EP3393974A1 - Production of graphene based composite nanostructures obtained through the growth of zinc-oxide nanorods or microrods on unsupported graphene nanoplatelets in suspension - Google Patents
Production of graphene based composite nanostructures obtained through the growth of zinc-oxide nanorods or microrods on unsupported graphene nanoplatelets in suspensionInfo
- Publication number
- EP3393974A1 EP3393974A1 EP16845329.8A EP16845329A EP3393974A1 EP 3393974 A1 EP3393974 A1 EP 3393974A1 EP 16845329 A EP16845329 A EP 16845329A EP 3393974 A1 EP3393974 A1 EP 3393974A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- growth
- gnps
- suspension
- zno
- microrods
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
Definitions
- the present invention relates to the nanotechnology sector and more precisely to an innovative method for the production of graphene nanoplatelets decorated with nanorods or microrods of zinc oxide (possibly doped with metal), with improved electrical, electronic, and mechanical properties.
- the graphene nanoplatelets (GNPs) are uniformly coated over their entire surface (on both sides of the flake) with nanorods (NR) or microrods (MR) of zinc oxide (ZnO), possibly doped with metals.
- NR nanorods
- MR microrods
- ZnO zinc oxide
- the morphological properties of the ZnO nanostructures and the coating density of the surface of the GNPs can be controlled during the growth process.
- the process takes place in aqueous or hydroalcoholic suspension and leads to the production of nanomaterials that can be used as fillers in polymer matrices to obtain nanocomposites that present specific electrical, electromagnetic, and electromechanical properties.
- the method used in the present invention is simple, economically advantageous, scalable for mass production, does not require the use of a catalyst, and the end product is free from impurities.
- the present invention has been developed within a research framework aimed at providing new nanostructured and graphene-based materials with controlled electrical, electromagnetic, and electromechanical properties.
- GNPs decorated with ZnO nano/microrods are of considerable applicational interest in multiple sectors, either as mechanical reinforcement in composite materials, or for possible exploitation of their piezoelectric or electroactive properties, for the production of composites with desired electrical and/or electromagnetic properties, such as, for example, radar- absorbent materials, as well as for catalytic or energy-harvesting applications.
- ZnO-GNP hybrid nano/microstructures are produced in the presence of a seed layer that favours the nucleation of ZnO structures and leads to a uniform and high-density coating of the GNPs.
- Deposition of the seed layer is carried out while maintaining the suspension of GNPs under stirring by various techniques, as described hereinafter, for the control of the density and uniformity of the coating .
- the main innovative characteristics of the invention rely on the simplicity and cheapness of the process proposed, which, by means of appropriate definition of the operating conditions during the steps of deposition of said seed layer and of growth of the ZnO micro/nanostructures, enables production of ZnO- decorated GNPs, having controlled morphological characteristics.
- the production technique developed according to the present invention is economically advantageous and suitable for mass production.
- Composite materials based on graphene and zinc oxide (ZnO) nanostructures form the subject of numerous studies owing to their potential applications in the production of new multifunctional materials with improved electrical and mechanical properties, and of new devices for the electronic and photonic sectors [1, 2]. It has been shown in the literature that, when inorganic materials, such as zinc oxide, are integrated with graphene, their electronic properties are considerably improved [3]. ZnO nanostructures generally behave as n-type semiconductors, and hence have the capability of enabling electron doping on graphene.
- the present invention consequently falls within this research framework and proposes an innovative technique for the production of graphenes decorated with nano/microstructures (in the case in point nanorods or microrods with controlled morphological properties) of ZnO or else of ZnO doped with metals.
- the graphene nanoplatelets according to the present invention constitute the growth substrate for the ZnO nano/microstructures, consequently enabling maximization of the effect of interaction between nanostructured ZnO and graphene. Growth of the ZnO nanostructures takes place in aqueous solution, in which the graphene nanoplatelets are dispersed in suspension.
- Junwei Ding et al. [10] have grown mixed zinc-oxide structures, constituted by nanoparticles and microspindles, via hydrothermal synthesis in aqueous solution on reduced graphene oxide and without the use of a seed layer.
- the GO was obtained via a modified Hummer's method and subsequently reduced via glucose and ammonia.
- ZnO microspindles present, however, a coating density of the rGO flakes lower than the one that can be obtained according to the present patent.
- the quality of the grown nanostructures is poor.
- the typical morphology that is noted is that of nanoparticles or nanorods with very low aspect ratio, with rather uneven characteristics, and a rather low density of coating of the surface of the graphene.
- the possibility of growing ZnO nanostructures doped with metals is not present.
- the patent KR20140037518 (A) "ZnO nanostructure including graphene” regards deposition of a ZnO nanostructured layer on a graphene sheet grown by CVD and supported by a substrate, for applications in devices used for photodetection.
- This patent, KR20140037518 involves the use of a support for the growth of graphene, presents high costs, is not easily scalable, and enables growth of the ZnO nanostructures on just one of the faces of the graphene plane.
