Patent Grant
11103923
The present invention relates to the composition of nanoparticles upon which stability against oxidation is dramatically improved, and, more specifically, a composition and microstructure of nanomaterial that consists of a radial composition change or alloy gradient that can be tuned to facilitate controlled atom diffusion, oxide growth, size and shape change, and reactivity.
Controlling the oxidation of metal surfaces is of as great importance today as it was a half century ago when discoveries related to oxidation theory, diffusion rates, and phase diagrams led to advances in super alloys, shape memory alloys, and stainless steels. Today, research at the interface of metals and metal oxide focuses on technologically important thin-films, and at the optimization of nanoscale parameters at which the metal oxide growth occurs. This is especially true for transition metal nanoparticles, where the bulk of research focuses solely on metal oxides. This is due primarily due to the ease upon which transition metals oxidize, which is even truer for nanoscale metals. Thus one technological hurdle that must be overcome is developing new compositions of nanoparticles that have some intrinsic ability to resist oxidation designed into their synthesis. If such a nanoparticle was available today, great advances in thin-film technology, magnetic fluids, magnetic imaging, and corrosion resistive remediation would be possible. The art described herein pertains to a discovered nanoparticle that has a radial composition gradient (a composition change as a function of distance from the center of the nanoparticle outward) variation that takes advantage of alloy properties and subsequent variations in oxidation tendencies. That is to say, the intricate differences in self-diffusion rates between metals, and the oxidation rates in those metals, is used as a synthetic tool to create the novel compositions and gradients. The oxidation of a metal surface is well-understood using Cabrera-Mott (CM) theory, and at times. Take for example self-diffusion in metallic iron (α-Fe), metallic chromium (α-Cr), and metallic nickel (Ni), see
The present invention comprises a novel composition of nanoparticle that consists of a radial composition gradient of multiple; metals, alloys, voids, oxides, or non-metals. The gradients consist of transition metals and oxides, however it is understood that additional noble metals, semiconductors, or ionic lattices could be used. In the present embodiment, the gradient is iron rich at the center, where the iron is in it's zero-oxidation state (i.e., metallic iron), and composition can change gradually from nickel in it's zero-oxidation state (i.e., metallic), to chromium, in it's zero-oxidation state (i.e. metallic), or vice-versa, or combined with additional metals, like cobalt, vanadium, manganese, tungsten, or any other suitable metal. Moreover, the gradient can also consist of mixtures of chromium and nickel in zero-oxidation states (i.e. metallic alloys), which can be combined with additional metals, like cobalt, vanadium, manganese, tungsten, or any other suitable metal. In addition, chalcogens may be introduced in the form of an oxygen anion (i.e., O2−), or sulfur anions (i.e., S2−) throughout the lattices where required, in the form of an oxide or sulfide. Finally, the nanoparticle gradient can be terminated with concentric domains of noble metals, like gold, silver, palladium, or platinum, or in segregated (phase separated) domains. With these compositions, the invention leads to nanoparticles with transformational performance improvements, such as in oxidation resistance, where stainless like properties and a long-term retention of the nanoscale metallic properties are preserved. Once such example is the nanoparticle's magnetism. The composition gradients described have magnetic properties that result from metallic ferromagnetic properties that result from the materials retaining a high percentage of metallic character, and not the properties characteristic of complete metal oxides of nanoparticles.
Controlling the oxidation of metal surfaces is of as great importance today as it was a half century ago when discoveries related to oxidation theory, diffusion rates, and phase diagrams led to advances in super alloys, shape memory alloys, and stainless steels. Today, research at the interface of metals and metal oxide focuses on technologically important thin-films, and at the optimization of nanoscale metal properties and performance. This is especially true for transition metal nanoparticles. While transition metals at the bulk scale can be forged and alloyed in high temperature furnaces to ensure alloying and oxidation control, one area of modern importance and that is under explored is the use of oxidation, and the intricate differences in diffusion rates between transition metals and their oxides, as a synthetic tool to manipulate nanoscale performance. The oxidation of a metal surface is well-understood using Cabrera-Mott (CM) theory, and at times, the results can be surprising to the colloidal synthetic chemist. Take for example self-diffusion in iron (α-Fe), chromium (α-Cr), and nickel (Ni). Iron atoms self-diffuse rapidly in a b.c.c. lattice, but diffuse slower in Ni and Cr, with diffusion in Cr being many orders of magnitude slower. Nickel atoms however self-diffuse in a f.c.c. Ni-lattice at modest rates in both Fe and Cr. Chromium on the other hand, has a slow self-diffusion rate, but diffuses orders of magnitude faster in both Fe and Ni. Interestingly, when a surface is oxidized, such diffusion can increase, as in the case of Fe in Fe2O3, or decrease, in the case of Ni in NiO. Moreover, oxidation rates depend highly on oxide thickness and type, where O2− anions diffuse slow in NiO and Cr2O3 oxides, but rapidly in Fe3O4, for instance. Thus, compositions of interfaces with mixed metals, oxide types, and oxides thickness can govern the flow of atoms and oxide growth, which at the nanoscale, can lead to novel behavior. This divergent diffusion trends and the ability to tailor it also leads to Kirkendall effects playing a major role at nano interfaces, particularly during oxidation. This results not only in oxidation, but often in voids being formed within the nanoparticles as a result of atom diffusion. Thus, to a synthetic materials chemist, the careful choosing of material combinations and oxidation control can lead to tuning the reaction conditions (ligand environment, oxygen pressure, annealing temperature, etc.), and thus, lead to new NP morphologies and microstructures.
The present invention involves the control of oxidation behavior at the nanoscale in order to preserve the magnetic properties of the material and also the materials ability to resist oxidation (it's stainless behavior). To achieve this, the present invention includes a “gradient nanoparticle”, where the composition of the nanoparticle changes from the center radially outward to the interface. By controlling the composition along the gradient, which includes both the metal type, but also its concentration, the present invention can improve the materials performance.
As discussed above, the multi-metallic alloy nanoparticles (NPs) are an important research topic as a result of the many combinations of metals that result in unique properties that might not resemble the bulk or individual NP counterparts, such as electronic, catalytic, and optical properties. The potential applications of these materials are varied, ranging from sensors to ferro-fluids, as a result of the combination of phases in discreet nanoscale dimensions. Unique properties of bimetallic nanomaterials are achieved depending on the moiety used during preparation. For instance, Fe3O4/Au NPs have the both the magnetic properties of the Fe3O4 and plasmonic properties of the Au, as well as magnetic and catalytic bifunctionality. Alloy NPs, such as FexCo1-x NPs, exhibit unique magnetic properties due to the combination of ferromagnetic Fe and Co. However, challenges arise in the fabrication of bimetallic NPs such as phase segregation, oxidation, and redox reactions. FeNi and FeCr alloy NPs are interesting due to interfacial oxidation and magnetic properties. When synthesized in nano-form, these NPs have attractive properties such as high saturation magnetization, low hysteresis, magnetic phase transition, high magnetic permeability, and corrosion resistance, allowing for potential applications in biomedicine, catalysis, electronics, nano-fluids, and magnetic data storage. Synthesis of FeNi alloy NPs typically involves the simultaneous decomposition of Fe and Ni precursors. Utilizing this method it is typically difficult to control composition and morphology. Oxidation of these particles results in the formation of alloy/ferrites, such as FeNi/NiFe2O4, which may affect the magnetic properties due to the formation of a magnetically dead oxide layer on the surface of the particle. Though classical Cabrera-Mott (CM) oxidation theory has been used to model and understand NP oxidation in monometallic systems, it has not yet been applied to bimetallic or multi-metallic systems, therefore, understanding the oxidation of these bimetallic FeNi NP systems via a theoretical model is of particular interest.
