end of each braking cycle for each test specimen is presented. It can be seen that specimen V5 has the lowest final surface temperature, approximately 100°C lower than specimen V1 (the reference specimen).

[0296] In addition, accelerated corrosion tests were conducted on the friction materials. The test conditions were as follows: 22 hours in an oven at 400°C. In a 5% NaCl salt solution for 2 hours (thermal shock) Store in a refrigerator at -5°C for 6 hours. Repeat each cycle 10 times.

[0297] Figure 80 Photographs of samples V1, V6, and V8 after three accelerated corrosion test cycles are shown. It can be seen that samples V6 and V8, with added nanoparticles, exhibit better corrosion resistance than the reference sample V1.

[0298] at last, Figure 81 The graph shows the Gogan C hardness and cold compressibility (5 MPa, whole pad) of the friction material containing niobium pentoxide nanoparticles in phenolic resin.

[0299] Figure 81 The following conclusions were drawn: the diluted resins (V2 and V6) increased the hardness and compressibility of the material (reduced the stiffness of the bulk) and increased the porosity of the material.

[0300] Not wishing to be confined to theory, it can be understood that the varying improvements in composite material properties resulting from a simple reduction in particle size (i.e., the so-called "scale effect") are generally attributed to the surface energy effect, since for particles of the same mass, the specific surface area increases directly with decreasing size. On the other hand, what has been overlooked until now is the rapid increase in the number of smaller particles obtained, and the potential correlation between a large number of particles and the resulting properties. In this respect, those skilled in the art would consider that the effect of very small numbers of particles might be negligible in practice, but current results unexpectedly show that a very large number of particles (even with a small total mass) can (i) significantly alter the properties of the material; or (ii) cause significant difficulties in processing and dispersion, thereby disrupting the delicate balance between optimal performance and economic feasibility. Given a particle size and mean free path between the nearest particles, the importance of considering the number of particles required to achieve the maximum gain in desired performance should be emphasized.

[0301] Not wanting to be confined to theory, it is understandable that the same positive correlation is observed between mean free path and particle number, and between mean free path and particle size, in both ultimate tensile strength and storage modulus, indicating that the degree of texture in the matrix surrounding the particles increases with increasing particle size. However, the dependence of stiffness on particle number is opposite to that of strength, suggesting that if the mean free path decreases (due to a larger number of particles in the polymer matrix), the expected forced orientation of the polymer chains will obviously be more prone to slippage, resulting in a composite material that is more flexible but also stronger.

[0302] Example 23 – Paste or film-like premix containing niobium pentoxide nanoparticles and its use in metal welding applications In this embodiment, various paste-like premixes were prepared using different polymers (including polyethylene glycol (PEG), polypropylene glycol (PPG) of different molecular weights, alkyl sulfonate phenyl ester, or butyl ethylene glycol), all of which used niobium pentoxide nanoparticles obtained according to the method described in this patent application (i.e., high-energy milling).

[0303] In one embodiment, a PEG 6000-containing premix is ​​prepared by mixing 50% (by weight) IPA (isopropanol), 30% PEG 6000, and 20% Nb₂O₅. The preparation process involves weighing the PEG and alcohol, stirring under gentle heating (≥70°C) until they dissolve, then adding Nb₂O₅ nanoparticles, and continuing stirring under heating for 10 minutes. Subsequently, the resulting material is heated in an oven at 100°C for 15 minutes until a film forms. The resulting premix is ​​a film that can be used directly as is, or it can be scraped off and used in powder or fragment form.

[0304] In another embodiment, a butyl glycol-containing premix is ​​prepared by mixing 65% (by weight) butyl glycol and 35% Nb₂O₅. The preparation involves weighing the materials, stirring the butyl glycol, and then adding Nb₂O₅ nanoparticles. The resulting material is then heated in an oven at 100°C until a paste is formed.

[0305] In another embodiment, a premix containing alkyl sulfonate is prepared by mixing 51% (by weight) of alkyl sulfonate and 49% of Nb₂O₅. The preparation involves weighing the material, stirring the alkyl sulfonate, and then adding Nb₂O₅ nanoparticles. In this case, dispersion is performed mechanically using a Cowles disperser or a basic mixer. The resulting material is then heated in an oven at 100°C until a paste is formed.