- the patent CN 102157315 (A) "Emitting cathode based on composite material of graphene/zinc oxide nanowire and preparation of same” regards the production of an electron field- emission cathode for applications in FEDs (Field-Emission Displays), constituted by a conductive electrode coated with graphene and overlaid by an array of ZnO nanowires.
- the conductive electrode (usually constituted by a glass coated via PVD with a metal layer), is coated with a graphene layer, starting from a previously sonicated aqueous suspension, using various techniques, such as spraying or electrophoresis.
- the ZnO nanowires can be grown via hydrothermal technique or CVD or PVD, preferably CVD.
- the patent CN102157315 involves the use of a growth substrate and the use of costly apparatuses.
- the nanostructures are moreover grown on just one face of the graphene plane.
- the patent US 20130099196 Al “Semiconductor-Graphene Hybrids Formed Using Solution Growth” regards the production of a composite constituted by graphene and ZnO nano-microrods by carrying out growth in aqueous solution (without the use of a seed layer) of ZnO on graphene grown by CVD and supported on a PMMA layer, to obtain a UV detector.
- An innovative aspect of this patent is the absence of the seed layer and the possibility of carrying out the growth with a graphene substrate placed face down, on the free surface of the reaction beaker, or face up on the bottom of the beaker, and supported in this case by a Si or glass substrate.
- the patent CN 103734188 (A) "Preparation method and applications of zinc oxide-graphene oxide composite nanomaterial” regards the production of a graphene oxide-zinc oxide composite, starting from a suspension of GO in an alcohol, and its use as antibacterial agent, in particular as antiseptic agent for biomedical instrumentation and equipment.
- This patent regards the production of a composite of GO and ZnO nanoparticles, for the production of which it is necessary to obtain first GO, applying a modified version of the well-known Hummer's method, and hence with the use of dangerous reagents.
- the patent CN 104007236 (A) "Preparation method and application of graphene/zinc oxide nanocomposite material” regards the production of a hybrid nanocomposite based on graphene/ZnO, obtained in aqueous suspension using ultrasounds.
- the patent involves ultrasound dissolution of Zn nitrate in aqueous solution, followed by the addition of GO and reduction in situ, once again by means of ultrasounds, via use of hydrazine.
- the patent CN104007236 involves the use of aggressive reagents both for the step of production of GO and for its subsequent reduction.
- the various steps of production comprise a large number of processes, which render implementation thereof long and technically demanding .
- the patent CN 103435033 (A) "Simple and convenient method for preparing graphene-zinc oxide nanorod composite material in ultrasonic wave” regards the production of a hybrid graphene-ZnO nanorod composite starting from sonication of finely ground metallic-Zn powder in the presence of expanded graphite in suspension in an aqueous ethanol solution.
- the patent CN 102580716 (A) "Method for synthesizing zinc oxide/graphene composite by solvothermal method" reports a method for producing hybrid composites constituted by ZnO- decorated GO with photocatalytic properties. The method involves a solvothermal synthesis at temperatures below 200°C (and simultaneous partial reduction of GO), carried out on a mixture of GO and zinc acetylacetonate in appropriate solvent (generally ethylene glycol or ethanol).
- This patent, CN102580716 involves the use of strong acids and oxidizing agents for the production of GO through a modified version of the known Hummer's method.
- the patent CN 101857222 (A) "Preparation method of large-area and continuous graphene/zinc oxide composite structure” regards the preparation of a composite formed by G/GO and ZnO nanostructures starting from an aqueous suspension or a suspension in organic solvents of graphene or GO. After suspending the G/GO into the solvent via sonication, the ZnO nanostructures (containing various geometries that include nanodots and nanowires/nanorods) are produced by means of hydrothermal growth starting from different reagents according to the structures to be obtained (zinc nitrate and HMTA or zinc acetate). Reduction is then carried out with hydrazine. Also this patent involves the use of aggressive reagents both for the step of production of GO and for its subsequent reduction. The different steps of production further comprise a large number of processes, which render implementation thereof long and problematical.
- the patent CN 10342614 (A) "Preparation method of graphene-ZnO nanoparticle composite material” regards the preparation of a GO-ZnO nanoparticle composite starting from simple Zn salts (nitrate, acetate, sulphate, chloride, etc.). The product is obtained by simple mixing of the salts in aqueous GO solution and subsequent thermal treatment between 150°C and 1000°C (particle size of 10 nm).
- the patent CN103482614 uses GO as precursor for the preparation of the GO-ZnO nanoparticle composite. The process employed moreover involves the use of high temperatures and long reaction times that may even reach 10 h.
- Step 1 production of aqueous suspension of graphene nanoplatelets (GNPs);
- Step 2 deposition of a seed layer on non-supported
- Step 3 growth of ZnO nanorods/microrods on nonsupported GNPs in aqueous suspension.
- Step 2 during initial deposition of a seed layer (SL) on GNPs in suspension, the uniformity and size of the nanoparticles that constitute the SL are controlled via :
- