WO2023023836A1 - Preparado de nanopartículas de tântalo, processo de obtenção de nanopartículas de tântalo e uso do preparado de nanopartículas de tântalo - Google Patents
Preparado de nanopartículas de tântalo, processo de obtenção de nanopartículas de tântalo e uso do preparado de nanopartículas de tântalo Download PDFInfo
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- WO2023023836A1 WO2023023836A1 PCT/BR2022/050337 BR2022050337W WO2023023836A1 WO 2023023836 A1 WO2023023836 A1 WO 2023023836A1 BR 2022050337 W BR2022050337 W BR 2022050337W WO 2023023836 A1 WO2023023836 A1 WO 2023023836A1
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- tantalum
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 82
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052715 tantalum Inorganic materials 0.000 title claims abstract description 64
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 238000000034 method Methods 0.000 claims abstract description 63
- 230000008569 process Effects 0.000 claims abstract description 54
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims abstract description 31
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000002245 particle Substances 0.000 claims description 103
- 238000009826 distribution Methods 0.000 claims description 23
- 238000000227 grinding Methods 0.000 claims description 22
- 239000000725 suspension Substances 0.000 claims description 21
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 14
- 239000000919 ceramic Substances 0.000 claims description 9
- 239000004094 surface-active agent Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 5
- 239000011521 glass Substances 0.000 claims description 5
- 230000006641 stabilisation Effects 0.000 claims description 5
- 238000011105 stabilization Methods 0.000 claims description 5
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 5
- 229910000831 Steel Inorganic materials 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 238000004146 energy storage Methods 0.000 claims description 4
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 4
- 239000010959 steel Substances 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 3
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002241 glass-ceramic Substances 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000011800 void material Substances 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- 238000011109 contamination Methods 0.000 abstract description 4
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000011707 mineral Substances 0.000 abstract description 2
- 238000003917 TEM image Methods 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 238000003801 milling Methods 0.000 description 7
- 230000001186 cumulative effect Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 230000000877 morphologic effect Effects 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004611 spectroscopical analysis Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 229910001936 tantalum oxide Inorganic materials 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001033 granulometry Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000000 metal hydroxide Inorganic materials 0.000 description 2
- 150000004692 metal hydroxides Chemical class 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- 229910001233 yttria-stabilized zirconia Inorganic materials 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- PGHQEOHSIGPJOC-UHFFFAOYSA-N [Fe].[Ta] Chemical compound [Fe].[Ta] PGHQEOHSIGPJOC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000007563 acoustic spectroscopy Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000005829 chemical entities Chemical class 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000039 congener Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010316 high energy milling Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000013035 low temperature curing Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000007734 materials engineering Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- -1 metallic tantalum Chemical compound 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- ZYTNDGXGVOZJBT-UHFFFAOYSA-N niobium Chemical compound [Nb].[Nb].[Nb] ZYTNDGXGVOZJBT-UHFFFAOYSA-N 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- VDRDGQXTSLSKKY-UHFFFAOYSA-K ruthenium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ru+3] VDRDGQXTSLSKKY-UHFFFAOYSA-K 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 230000035899 viability Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B02—CRUSHING, PULVERISING, OR DISINTEGRATING; PREPARATORY TREATMENT OF GRAIN FOR MILLING
- B02C—CRUSHING, PULVERISING, OR DISINTEGRATING IN GENERAL; MILLING GRAIN
- B02C7/00—Crushing or disintegrating by disc mills
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G35/00—Compounds of tantalum
Definitions
- the present invention lies in the field of materials engineering and nanotechnology. More specifically, the invention describes a preparation of tantalum nanoparticles, its use, and a process for obtaining it by comminution, that is, a top-down process.
- the invention provides high purity tantalum pentoxide nanoparticles in large quantity.
- the preparation of nanoparticles of the invention solves these and other problems and has peculiar composition, purity, granulometric profile and specific surface area, being useful in a variety of applications.
- the invention also reveals a process for obtaining nanoparticles of mineral species containing Tantalum, through controlled comminution and without chemical reactions or contamination with reagents typical of the synthesis of nanoparticles.
- the present invention in sharp contrast to the state of the art, provides for the large-scale production of tantalum pentoxide nanoparticles with high purity, determined granulometric profile and very high specific surface area, enabling its use in practice in several industrial applications.
- Preparations of tantalum particles may eventually contain small fractions of nanoparticles, but the predominance of much larger particles, in the range of micrometers/microns, prevents the characterization of such preparations as real preparations of nanoparticles.
- the behavior of materials at the nanoscale changes substantially and therefore, the availability on a large scale and with high purity of a preparation containing tantalum particles predominantly or entirely in the nanometer range and with high purity is highly desirable, without contamination typical of synthesis processes.
- the present invention solves these and other technical problems.
- the literature includes examples of methods of synthesis of nanoparticles containing tantalum, in processes called bottom up.
- processes involve chemical reactions, reagents and products, so that the product obtained normally contains a lot of contamination with residues of inputs or reaction by-products.
- nanoparticles obtained by bottom up processes are limited to certain chemical species that are reaction products.
- these processes are not technically and/or economically viable on large scales, which are some of the reasons why no preparation of tantalum nanoparticles that is stable, pure and with a predominantly or predominantly granulometric distribution is available on an industrial scale. entirely in the nanometer range.
- the present invention solves these and other technical problems.
- the methods of grinding/comminuting/pulverizing transition metals usually aim to increase the specific surface area and enable various industrial uses.
- the known methods are limited to obtaining particles with granulometry in the micrometer range, not being known to the present inventors until the date of filing of this patent application milling methods that provide preparations entirely containing nanoparticles.
- Tantalum has a higher dielectric constant than some other transition metals, which makes it a very useful material in electronic components, such as capacitors for example.
- obtaining predominantly or entirely nanometric particles of tantalum and tantalum pentoxide by milling (top down process) was a challenge considered technically impossible, having been the object of unsuccessful attempts.
- the present invention solves these and other technical problems.
- the document Jamkhande et al. (2019) provides a general review on metal nanoparticle preparation methods. Among other techniques, the document Jamkhande et al. (2019) cites top-down approaches with mechanical fragmentation of particles, which can be performed in mills containing spheres. Jamkhande et al. (2019) also cites low-energy and high-energy milling. Jamkhande et al. (2019) does not reveal specific parameters of the cited processes, making only a review of existing techniques. Much less reveals a preparation of tantalum pentoxide nanoparticles.
- Document CN1 12456556 discloses tantalum oxide nanospheres with particle size in the range of 300-400 nm in diameter, uniform granularity and good dispersion. However, document CN1 12456556 addresses a “bottom-up” type process which is opposite to the process defined in the present patent application and, additionally, document CN1 12456556 does not disclose a preparation of tantalum pentoxide nanoparticles as defined in the present invention.
- the nanoparticles disclosed in said document are of a metal chalcogenide containing Sulphur, Selenium, Tellurium or Oxygen and a polymer selected among several types of polymers, including acrylates, acids, halides or esters, and are intended to be used as a lubricant. It does not disclose a preparation of tantalum pentoxide nanoparticles like the present invention.
- US patent application US2007185242A1 filed by Huang Yuhong and abandoned, discloses a low temperature curing ink comprising nanometer metal hydroxide.
- the focus of said document is the composition for coating an electrode or a capacitor.
- the composition comprises submicrometer particles obtained by mechanochemical process, using ruthenium hydroxide nanoparticles.
- metal hydroxide nanoparticles are manufactured by reacting a metal chloride with sodium hydroxide in water. It does not disclose a preparation of tantalum pentoxide nanoparticles like the present invention.
- a mill is used in which a metallic powder is comminuted together with ceramic nanoparticles to generate a metal-ceramic composite.
- the mill balls and its interior are ceramic. It does not disclose a preparation of tantalum pentoxide nanoparticles like the present invention.
- the present invention solves several problems of the state of the art related to tantalum preparations with predominantly or integrally nanometric granulometry.
- nanoparticles of the invention is useful in several applications, including: the modulation or improvement of the mechanical properties of steels, metallic and non-metallic alloys, ceramics and/or polymers; the doping of materials to modulate electromagnetic properties for use in electronic components, battery cells, energy storage systems, solar panels, sensors and piezoelectric actuators; the modulation of optical properties of glasses or other transparent or translucent materials; use as a component of catalysts; in the preparation of stable liquid/colloidal compositions.
- the process of obtaining tantalum nanoparticles comprises the steps of:
- comminutor equipment selected among: high energy mill, steammill and jetmill;
- the stabilization of the colloidal suspension to be placed in the grinding chamber of the high energy mill referred to above is selected from: adjusting the pH of the polar liquid medium to the range between 2 to 13, and optionally adding surfactants ; or the addition of surfactants in an apolar liquid medium.
- the process for obtaining tantalum nanoparticles includes grinding in a high-energy mill operating with spheres of special materials, such as zirconia, zirconia stabilized with yttria, zirconia stabilized with niobium pentoxide, or combinations thereof, through the adjustment of specific parameters.
- the process of obtaining tantalum nanoparticles includes milling in a jet mill with superheated steam, superheated steam or steammill, by adjusting specific parameters.