The present invention will be more fully understood and appreciated by reading the following Detailed Description in conjunction with the accompanying drawings, in which:
The present invention involves forming a nanoparticle with a composition that varies radially from the center. In a simple embodiment, consider the formation of a nanoparticle with a metallic iron center (Fe), and increasing concentrations of nickel (Ni), chromium (Cr), alloys of nickel and chromium (NiXCrY), or empty void or hollow regions (denoted as “v”). Such nanoparticles are denoted for simplicity as; Fe—Ni, Fe—Ni—Cr, Fe—Cr—Ni, Fe—CrXNiY, Fe-v-Ni, Fe-v-Cr, Fe-v-Ni-v-Cr, and Fe-v-NiYCrX. A key characteristic of these nanoparticles is that they initiate from, and retain metallic characteristics. For instance, care much be paid to ensure that the Fe center is metallic, and that reduction-oxidation chemistry does not result in electrochemical plating or oxidation of the gradient. While in the present system the materials were prepared under air free conditions, other conditions, chemicals, and treatments should also ensure that these compositions can be prepared.
The change in composition of the gradient nanoparticles, as well as their metallic nature was further confirmed via X-ray photoelectron spectroscopy (XPS). Table 1 shows the respective compositions, and composition changes upon introduction of O2−. For instance, the total Fe-composition was 53.1%, 48.8%, and 31.2% and Ni-composition was 46.9%, 51.2%, and 68.8% for low-, medium-, and high-Fe—Ni gradients respectively, demonstrating the increased Ni-content. Upon introduction of O2− to the gradient, the Fe-composition remained high at 55.3% and 87.4% for low- and medium-gradients, respectively. This suggests the diffusion of Fe atoms outward during oxidation, resulting in the formation of an outer metal oxide layer that is Fe-rich but still contains Ni. Ni composition remains high at 73.3% after oxidation for the thick-Ni—Fe gradient, suggesting that this Ni-gradient composition is required for complete passivation of the Fe-gradient, leading to the improved oxide resistance.
After oxidation (c-d) both Fe2p and Ni2p show a small increase in percentage of higher BE signals, confirming the oxide growth of the NPs. However, of particular interest is the observation of metallic Fe0 being observed (BE≈707 eV) even after extensive oxidation. This observation is increasingly rare in nanoparticle systems constructed with iron, where iron oxides of Fe3O4 or Fe2O3 are observed. Taken together, these results strongly support the importance of the metallic Fe—Ni gradient in the oxide resistance and property performance.
The results above suggest the outward Fe diffusion from the nanoparticle center through the Ni interface during synthesis and oxidation. Given this, additional composition gradients were explored, including tri-metallic system consisting of Fe—Cr—Ni, Fe—Ni—Cr, and Fe—CrxNi1-x nanoparticles of similar dimensions and shapes. In these systems, the importance of the Cr layers is to provide a third diffusion barrier or promoter, which is predicted above to lead to more transformations during alloying or oxidation, whereas the gradients of the CrxNi1-x alloys introduce new barriers for oxide growth.
The tri-metallic gradient nanoparticles were characterized by TEM. The Fe—Cr—Ni gradients showed diameters of d=7.0±3.0 nm before oxidation, and a similar size after oxidation d′=7.6±3.6 nm. The Fe—Ni—Cr had sizes of d=8.7±2.3 nm before and d′=12.3±3.3 nm after oxidation. The Fe—CrxNi1-x had d=11.0±1.8 nm before and d′=10.9±2.0 nm after oxidation.
The tri-metallic compositions and elemental states were characterized by XPS. Fig. X shows the Fe—Cr—Ni gradients (red). Before oxidation, the Fe (a, i) shows metallic character with the presence of 2p3/2 and 2p1/2, BE at 712.02 eV and 726.64 eV, respectively. After O2− introduction, the 2p3/2 BE (d, i) slightly shifts to higher energy to 714.6 eV. The Ni 2p BE before oxidation (b, i) is predominantly metallic at 875.56 eV, with Ni2+ forms at 852.94 eV, and 856.04 eV (2p1/2). After O2− introduction, the 2p3/2 peak (e, i) is shifted to 880.65 eV, and 2p1/2 peaks are shifted to 856.75 eV, 861.91 eV indicating only minimal oxide growth. The Cr 2p signatures have higher BE value and show almost no change prior to (c, i) and after oxidation (f, i) which suggests that the oxidation has occurred. Cr 2p3/2 peaks are observed at 578 eV and 2p1/2 peaks are at 587 eV.
In case of Fe—Ni—Cr gradients (blue), the Fe 2p3/2 peaks before (a, ii) and after (d, ii) O2− introduction are present at 711.56 eV, 716.80 eV and 711.76 eV, and 2p1/2 Peaks are present at 730.12 eV, and 732.33 eV, respectively. Unoxidized Ni BE (b, ii) are at 852.70 eV, 858.66 eV (2p3/2) and 877.74 eV (2p1/2). After oxidation, peaks (e, ii) are shifted to higher energy at, 856.34 eV, 860 eV (2p3/2) and 880.23 eV (2p1/2). High BE values of Cr peaks indicate chromium oxidation. Cr 2p3/2 peaks for unoxidized (c, ii) and oxidized (f, ii) samples are present at 581.32 eV and 577.84 eV, and 2p1/2 peaks are present at 590.56 eV, and 587.55 eV, respectively.
For these NPs, XPS results show oxidation which is in well agreement with the PXRD results. Table 1 lists the elemental compositions of these gradient nanoparticles. In each case, the presence of both nickel and chromium is confirmed, with only the Fe—Ni—Cr showing a considerable increase in nickel content. Post oxidation, the concentrations remain similar except in the Fe—Ni—Cr case, which shows a considerable increase inc chromium concent, suggesting a loss of either nickel or iron as a result of the oxidation step.
The Fe—CrXNi1-x gradients show Fe 2p BE regions with clear energy changes. Before O2− introduction, the Fe 2p regions (a, iii) are broad and spread out while oxidized Fe 2p peaks (d, iii) are localized and are in multiple positions. Ni 2p3/2 peaks before oxidation (b, iii) are present at 853.04 eV and 856.73 eV but after oxidation (e, iii) are shifted to 856.24 eV and 862.27 eV. Ni 2p1/2 peaks before oxidation are present at 872.75 eV and 880.25 eV, but after oxidation are shifted to 875.17 eV and 881.75 eV. Cr peaks as seen in other systems, were present at higher BE values. Importantly, metallic Cr BE characteristics are shown to be present at 576.95 eV, 577.72 eV (2p3/2), and 586.95 eV (2p1/2), indicating that the Fe—CrXNi1-x have metallic Fe, Ni, and Cr.
Taken together, the XPS results of the trimetallic gradients show evidence of the metallic rich nature of the nanoparticles, that oxidation can be tailored by gradient sequence and composition, and that gradients have been discovered with strongly retain the metallic characteristics of the nanoparticle.