[0306] A butyl ethylene glycol paste premix, as described above, is applied to a region of a steel metal part, and then welding is performed directly on the region containing the applied premix. In this embodiment of the invention, the premix carrier is "sacrificial" because it vaporizes during welding, while the nanoparticles are incorporated into the metal alloy formed during the welding process. The resulting welded metal part exhibits improved properties: in addition to improved microstructure due to reduced vacancies (resulting in a microstructure containing less initial Widmanstätten ferrite, etc.), particularly better toughness, mechanical strength, heat dissipation (HAZ reduction), and more consistent hardness. This novel method of incorporating nanoparticles into welding materials simply by pre-applying a paste to the area to be welded is unexpected for those skilled in the art and solves several technical challenges, such as: enabling better welding processes without changing other materials used; the paste form of the premix ensures proper application; adjusting the concentration of nanoparticles in the premix according to the amount of nanoparticles required for welding; and other technical advantages.

[0307] Those skilled in the art will understand the knowledge disclosed herein and will be able to reproduce the invention with the disclosed embodiments as well as other variations and alternatives, all of which are included within the scope of the appended claims.

Claims

1. A functional premix, characterized in that, It comprises: a solid, semi-solid, paste, or liquid carrier or compatibilizer; and 0.0001 to 50% by weight of nanoparticle filler, said nanoparticles having a defined particle size and a defined chemical composition.

2. The premix according to claim 1, characterized in that, The carrier or compatibilizer is selected from polymers, ceramics, metals, or combinations thereof.

3. The premix according to claim 2, characterized in that, The polymer material is selected from: diols, polyols, adhesives / plasticizers such as alkyl sulfonates, elastomers, rubber, 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. The premix according to claim 3, characterized in that, The diol or polyol is selected from: alkyl glycols, alkylene glycols, polyalkylene glycols, ethylene glycol, propylene glycol, butyl ethylene glycol, polyethylene glycol, polypropylene glycol, or combinations thereof.

5. The premix according to any one of claims 1-4, characterized in that, The nanoparticles are nanoparticles of metals, transition metals, non-metals, oxides, ceramic oxides, rare earth elements, or combinations thereof.

6. The premix according to claim 5, characterized in that, The nanoparticles are materials containing niobium, titanium, tantalum, their oxides, hydrates, carbides, oxalates, graphene, graphene oxide, or combinations thereof.

7. The premix according to claim 6, characterized in that, The nanoparticles are niobium pentoxide, niobium oxalate, niobic acid, FeNb, titanium dioxide, tantalum pentoxide, or a combination thereof.

8. The premix according to any one of claims 5-7, characterized in that, The size of the nanoparticles is less than 750 nm, preferably less than 500 nm.

9. The premix according to claim 8, characterized in that, The crystallinity of the nanoparticle filler is less than 81% or the amorphization is at least 19%.

10. The premix according to claim 9, characterized in that, The nanoparticle filler comprises: (i) a crystallinity of less than 61%, preferably less than 45%, and more preferably less than 30%; or (ii) an amorphization of at least 39%, preferably at least 55%, and more preferably at least 70%.

11. A method for obtaining the functional premix as described in claim 1, characterized in that... The method includes the following steps: - Incorporating 0.0001 to 50% by weight of nanoparticles of metals, transition metals, nonmetals, oxides, ceramic oxides, rare earth elements, or combinations thereof into a carrier or compatibilizer selected from polymers, ceramics, metallic materials, or combinations thereof; and - Homogenize until a solid, semi-solid, or paste-like premix is ​​obtained.

12. A method for modifying materials, characterized in that, The method includes one or more steps in a processing step of adding the functional premix as described in claim 1 to a metal, ceramic, polymer material, or a combination thereof.

13. A material with altered properties, characterized in that, The material is obtained by the method of claim 12.

14. The material as claimed in claim 13, characterized in that, It contains nanoparticle concentrations ranging from 1 to 500 ppm.

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