- Figure 1 shows the particle size distribution of an embodiment of tantalum pentoxide nanoparticle preparation of the invention, showing the granulometric profile obtained in an electroacoustic spectrometer model DT1202 from Dispersion Technology Inc. Shown are: the granulometric distribution or equivalent diameter on the volumetric base of the particles in micrometers (horizontal axis), the relative fraction of the nanoparticles (vertical axis on the left) and cumulative fraction (vertical axis on the right).
- Figure 2 shows cumulative particle size distributions (DTP) obtained by electroacoustic spectrometry for Ta2Ü5 milled for 12 hours.
- Figure 3 shows differential particle size distributions (DTP) obtained by electroacoustic spectrometry for Ta2Ü5 ground for 12 hours.
- Figure 4 shows a brightfield TEM image at 20,000X magnification showing tantalum nanoparticles from sample 1 (Ta 12h - raw).
- Figure 5 shows brightfield TEM images named A, B and C with 100,000X magnification showing tantalum nanoparticles from sample 1 (Ta 12h - raw).
- Figure 6 shows brightfield TEM images labeled A, B and C with 200,000X magnification showing tantalum nanoparticles from sample 1 (Ta 12h - raw).
- Figure 7 shows brightfield TEM images at 100,000X magnification showing tantalum nanoparticles from sample 1 (Ta 12h - raw) and, respectively, next to each image, another image illustrating the identification process, counting and measuring.
- Figure 8 shows a histogram resulting from the morphological analysis that illustrates the particle size distribution of sample 1 (Ta 12h - raw).
- Figure 9 shows a brightfield TEM image at 20,000X magnification showing tantalum nanoparticles from sample 2 (Ta 12h - Centrifuged Supernatant).
- Figure 10 shows brightfield TEM images named A, B and C with 100,000X magnification showing tantalum nanoparticles from sample 2 (Ta 12h - Centrifuged Supernatant).
- Figure 1 1 shows brightfield TEM images named A, B and C with 200,000X magnification showing tantalum nanoparticles from sample 2 (Ta 12h - Centrifuged Supernatant).
- Figure 12 shows brightfield TEM images at 100,000X magnification showing tantalum nanoparticles from sample 2 (Ta 12h - Centrifuged Supernatant) and, respectively, next to each image, another image illustrating the identification process , counting and measuring.
- Figure 13 shows a histogram resulting from the morphological analysis that illustrates the particle size distribution of sample 2 (Ta 12h - Centrifuged Supernatant).
- the present invention solves several problems of the state of the art and provides a preparation of tantalum nanoparticles that concomitantly contemplates the following technical characteristics: particles predominantly or entirely in the granulometric range of nanometers; high purity; an industrial-scale process that enables supply and use on an economic scale. Said preparation can also be called tantalum nanoparticle preparation.
- tantalum particles covers various chemical entities containing tantalum, including metallic tantalum, oxides, hydrates, hydrides, carbides, or nitrides of tantalum, tantalum iron or tantalum bound to other metals or transition metals , or combinations thereof. It also includes tantalum pentoxide.
- nanoparticles described above wherein said particles have a size in the range of 10 to 492 nanometers (nm). In one embodiment, said nanoparticles have an average size of 89.5nm.
- nanoparticles described above wherein said particles have a size in the range of 10 to 339 nanometers (nm). In one embodiment, said nanoparticles have an average size of 79.44nm.
- the particle size distribution is: d10 between 83 and 97nm; d50 between 342 and 455nm; d90 between 1402 and 2127nm; or d99 between 5755 and 9938nm.
- the particle size distribution is such that d10 is 89nm.
- the particle size distribution is such that d50 is 391 nm.
- the particle size distribution is such that d90 is 1720nm.
- the particle size distribution is such that d99 is 7580nm.
- the specific surface area of the particle is: d10 between 7.54 and 8.82 m 2 .g -1 ; d50 between 1.61 and 2.14 m 2 .g' 1 ; d90 between 0.34 and 0.52 m 2 .g -1 ; or d99 between 0.07 and 0.13 m 2 .g' 1 .
- the particle specific surface area is such that d10 is 8.22 m 2 .g' 1 .
- the particle specific surface area is such that d50 is 1.87 m 2 .g' 1 .
- the specific surface area distribution is such that d90 is 0.43 m 2 .g' 1 .
- the particle specific surface area is such that d99 is 0.10 m 2 .g 1 .
- nanoparticle preparation for the preparation of: stable colloidal compositions; steels, metallic and non-metallic alloys, ceramics and/or polymers; electronic components, battery cells, energy storage systems, piezoelectric sensors and actuators, solar panels; glass, glass ceramics or other transparent and translucent materials; catalysts.