Iron oxide nanoparticles have long been studied for their size-tunable magnetic properties, which are known to demonstrate superparamagnetic properties. On the contrary, metallic nanoparticles originating from ferro-magnetic metals may have additional magnetic strength and coercivity (Hc). This area of research is not well known, due to the challenge of preparing nanoparticles with metal states. As shown above, the gradient nanoparticles described herein are strongly metallic, and the magnetic characteristics are described below.
Table 2 shows the magnetic properties of the Fe—Ni gradient nanoparticles as prepared and after oxidation. The gradients are superparamagnetic at low and medium-gradients, wherease the high gradients show ferromagnetic properties due to an increase in Hc from zero (superparamagnetic state) to ˜100 Oe. Also shown are preliminary magnetization saturation values (Ms) listed in raw emu and normalized emu/g values, where g is the mass of the nanoparticles. The systems have some early variations, however the high emu/g values of >120 show the potential for these materials to be used in many magnetic applications. The magnetization hysteresis loops for these samples are shown in
Table 3 shows the corresponding magnetic values for the Fe—Cr—Ni, Fe—Ni—Cr, and Fe—CrNi gradient nanoparticles. Compared to the Fe—Ni gradients, these materials show considerable higher Hc indicating improved ferromagnetic characteristics, moreover, the preliminary emu/g values of 140-156 for the Fe—CrNi gradients show tremendous magnetic properties, and also magnetic stability due to the decreased oxidation tendency of the nanoparticles.
The magnetization hysteresis loops for these samples are shown in
The results above indicate that the gradient nanoparticles have highly responsive oxidation properties at the atomic scale and these were further tested for applicability as a passivation layers for bulk substrates. For this, purified gradient nanoparticles were purified as described and dissolved in hexane. These gradient solutions were then used as the ink or paint like material in spray coating, in which compressed gas is used to propel thin coatings of the nanoparticles onto substrates.
The gradient coated substrates were then tested at high temperatures and in salt-water, and compared to un coated substrates.
The ability of the gradient nanoparticle to protect rare earth magnets from corrosion was also demonstrated.
The high magnetic strengths of the gradient nanoparticle was also used to absorb electromagnetic (EMI) radiation.
In addition to PDMS, the gradient nanoparticles were shown to be excellent candidates to magnetically enhance plastics and composites.
The use of the gradient nanoparticles as magnetic bead supports for life sciences applications was studied. Owing to the tunable nanometer diameters, and the favorable magnetic properties (high magnetic susceptibility, superparamagnetic, etc.), gradient nanoparticles are excellent candidates for life sciences, considering the lack of commercially available nano-sized beads with such properties.
As a proof of principle, when the gradient nanoparticles were processed as magnetic beads as described above, they were found to collect short strands of ssDNA.
Thus, the present invention involves the tuning of the nanoparticles to achieve particular characteristics. As explained herein, the step of tuning the nanoparticles gradient composition and concentration can involve annealing a metallic center of at least one metal in the presence of an interface with at least one second metal, annealing a metallic center of at least one metal in the presence of an interface with at least one second metal whose interface thickness is 0.5-100 nanometers. The particle can range in size from 5-500 nanometers, and exist as any shape or morphology. In the present invention the annealing described is thermal, where the nanoparticle is heated to temperatures of 50-500° C. This annealing of the nanoparticle can be carried out at constant temperatures for extended periods of times, and also employ thermal cycling during the annealing of the nanoparticle, where low, high, and varied temperature ramps are employed. It is envisaged that additional annealing techniques could also be employed, such as microwave irradiation, ultrasonic vibrations, ultraviolet, visible, and near infrared laser light, magnetic fields, as well as radiation. Moreover, the environment the nanoparticle is exposed to during annealing can also be varied to tune the gradient, such as changes to pressures, gas types, oxygen partial pressures, vacuum levels, solvent type, and humidity.
Taken together, these results show that nanoparticles with composition gradients can be used to alter nanoparticle oxidation characteristics, morphology/microstructure change, and magnetic performance of materials. The gradients can be varied to allow for purposed gradients for specific applications in fields ranging from corrosion, magnetics, information technology, imaging, electromagnetic absorption, coating technologies, and immunoprecipitation. The simple proof of principle examples shown herein can be easily expanded upon to expand into many areas of industry, technology, and life sciences in the future.
Crystalline b.c.c. Fe nanoparticles were used. The metallic Fe nanoparticles could be prepared in a number of ways, in this example, it was prepared using the decomposition of iron (0) pentacarbonyl (Fe(CO)5) in the presence of ligands, like oleylamine (OAm), and hexadecylamine chloride (HDACl). In a simple case, 19.0 mL of a high boiling point solvent, like octadecene (ODE), ˜200 mg HDACl, and ˜1.0 mL OAm were combined and degassed at 120° C. for 0.5 h. This mixture was then heated to 180° C. in a four neck flask under Ar, then 0.35 mL of Fe(CO)5 (1.0 M in THF) was injected via an airtight needle into the solution under Ar forming the iron nanoparticle centers. While in this example the sizes of centers were on the order of 8-12 nanometers and are largely spherical, it is anticipated that the subsequent steps described herein would also work for larger size diameters (5-500 nm), as well as for centers of different shapes (cubes, rods, polyhedral, etc.) after adjustments to concentrations and annealing conditions. For example, after annealing the iron centers for 30 minutes at 180° C., metallic nickel was introduced into the system, where [Ni]:[Fe] molar feed ratios were controlled. In this example, the nickel source was Ni(PPh3)2(CO)2 and was chosen due to it's nickel being in a metallic (Ni0) state, however other comparable Ni sources can also be used. In a typical synthesis, 1.5 mmol Ni(PPh3)2(CO)2 (3 mL of 0.1 M in THF) was added to the Fe containing solution. The Ni-injection was separated into at least ten separate injections (0.3 mL each) with 15 minute annealing time between injections. The temperature was maintained at least 180° C. The Fe—Ni gradient NPs were purified by precipitation in dry ethanol (EtOH, 200 proof) under Ar. After centrifugation (10 min, 4400 RPM), the product was re-dispersed in dry hexane and stored in Ar. If direct oxidation of the NPs was tested, this was performed by opening the un-cleaned reaction solution to air at 100° C. for 5.0 h, followed by EtOH precipitation. The higher Ni-content gradients could be prepared by increasing the number of Ni-additions, increasing the concentration of Ni per addition, or decreasing the [Fe]:[Ni] molar ratios. See
In the tri-metallic gradient nanoparticle the Cr-precursor was introduced at different points in the synthesis. The hexacarbonyl chromium (0) (Cr(CO)6) precursor solution was prepared by dissolving 650 mg Cr(CO)6 in 20 mL of dioctylether at 100° C. under inert atmosphere. In this example, the Cr(CO)6 precursor was chosen due to its metallic Cr (Cr0), but it is understood that other precursors could be used. The Ni-precursor was prepared similarly to that described above.