- comminutor equipment selected among: high energy mill, steammill and jetmill;
- Process as described above in which the stabilization of the colloidal suspension to be placed in the grinding chamber of the high-energy mill is selected from: adjusting the pH of the polar liquid medium to the range between 2 to 13, and optionally adding surfactants ; or the addition of surfactants in an apolar liquid medium.
- the high-energy mill is of the agitated medium type and said spheres are selected from: zirconia, silicon carbide, alumina, said spheres optionally being stabilized with yttria or niobium pentoxide, or combinations of the same.
- Process as described above comprising a step in a jet mill with superheated fluid or Steammill, with adjustment of the speed of the air classifier between 1,000 and 25,000rpm, preferably between 5,000 and 25,000rpm, more preferably between 10,000 and 25,000rpm, even more preferably between 15,000 and 25,000rpm, even more preferably between 20,000 and 25,000rpm; adjusting the pressure of the compressed steam between 10 and 100 bar, preferably between 20 and 90 bar, more preferably between 30 and 80 bar, even more preferably between 40 and 70 bar, even more preferably between 45 and 60 bar; and temperature between 230 and 360°C, preferably between 240 and 340°C, more preferably between 250 and 320°C, even more preferably between 260 and 300°C, even more preferably between 270 and 290°C.
- Process as described above comprising a step in a jet mill or Jetmill, with adjustment of the aeroclassifier rotation between 1,000 and 25,000rpm, preferably between 5,000 and 25,000rpm, more preferably between 10,000 and 25,000rpm, even more preferably between 15,000 and 25,000rpm, even more preferably between 20,000 and 25,000rpm; adjusting the compressed air pressure between 1 and 50 bar, preferably between 1 and 40 bar, more preferably between 2 and 30 bar, even more preferably between 3 and 20 bar, even more preferably between 4 and 10 bar; and temperature less than 40 °C [0070] In one embodiment, a preparation of tantalum pentoxide nanoparticles with purity equal to or greater than 99% is provided.
- the tantalum nanoparticle preparation of the present invention has a particle size between 50 to 1000 nanometers.
- the preparation of nanoparticles of the invention comprises particles with defined granulometric fractions, for example, a preparation with particles integrally between 50 and 800nm, and preparations with particles in intermediate values and with granulometric fractions of defined value.
- the distribution of particle size fractions is defined by d10, d50, d90 and occasionally d99, notations that reflect the accumulated % volume of particles corresponding to each notation, d10 referring to 10% of the particles volume, d50 to 50% of the volume and so on.
- the invention provides a preparation of tantalum particles in the granulometric range below 100 nanometers.
- the preparation of nanoparticles of the invention is useful in several applications, including: the preparation of stable colloidal suspensions; modulation or improvement of the mechanical properties of steels, metallic and non-metallic alloys, ceramics and/or polymers; the doping of materials to modulate electromagnetic properties for use in electronic components, battery cells, energy storage systems, solar panels, sensors and piezoelectric actuators; the modulation of optical properties of glasses or other transparent materials; use as a component of catalysts.
- the use of the preparation of nanoparticles of the invention provided the obtainment of liquid compositions or stable colloidal suspensions, in which the nanoparticles remain in suspension for a long time, providing a long shelf life.
- the process for obtaining tantalum nanoparticles differs from other congeners because it is a top-down process, without chemical reactions or mechanochemistry.
- the fact that pure or high-purity tantalum particles are used for comminution makes it possible to obtain high-purity nanoparticle preparations, since the process does not add impurities or lead to the formation of reaction products, as is the case with processes bottom up, synthesis or state-of-the-art mechanochemicals.
- the process involves wet milling in a high-energy mill and makes it possible on an industrial scale to obtain tantalum pentoxide particles predominantly or entirely in the granulometric range of nanometers.
- the stabilization of the colloidal suspension to be placed in the grinding chamber of the high-energy mill is a very important step, being selected among: the adjustment of the pH of the polar liquid medium for the range between 2 to 13, and optionally adding surfactants; or the addition of surfactants in an apolar liquid medium.
- a mill known from the state of technique such as, for example, a high-energy mill with yttria-stabilized zirconia beads (ZrÜ2 + Y2O3), by adjusting specific parameters, including rotation time, pH and temperature.
- the grinding media includes zirconia balls, ZTA (alumina or yttrium-reinforced zirconia), and alumina.
- zirconia spheres stabilized with 5% m/m yttria are used.
- the process involves comminution by a jet mill with superheated steam (steammill), to which particles smaller than 40 microns are fed, the air classifier rotation being adjusted between 1,000 and 25,000rpm, the steam pressure compressed between 10 and 100 bar, and the temperature between 230 and 360°C.
- steammill superheated steam
- Example 1 Wet grinding process of tantalum pentoxide in high energy mill
- the preparation of tantalum pentoxide nanoparticles was obtained by milling with adjustment of parameters that include rotation speed, pH, temperature.
- the grinding conditions of the referred material, to obtain the tantalum pentoxide nanoparticle powder included: rotation speeds between 1000 and 4500 rpm, temperatures below 40 s C maintained with the aid of a forced cooling system external to the referred mill. After 30 to 120 minutes of operation under these conditions, a powder preparation containing tantalum nanoparticles was obtained.
- Example 2 Particle size measurement
- the particle size distribution was measured by the electroacoustic spectroscopy method, using the DT1202 brand Dispersion Technology Inc. As shown in figure 1, the preparation of tantalum nanoparticles of the invention has a granulometric distribution integrally in the range of nanoparticles.
- Figure 1 shows the particle size distribution or equivalent diameter of the particles in nanometers (horizontal axis), the relative fraction of the nanoparticles (left vertical axis) and cumulative fraction (right vertical axis).
- Figure 1 shows that the tantalum nanoparticles of this embodiment of the invention have an equivalent diameter between 60 and 1000 nanometers (nm), with 99% between 60 and 776 nm, 90% between 60 and 480 nm, 50% between 60 and 275 nm, 10% between 60 and 157nm. Table 1 shows the average diameters obtained in each fraction:
- Example 3 Stable colloidal suspension - Stability test of tantalum particles as a function of pH and in aqueous solution
- the nanoparticle preparation obtained according to example 1 was used to obtain a stable colloidal suspension and stabilization tests as a function of pH were performed.
- the stability of tantalum nanoparticles is dependent on the pH of the medium, and at pH between 3 and 5 the particles reached its greatest instability.
- Pre-comminution can be done with any conventional grinding technique known to those skilled in the art (non-limiting examples: ball mill with micrometric balls (5-10 micrometers), disk mill, high energy mill or Jetmill).
- a jet mill or jetmill was used to pre-comminute the tantalum pentoxide particles, in order to improve the performance of the subsequent comminution process until the integral particle size distribution (d99) below 40 micrometers , preferably in the nanometer range.
- TazOs particles smaller than 40 micrometers were fed to a steammill.
- the rotation of the air classifier was adjusted to 20,000 rpm and the compressed steam pressure to 50 bar.
- the temperature of the superheated fluid was 280 °C.
- Jetmill was used to comminute the particles of Ta2Ü5 to granulometric ranges in which d99 was in the range of less than one micrometer.
- the comminution conditions tested on a jetmill are summarized in Table 3.
- Example 7 Measurement of particle size and surface area
- Example 8 Morphological, structural and statistical analysis of particles using transmission electron microscopy (TEM)
- the analyzed samples are suspensions containing tantalum oxide nanoparticles that were subjected to a period of 12 hours of milling, sample 1 being the crude homogeneous suspension and sample 2 being the supernatant resulting from the separation by centrifugation.
- Figures 4, 5 and 6 show the morphology of the sample 1 particles.
- Figure 7 shows the process of identification, counting and measurement from the TEM images of sample 1. The morphological analysis of sample 1 generated the results illustrated below in table 8 and in the histogram of figure 8.
- Figures 9, 10 and 11 show the morphology of the particles in sample 2.
- Figure 12 shows the process of identification, counting and measurement from the TEM images of sample 2.
- the morphological analysis of sample 2 generated the results illustrated below in table 8 and in the histogram of figure 13.
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IL310916A IL310916A (en) | 2021-08-27 | 2022-08-26 | Tantalum nanoparticle preparation, process for obtaining tantalum nanoparticles and use of tantalum nanoparticle preparation |
CN202280057892.1A CN117858848A (zh) | 2021-08-27 | 2022-08-26 | 钽纳米颗粒制剂、获得钽纳米颗粒的方法以及钽纳米颗粒制剂的用途 |
KR1020247006798A KR20240055740A (ko) | 2021-08-27 | 2022-08-26 | 탄탈륨 나노입자 제조물, 탄탈륨 나노입자를 얻기 위한 프로세스 및 탄탈륨 나노입자 제조물의 용도 |
CA3229928A CA3229928A1 (en) | 2021-08-27 | 2022-08-26 | Tantalum nanoparticle preparation, process for obtaining tantalum nanoparticles and use of tantalum nanoparticle preparation |
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