In a typical synthesis, 6.8 mL of the Cr precursor was added into solution of Fe NP (prepared as shown above) under Ar at 180° C. For instance, a 2.3 mL aliquot was added slowly then annealed for 15 min before additional components. Next, a total of 9.4 mL of the Ni precursor was slowly added. The temperature was maintained at a minimal of 180° C. Injection amount of Ni precursor was split equally in smaller volumes and added over 50 min to avoid dramatic temperature loss. Solution was annealed for 45 min at 180° C. See
The Fe—Ni—Cr gradients were prepared similarly, with varied precursor sequence. In this example, a total of 9.4 mL Ni precursor was slowly deposited at temperatures of at least at 180° C. Next, 6.8 mL of the Cr precursor was slowly added at temperatures of at least 180° C. The nanoparticles were purified as described above. See
The Fe—CrxNi1-x gradients were described using the same chemical sources as described above. The CrxNi1-x gradients were added from stock solutions containing both Cr- and Ni-precursors. The [Cr]:[Ni] molar ratios of the stock solutions were varied over the course of a typical injection to produce varied x-compositions at a given position in the nanoparticle. In a typical synthesis, 6.8 mL Cr-precursor and 9.4 mL of Ni-precursor solutions were pre-mixed and then slowly injected into a solution containing the Fe-rich solutions, prepared as described above. In this example, the synthesis solution was maintained at temperatures of at least 180° C. See
Gradient nanoparticles with Fe—FexMn1-x gradient concentrations were prepared using an analogous approach, where the addition of Mn(CO)6 was introduced shortly after the additional of Fe(CO)5. The [Fe]:[Mn] molar ratios were tailored (100-0) over the course of the synthesis to adjust the gradient. In this system, the use of Mn(CO)6 was employed as a manganese source, however other precursors and metal salts could also be used. See
Gradient nanoparticles with Fe—FexCr1-x gradient concentrations were also prepared using of Co(CO)6 was introduced shortly after the additional of Fe(CO)5. The [Fe]:[Co] molar ratios were tailored (100-0) over the course of the synthesis to adjust the gradient. In this system, the use of Co(CO)6 was employed as a manganese source, however other precursors and metal salts could also be used. See
Gradient nanoparticles with Fe—MoXCr1-x gradient concentrations were also prepared using of Mo(CO)6 was introduced shortly after the additional of Fe(CO)5. The [Fe]:[Co] molar ratios were tailored (100-0) over the course of the synthesis to adjust the gradient. In this system, the use of Mo(CO)6 was employed as a molybdenum source, however other precursors and metal salts could also be used. See
Gradient nanoparticles with a general composition of Fe—Cr—Fe—Ni—Co—Mn or Fe—CraFebNicCodMne, where a-e are compositions that may vary radially from the center of the nanoparticle can be prepared this way, and the alternation of the composition gradient position within the nanoparticle can be similarly controlled by combining the synthesis of two or more of examples 1-6. Annealing temperatures ranging from 180 to 500° C. can be utilized, and elemental introduction and gradient control can utilize multiple injection needles, or more precisely, the multiple syringe pumps that can be automated to control timing and concentration/volume of precursors. Moreover, the addition of additional metals, such as tungsten, and molybdenum can be introduced using precursors such as W(CO)6 and Mo(CO)6, or other suitable metallic precursors. See
Gradient nanoparticles prepared in example 1-7 could be terminated with a range of ceramics, oxides, sulfides, and phosphides. For oxides, the nanoparticles could be heated from 80-200° C. in oxygen rich solvent (provided via bubbling of O2 through the solvent) or by various chemical oxidizers. For sulfides, molecules rich with reactive sulfur species are added, such as molecular sulfur (S8) dissolved in octadecene, and sulfurs bound to reactive phosphine's, such as tributylphopshine (TBP), trioctylphospine (TOP), or triphenylphosphine (P(Ph)3). For phosphide gradient growth, reactive phosphine's such as TBP and TOP are added in excess at tempertures of >200° C. The oxide, phosphine, or sulfide concentration can be altered throughout the gradient by varying introduction of chemicals and temperature ramping.
The gradient nanoparticles described in examples 1-8 can be terminated with various noble metals or alloys thereof by reducing the metal salts in the presence of a reducing acid. Precursors include, but are not limited to [AuCl4]−, [PtCl4]2−, [PtCl6]2−, [PdCl4]2−, and Ag+. In these situations, the noble metal salt can be complexed with ligands or other surfactants or phase transfer agents to promote solubility in the gradient nanoparticle host solution. Reducing agents employed include: H2 gas purge, sodium borohydride, lithium aluminum hydride, and reduction via the excess amines in gradient nanoparticle solution. By varying the deposition temperature, pressure, and concentrations, noble metal gradient thickness could be controlled from sub-monolayer coverage to multi-nanometer.
The gradient nanoparticles described in examples 1-9 could be terminated or functionalized with gradients rich in aluminum, titanium, vanadium, or alloys thereof. To a solution of gradient nanoparticles during synthesis, reactive aluminum precursors, like alane are added. For titanium, precursors such as TiCl4 in the presence of reducing agents like superhydride are used, or organometallic complexes such as Bis(cyclopentadienly)dicarbonyl titanium (II) or Bis(cyclopentadienly)titanium dichloride μ-Chloro-μ-methylenebis(cyclopentadienyl)titaniumdimethylaluminum can be used. To facilitate alloying, these gradients precursors can be added at controlled times during synthesis and in combination, as well as being heated to elevated temperatures. The addition of vanadium is facilitated by V(CO)6 and VCl4 precursors.
The gradient nanoparticles described in examples 1-10 could be terminated with or contain gradients of rare earth elements, rare earth ceramics, lanthanides or actinides. To a solution of gradient nanoparticles rare added earth elements precursors such as neodymium (III) acetate or Tris(tetramethylcyclopentadienyl)neodymium can be added to form interfaces of varied thickness and concentration. Similarly, other rare earths such as cerium (via cerium (III) acetylacetonate or other similar precursor), samarium (via samarium(III) acetylacetonate or other similar precursor), europium (via europium (III) acetate or other similar precursor), galodynium (via gadolinium (III) acetylacetonate or other similar), and yttrium (via Yttrium(III) acetylacetonate or other similar precursor) can be used. In these combinations, allowing with a gradient like those described above would be facilitated by addition of a reducing environment and high temperature annealing. Similarly, rare earth magnetic gradient nanoparticles could be facilitated by addition of Fe (see examples above) and Boron rich precursors (via borane or similar precursors), forming NdFeB-gradient nanoparticles. Such nanoparticles could be terminated with corrosion resistant gradients like those described in examples 1-10 forming highly stable NdFeB nanomagnets. Similarly, gradient nanoparticles terminated with cerium-rich gradients and oxides may also prove effective at corrosion resistance at the nanoscale and bulk form.
The gradient nanoparticles prepared in examples 1-11 and combinations thereof can be deposited as thin films and coatings in a number of ways. In the simplest form, the gradient nanoparticles are purified as described above and redispersed in a highly volatile solvent at concentrations of at least 10 mg/ml (metal weight). These can then be combined with a paint gun, air brush, or similar device in which compressed air is used to produce a thin stream of the gradient nanoparticles. Controlling spray time, particle concentration, temperature, pressure, and surface treatment, gradients can be deposited on metals, ceramics, glasses, plastics, rubbers, or other objects with varied sizes and shapes. The films can them be further processed in a number of ways, by exposing them to: different temperatures and pressures, excitation or irradiation, or chemical treatment.
The gradient nanoparticles can be deposited using electrophoretic deposition approaches as well, or other deposition forms closely associated with electrophoretic deposition. For this, highly uniform nature and colloidal stability of the nanoparticle, as well as the charged nature of the metallic gradient interface in association with its ligand surrounding, can be use for deposition. Here, highly charged chemical additives can be added as needed to interact with the nanoparticles interface or surface to increased charge. The concentration of the gradient solutions, field strengths, and time can be used for deposition control.
The strong magnetic properties can also be used to prepare thin films, coatings, and other layering of gradient nanoparticles, where a magnetic field is placed in close proximity to a substrate of choice that has been submerged in a solution of gradient nanoparticles. By controlling the magnetic field and strength, gradient nanoparticle deposition, patterning, and thickness can be controlled.
The gradient nanoparticles can be used as metal sources for aerogels and metal foams. In this process, the gradient nanoparticles are dissolved in supercritical carbon dioxide or a similar supercritical material and placed in a pattern, grid, or other high surface area host material; or combined with polymers and other binders. Upon evaporation of the supercritical fluid complex matrices of interlocked gradient nanoparticles with exist. When combined with gradient nanoparticles rich in voids (v), surface area and weight reduction can be maximized. The dried gradient aerogels can then be processed at different temperatures and conditions depending on final application.
The gradient nanoparticles were tested for initial corrosion resistance by spray coating following example 11 onto sanded iron nails, acid cleaned glass, and galvanized nut and bolt examples. The iron nail samples were prepared using gradient nanoparticles from examples 1-10 with coatings that were thick enough to cover the sanded iron surface of the nail. The final appearance of the gradient coated nails is a black-matte finish. These samples were exposed to heating at high temperatures (190° C. or higher) in air for at least 40 h, or submerged into salt water solutions ([NaCl]>1.0 M). The samples were then observed for oxidation, mass change, or appearance change. Similarly, NdFeB magnets were coated after gentle removal or protective metal covering. These too were submerged into salt-water solutions ([NaCl] ˜5%) and photographed for surface or solution change over time.
The gradient nanoparticles were tested for electromagnetic radiation (EMI) absorption by first drying the nanoparticles under vacuum for 4 h. Next, a desired volume of stylgard polydimethylsioxane (PDMS) was measured and the dried nanoparticles were added. This was followed by vigorous mixing via an overhead mechanical stirrer, upon which the nanoparticles become evenly dispersed. Next the mixture was added to a desired mold, the curing agent was added, and the sample was let to anneal at 80° C. for 6 h. The weight percentage of gradient nanoparticle in the PDMS was varied by simple weight changes to either the amount of PDMS or nanoparticle. A similar approach was used to prepare an iron oxide control, where Fe3O4 nanoparticles of comparable size to the gradient nanoparticle ones were prepared, and dispersed in PDMS at itenticle weight loading ratios. Finally, the samples were analyzed from 8-12 GHz using a frequency analyzer and a suitable electromagnetic source.
The gradient nanoparticles were also prepared embedded in plastics. Similarly to that above, the gradient nanoparticles were dried thoroughly, and added to either a molten mixture of plastic, or a solution of plastic precursors or monomers, and desired weight percentages. The resulting mixtures were either molded or extruded via a home built set-up. The magnetic properties were studied via both qualitative experiments using different loading ratios, or quantitatively via instrumentation.
To utilize the gradient nanoparticles as magnetic beads, the surface alloy composition as well as the surface inorganic- or organic-chemistry encapsulation was varied to render the particles hydrophilic. Using the examples described above, the surfaces further could have a range of different chemistries. The gradient nanoparticle beads were dispersed in water or buffers, and characterized for colloidal stability via UV-vis and Dynamic Light Scattering, whereas composition stability was followed by X-ray diffraction run after exposure to buffer conditions (i.e., salt, water, etc.). The gradient nanoparticle beads were tested for bead clearing efficiency, bead clearing time, and loading efficiency, and compared to commercially available magnetic beads.
The gradient nanoparticle magnetic beads prepared in example 18 were designed and constructed to bind to short strands of single-stranded oligonucleotides (ssDNA) or double-stranded DNA (dsDNA). In typical experiments, the inorganic- or organic-surface of the gradient nanoparticles were tailored to selectively absorb short (<100 bp), intermediate (100˜300, 300˜800 bp), or long (>800 bp) lengths of DNA. To further facilitate this, the gradient nanoparticle size was also varied from 10-100 nm. The absorption of ssDNA and dsDNA was followed by UV-vis, where a desired concentration was prepared, and monitored after exposure and bead clearing by gradient nanoparticles. The absorption was carried out at various ionic strengths, various DNA to nanoparticle concentration ratios, and either in the presence or absence of additives (i.e., PEG, surfactants, BSA, etc.). Efficient binding and release was found to vary depending on magnetic properties, as well as gradient nanoparticle compositions, as well as nanoparticle size, surface charge, surface chemistry, hydrodynamic radius, and surface double-layer.
Instrumentation
All optical absorption data was acquired using a Varian Cary Bio100 UV-Visible Spectrophotometer (UV-vis). The transmission electron micrographs (TEM) were obtained using a JEOL 2000EX transmission electron microscope operated at 100 kV. Samples were drop cast onto a carbon coated copper grids. The high-resolution TEM (HRTEM) images were collected on a JEOL JEM2100F Field emission TEM operated at 200 kV at the Analytical and Diagnostics Laboratory (ADL) at State University of New York at Binghamton. The instrument was equipped with a STEM detector and an Energy dispersive x-ray spectroscopy (EDS) detector. The Fourier Transform Infrared (FTIR) data was acquired using a Nicolet 6700 FTIR Spectrometer equipped with a diamond smart iTR attenuated internal reflectance accessory, and a liquid N2 cooled MCT-A detector. Samples were drop cast as neat solutions, or dried powders on the ATR crystals. The powder X-ray diffraction (XRD) patterns were taken on a Bruker D8 Advance powder diffractometer using Cu Kα radiation (1.5406 Å). Samples were drop cast and dried on a zero diffraction SiO2 crystal (MTI Corp.). X-ray Photoelectron Spectroscopy (XPS) measurements were performed on Surface Science Instruments (SSI) model SSX0100 that utilized monochromatic aluminum K-α X-rays (1486.6 eV) (Cornell Center for Materials Research, CCMR). The NP powders were dispersed on freshly cleaved Si substrates before analysis. The XPS analysis of peak binding energy and deconvolution was performed using CasaXPS software, in which a Shirley background subtraction was used, as was a 50:50 Guassian:Lorentzian line widths. All XPS were corrected for charging using the C is peak position of 284.8 eV. The magnetic measurements were also conducted at the CCMR on a Quantum Design Physical Property Measurement System (PPMS) with a Vibrating Magnetic Sample (VSM) attachment at an applied magnetic field ranging from −20 kOe to 20 kOe at 300 K and 10 K. Powder magnetic samples were prepared via ethanol precipitation and air-drying, followed by mass readings before measurements.
We expect those skilled in the art to take advantage of the composition of the gradient nanoparticles, the idea of gradient nanoparticles, the oxidation resistance properties of the gradient nanoparticles, and the electronic properties of gradient nanoparticles herein described for various applications as described herein.
Corrosion resistant coatings. Someone skilled in the art can spray coat, spin coat, evaporate, deposit, electrophoretically coat, magnetically coat, or chemically graft the gradient nanoparticles onto surfaces consisting of; metals, plastics, carbon fiber, composites, glasses, ceramics, magnets, semiconductors or any other surface or interface where corrosion in any form is detrimental to performance. It is envisaged that someone skilled in the art would further process these coatings by way of high temperature annealing in a range of temperatures, atmospheres, and pressures to ensure effective coating. Furthermore, it is envisaged that alternating layers of gradients particles of different compositions can be used, and that the gradient nanoparticles can be combined with polymers, plastics, epoxies, silanes and or rare earth additives to promote adhesion and further protect against corrosion.
Information Technology. Someone skilled in the art of crafting magnetic bites of information can take advantage of the uniform size, stability, high magnetic strength, and low coercivity of the gradient nanoparticles for individual bites of information, or in toe construction of magnetic domains which can serve as individual bites of information. It is envisages that thin films, coatings, or patterns of the gradient nanoparticles will be created using the technologies like those described herein. It is further envisaged that the said gradient will be modified and altered in order to tailor magnetic performance, which may or may not include; increased oxide concentrations, incorporation of rare earth lanthanide ions or atoms, such as; neodymium, yttrium, and samarium, or preparation of novel magnetic solids analogous to heuslar alloys or alnico alloys.
Electromagnetics. Someone skilled in the arts of electromagnetics may take advantage of the unique size, composition, and magnetic properties of the gradient nanoparticles for absorption, reflection, or generation of electromagnetic signals crucial for telecommunications, signal generation and interception technologies, guidance systems. It is envisaged that those skilled in the art will take advantage of the novel stability, magnetism, and composition of the gradient nanoparticles by way of its interaction with the electromagnetic spectrum, and in particular, its absorption, reflection, generation, or detection of microwave irradiation. One such spectrum frequency is called the C-band which ranges from the 4-8 GHz, the X-band which ranges from 8-12 GHz, and K-band, which ranges from the 18-27 GHz, and the K-a-band, which ranges from the 26-40 GHz, and the K-u-band, which ranges from 12-18 GHz and the V- and W-bands, which range from 40-75 GHz, and 75-110 GHz respectively. It is envisaged that devices with said gradients can be deposited onto common ceramic substrates and incorporated into existing technologies. Such deposition methods can include those described herein. It is further envisaged that the gradient nanoparticles will be combined with existing materials of interest to this embodiment, and further, may include combining the said nanoparticles with inert binders, such as carbon and its polymorphs and nano-forms, ceramics and oxides, rubber, or composites thereof. It is envisaged that those skilled in the art will further take advantage of the ability to have varied void concentrations and or additional intermediate layers of metals and oxides.
Magnetic Imaging: Someone skilled in the art of magnetic imaging may take advantage of the size-, functionality-, magnetism-, stability-, and oxidation resistant-properties of the gradient nanoparticles for magnetic resonance imaging (MRI). In this embodiment, the gradient nanoparticle itself is used as the contrast agent allowing for imaging to occur. Those skilled in the art will take advantage of the improved magnetic and corrosion resistance properties of the gradient nanoparticles as compared to the current convention of iron-oxide nanoparticles, of which, the gradient nanoparticles has higher magnetic strength and stability. Furthermore, it is envisaged that the gradient can be designed to improve magnetic response while promoting biocompatibility by terminating the gradient with a medical alloy like composition, as envisaged herein. Due to the stable nature of the gradient nanoparticle, the magnetic properties (susceptibility, strength) will not change over the course of the treatment, allowing clinicians to use lower concentrations of the nanoparticles, which may in turn, limit side effects of the therapy and limit exposure to the nanoparticle.
Drug Delivery: Someone skilled in the art of drug delivery may take advantage of the approach herein to add therapeutic-chemicals, -biomacromolecules, -drugs, -performance enhancers, -vitamins, and -biocompatible components to the chemical interface of the gradient nanoparticles. It is envisaged that those skilled in the art will take advantage of the superior magnetic and corrosion resistant properties of the gradient nanoparticle to magnetically guide the ‘drug’-modified gradient nanoparticles to a region of interest (i.e., tumor) where the drug can be released by passive diffusion, and built in release mechanism, or heat generated by a oscillating magnetic field, as described herein. Due to the size of the gradient nanoparticles being tunable, those skilled in the art will be able to design delivery, and temperature gradients, specific to the field of use.
Medical Therapies. Someone skilled in medical treatment via magnetic hyperthermia will take advantage of the magnetic and corrosion-resistant properties of the gradient nanoparticles for therapy, such as heating active tumors. In this embodiment, those skilled in the art will take advantage of the approaches described herein to deliver (or guide) the gradient nanoparticle to a tumor site and heat the tumor via an magnetic field. Due to the stable nature of the gradient nanoparticle, the magnetic properties (susceptibility, strength) will not change over the course of the treatment, allowing clinicians to use lower concentrations of the nanoparticles, which may in turn, limit side effects of the therapy and limit exposure to the nanoparticle. Moreover, because the magnetic strength generated by the gradient nanoparticles is many times higher than typical materials like iron-oxide particles, increased temperatures can be generated, further decreasing treatment times and visits, as well as increase the local efficacy.
Augmented Tumor Surgery. Someone skilled in the art of tumor surgery can visualize the tumors sites by combining the approached herein with magnetic imaging, or by further incorporating a luminescent metal, ion, biomolecule, or molecule to the gradient nanoparticle interface. In this embodiment, those skilled in the art will take advantage of the gradient's magnetic properties, corrosion resistance, and composition functionality to incorporate luminescent ions, such as gallium or other lanthanides into ceramic or oxide layers at the outer periphery of the particle, thus imparting a luminescence to the gradient nanoparticle. In other embodiments, the approaches herein will be used to modify the interface with fluorescent molecules, or bioluminescent enzymes or proteins. These light sources can thus be activated after the delivery of the gradient to the tumor sites by the clinician.
Battery components. Someone skilled in the art of battery construction and electrode design can take advantage of the corrosion resistant properties of the gradient nanoparticles while also taking advantage of the particles rich in void concentration for improved lithium or sodium intercalation, battery stability towards long term cycling, and increased storage densities. It is envisaged that those skilled will utilize said gradient nanoparticles that posses high void concentrations and anion rich surfaces to promote stable lithium- or sodium-ion intercalation. Furthermore, it is envisaged that gradient nanoparticles that are both conductive, but also possess oxide or sulfide rich gradients will provide greatest opportunity.
Fuel cell components. Someone skilled in the art of fuel cell construction, electrode design, and catalyst preparation may take advantage of gradient design and composition to produce a nanoparticles that act or protect the main electrodes or electronics from corrosion, but also produces catalysts consisting a corrosion resistant inner gradient followed by ceramic or oxide rich layer, and terminated with thin gradients rich in noble metals. It is envisaged that such catalysts will reduce catalyst costs while increasing efficiency by proving a cost effective and conductive inner gradient, and active oxide layer, and small but active amount of noble metal, such as; platinum, palladium, silver, gold, or said noble metals in alloy forms combined with nickel, vanadium, iron, copper, cobalt, chromium, or vanadium. It is further envisaged that those skilled in the art will combine said gradient nanoparticles with conductive supports, such as carbon (carbon black, HOPG, etc.) and it's polymorphs and nano-forms (graphene, C60, nanotubes, etc.), and that additional thermal annealing of the gradients at elevated temperatures, varied atmospheres, and varied pressures will be performed, and that the final products will be combined with ion conductive polymers in final fuel cell constructions.
Gas Storage and Remediation. Someone skilled in the art of gas storage and remediation (catalytic processes) may take advantage of a gradient nanoparticle with; high void concentrations, specific void sizes, and specific void interface reactivity (metal sites), to collect, absorb, or convert gases rich in oxygen, sulfur or nitrogen. It is envisaged that said gradients could be combined with solid supports, liquids, ionic liquids, and other devices to absorb gases emitted from refineries, power plants, automobile and other transportation exhausts. Further, the gradients can be further used as gas scrubbers to remove/convert said contaminants or others in living areas like those found in medical centers, hospital rooms, aircraft, maritime vessels, and spacecraft, as further described herein.
Heterogeneous catalysis. Someone skilled in the art of heterogeneous catalysis; may take advantage of a gradient nanoparticle whose composition is stable to high temperatures and whose outer gradient has a composition rich in particular oxides or ceramics and is when needed terminated by gradient rich in noble metals or other metals that either cover, or partially cover the ceramic interface. It is envisaged that said gradients could be used in; automobile catalytic converts and exhaust management devices/programs, conversion or remediation of toxic gases. It is further envisaged that said nanoparticles could be prepared as coatings, films, patterns, and sprays like that described in herein, or on supports, such as described herein.
Lubrication. Someone skilled in the art of lubrication may take advantage of the high temperature stability of the gradient particles as additives for dry and liquid lubrications. In this embodiment the gradient will consist of a high temperature corrosion resistant inner gradients and will be terminated with increasing concentrations of metal-oxides or metal-sulfides, and will reduce wear by movement of the gradient nanoparticles within the film, and also the molecular layers within gradients. The gradient lubricant can be deposited before assembly as films using technologies like that described herein or deposited/re-deposited by adding said lubricant as an additive to existing oils and liquid lubricants.
Carbon Composites. Someone skilled in the art of constructing carbon composites, such as carbon fiber, can take advantage of solution processability of the gradient nanoparticles to infuse composites with specific concentrations of metals, thereby endowing the composite with new or improved properties; such as, mechanical wear, magnetism, corrosion resistance, electromagnetic absorption, conductivity, reflectance, strength. The gradient nanoparticle can be either be deposited before and after graphitization of carbon, or infused by using as an additive to epoxy hardener.
Steel. Someone skilled in the art of creating and processing steel can take advantage of the composition control, corrosion resistance, and nano size of the gradient nanoparticles to create steel coatings, wires, films, and patterns. Steel coatings will be prepared by depositing thin films, where thicknesses are between 1-1000 nanometers of the gradient nanoparticles followed by heating to temperatures of >200° C. in various atmospheric conditions to create continuous steel layers. Similar approaches can be used to make thin wires (deposited gradients into molds), and patterns (where pattern dimensions can range from nano- to micro-meter dimensions). It is envisaged that those skilled in the art can prepare gradients of all common steel compositions and grades, and defined by the AISI/SAE organizations, namely; 10XX, 11XX, 12XX, 13XX, 23XX, 25XX, 31XX, 32XX, 33XX, 34XX, 40XX, 44XX, 41XX, 43XX, 47XX, 46XX, 48XX, 50XX, 51XX, 50XXX, 51XXX, 52XXX, 61XX, 72XX, 81XX, 86XX, 87XX, 88XX, 92XX, 93XX, 94XX, 97XX, 98XX. Where the host gradient (high concentration) is metallic iron, the first two numbers are Nickel-Chromium-Molybdenum concentrations, and the “XX” correspond to carbon concentrations. Moreover, those skills in the field will take advantage of the nanoscale dimensions of the gradients to process such steels at temperatures much lower than those typically required to craft steel. It is further envisaged that different classes of stainless steel can be imparted in different regions of the nanoparticle gradient, and those regions may also contain functional voids.
Steel Management and Preparation. Someone skilled in the art of crafting steel uses the gradient nanoparticles to induce phase changes, reduce or create grain boundaries, induce or control precipitation, and improve processing. Unlike other embodiments herein, those skilled in the art will take advantage of the gradient nanoparticles as additives to manipulate bulk steel processing. In addition to promoting corrosion resistance as described herein, and preparation of steel films, wires, and patterns herein, the composition of the gradient nanoparticles and their size, size ratios, concentrations control will be used to; refine the microstructure of steel, and the incorporation of metals and ceramics that otherwise cannot be easily integrated (including carbides, intermetallics, carbonitrides, and nitrides, sulfides, phosphides, oxides, and ceramics). It is further envisaged that final processing of bulk steel with the nanoparticle gradients will passivate large grain boundaries, extended defects, and interfaces during the processing. It is envisaged that the gradient nanoparticles can be combined during the steel smelting, or added to it's interface during cooling, or added as a final step to the cooled and forged steel, allowing for rapid compositional changes, or added after the final cooling of the bulk steel followed by additional annealing steps like those described herein. It is envisaged that changes to the steels corrosion resistance, toughness, yield strength, ductility, abrasion resistance, and magnetic properties will be tailored in this manner.
Stainless Steels: Someone skilled in the art of crafting stainless steel uses the gradient nanoparticles to prepare stainless steel coatings, thin films, wires, patterns and additives. Like that described herein, the Stainless Steel coatings will be prepared by depositing thin films, where thicknesses are between 1-1000 nanometers of the gradient nanoparticles followed by heating to temperatures of >200° C. in various atmospheric conditions to create continuous steel layers. Similar approaches can be used to make thin wires (deposited gradients into molds), and patterns (where pattern dimensions can range from nano- to micro-meter dimensions). It is envisaged that those skilled in the art can prepare all stainless steel grades, as defined by the SAE as: J405, 904L, 440F, 440C, 440B, 440A, 430, 410, 409, 32iH, 321, 317L, 316Ti, 316LN, 316L, 316, 312, 310S, 310, 305, 304LN, 304L, 304H, 301LN, 301, 254SMO, 2304, 2205, or other 200-, 300-, and 400-series forms that include Austenitic-Superaustenitic-, Ferritic-, Matensitic-, and Duplex-steels or combinations thereof. It is further envisaged that different classes of stainless steel can be imparted in different regions of the nanoparticle gradient, and those regions may also contain functional voids. Moreover, those skills in the field will take advantage of the nanoscale dimensions of the gradients to process such steels at temperatures much lower than those typically required to craft steel.
Medical Alloys. Someone skilled in the art of crafting and implementing medical alloys may take advantage of the gradient nanoparticles to prepare stable metal coatings and films that are composed of alloys commonly referred to as medical alloy compositions, which aluminum, chromium, cobalt, molybedum, vanadium and titanium. It is envisaged that gradient nanoparticles with Grade 5—like titanium alloys (Ti6Al4V, Ti-6Al-4V, Ti6-4) can be constructed in which the nanoparticle retains its magnetic and corrosion resistant properties but is imparted with the properties commonly found in Grade-5, such as biocompatibility, strength, and corrosion resistance in biological environments, solutions and interfaces. It is further envisaged that coatings, films, and patterns of medical alloys can be deposited onto; other metals, plastics, ceramics, implants, devices, and surgical tools by following the procedures discussed herein.
Titanium Alloys. Someone skilled in the art of crafting titanium may take advantage of the gradient nanoparticle to prepare nanoparticles with titanium rich gradients, circumventing the need to produce a wholly titanium particle. It is envisaged that careful selection of the gradient will allow titanium rich gradients to be formed, and subsequent alloys in a similar manner. These alloys can then be used in embodiments similar to those herein. It is further envisaged that the titanium rich gradient nanoparticles can be used to craft thin films, coatings, wires, and patters in ways similar to that described herein.
Aluminum Alloys. Someone skilled in the art of crafting aluminum may take advantage of the gradient nanoparticle to prepare nanoparticles with aluminum rich gradients, like that of titanium envisaged herein.
Magnetic Refrigeration. Someone skilled in the art of magnetic refrigeration uses gradient nanoparticles as the magnetic components in refrigeration by taking advantage of the low coercitivity, high magnetic moment, and high stability of the gradient nanoparticles. It is envisaged that gradient nanoparticles rich in iron cobalt and nickel whose interface is stainless, will have high performance in magnetic refrigeration, wherein rapid switching of high magnetic fields is a necessity to improve efficiency.
Propulsion. Someone skilled in the art of crafting propulsion components uses the gradient nanoparticles as energy sources for thrust. In this embodiment, the gradient nanoparticle would be made of materials with high energy density that are known to promote combustion.
Ballistics. Someone skilled in the art of ballistics uses the gradient nanoparticles as high stable and compact source of combustible energy. The ballistics can be prepared as thin-films, powders, or additives of existing technologies. It is envisaged that such gradients will be rich in metallic iron, carbon, magnesium, or aluminum.
Life Sciences. Someone skilled in the general art of life-sciences used the gradient nanoparticles as highly stable magnetic supports. It is envisaged that the properties described herein will be used to separate, collect, or process biomolecules, biomacromolecules, proteins, enzymes, antibodies, small molecules, conjugates, self-assembled structures, and drugs by attaching said molecules to the gradient nanoparticles interface followed by separation via a magnetic field supplied by a strong portable magnet. Here those skilled in the art may take advantage of the nano size of the gradients, their strong magnetic properties, and the functionality to separate with high efficiency.
Life Sciences. Someone skilled in the general art of life sciences uses the gradient nanoparticles as highly stable magnetic supports, also known as magnetic beads. It is envisaged that the gradient nanoparticle properties, and magnetic bead studies (
Environmental Remediation. Someone skilled in the general art of environmental remediation uses the gradient nanoparticles magnetic properties to collect toxins from soil, water bodies, buildings, air, or surfaces. Using the embodiments described herein those skilled in the art can modify the interface of the gradients to absorb said toxins followed by collection via magnetic field. It is envisaged that the added corrosion resistance, magnetic stability, and strong magnetic properties of the gradients will allow for increased recyclability of the materials, allowing for the same materials to collect multiple times.
Ferrofluids. Someone skilled in the art of creating and using ferrofluids uses the gradient nanoparticles as additives of said fluids and other components. Using the properties described herein it is envisaged that the gradient nanoparticles can be dispersed in solvents at high concentrations upon which the viscosity of the solution can be tailored via applied magnetic field. It is envisaged that those skilled in the art will use the strong magnetic properties and low coercivity of the gradient nanoparticles to prepare increasing smaller and more responsive ferrofluid components, such as active shock absorbers, seals, active lubrication, optics, heat transfer, and propulsion.
Conductive Surfaces. Someone skilled in the art of creating conductive surfaces uses gradient nanoparticles as precursors to making such surfaces. Thin films, coatings, or patterns of gradient nanoparticles can be formed and then heated (via a furnace, laser, etc.) in order to sinter the gradients nanoparticles into continuous metals. Here it is envisaged that the composition, corrosion resistance, and processability of the gradients will be beneficial as compared to conventional technologies and approaches.
Aerogels. Someone skilled in the art of creating metallic aerogels or metal foams uses gradient nanoparticles as the metallic precursor. Owing to the nature of it's interface, it is envisaged that the gradient nanoparticles can be dissolved in supercritical solvents with ease, and combined with additional components as necessary. Once formed via evaporation of the supercritical chemical, the gradient nanoparticles will be interconnected and can be further processed via steps from those arts. In this embodiment it is expected that the stainless properties of the gradients will improve the long term performance of the aerogels, the nano size will lead to new interconnected microstructures, and gradient nanoparticles with high concentrations of voids will decrease weight, increase surface area, and also increase reactivity of aerogels where needed.
3D Printing. Someone skilled in the art of 3D printing plastics, metals, or other materials can take advantage of the gradient nanoparticles to impart metallic, magnetic, or stainless properties into or onto 3D printed objects. Owing to the nature of the properties, size, and processability of the gradient nanoparticles, it is envisaged that they can be infused into 3D printing filaments, allowing for the direct printing of metal rich objects. It is further envisaged that the printed 3D objects could be spray coated with a final coating of gradient nanoparticles to improve, protect, or decorate the object. It is finally envisaged that metal 3D printing and laser printing can further take advantage of gradient nanoparticles as a metal writing source, or by using films of gradients that can be laser engraved, which would allow for conductive patterns to be created.
Rare Earth Magnets. Someone skilled in the art of crafting rare earth magnets, or similar materials can take advantage of the gradient nanoparticle approach to either craft nanoscale magnets, or protect bulk magnets from corrosion. Owing to the nature of the gradient technology and its corrosion resistance, it is envisaged that the nanoscale magnets would have strong magnetic properties and high susceptibility. Moreover, as films and coatings, the gradients can be used a cost effective and space/weight saving solution to coat or modify bulk magnets, such as those found in wind turbines, hybrid electric vehicles and electric vehicles. The coatings would extend the lifespan of the magnets, especially when operated in humid or salt rich environments. The coating could be either functional to the magnet itself, such as reducing Nd-hydroxide formation, bonding or filling cracks and grain boundaries, or passivate impurities (such as Nd or Fe filings produced during manufacture). Such coatings could be used to replace current technologies, such as nickel-copper-nickel plating or epoxy/organic coatings, thus reducing protective layer thickness and cost.
Microfluidics. Someone skilled in the art of microfluidics design and usage can take advantage of the high compositional stability, as well as the controlled colloidal stability of gradient nanoparticles for use inside microfluidic channels. Here, the channels, reservoirs, and mixing chambers of the microfluidic can be designed in such a way as to optimize flow of the magnetic gradient nanoparticle continuously, as well as to use the gradient nanoparticle to perform magnetically induced; channel blockage, pumping, mixing, immunoprecipitation, analysis, diagnostics, or delivery. It is envisaged that each microfluidic device would employ multiple gradient nanoparticle variations in tandem, and may take further advantage of the composition and size dependence magnetic properties to tune response.
Anti-Counterfeit Technologies. Someone skilled in the art of designing and producing anti-counterfeit materials and devices can take advantage of the colloidal nature, high and addressable magnetism, ease of embedding into plastics, and high EMI absorption properties to of the gradient nanoparticles to prepare security inks, radio-frequency identification (RFID) tags, and other addressable magnetic devices. It is envisaged that different printed patterns, 3D features, or alternating layers, of gradient nanoparticles can be easily crafted, printed, patterned, or machined, allowing for tunable electromagnetic absorption characteristics not currently available. In addition to such features, multiple versions, compositions, sizes, and formulations of gradient nanoparticles can be used simultaneously to further craft magnetic response. Further, it is envisaged that said gradient nanoparticles can be combined with additional nanomaterials (metallic, ceramic, semiconductive), polymers (conductive and non-conductive) and surfaces (glasses, metals, ceramics, semiconductors) to alter conductivity or further refined antennae characteristics.
The present application claims priority to U.S. Provisional No. 62/257,665, filed on Nov. 19, 2015.
This invention was made with government support under Grant No. 1410569, awarded by the National Science Foundation (NSF). The government has certain rights in the invention.
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/US2016/062666 | 11/18/2016 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2017/087744 | 5/26/2017 | WO | A |
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| Number | Date | Country | |
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| 20180326479 A1 | Nov 2018 | US |
| Number | Date | Country | |
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| 62257665 | Nov 2015 | US |
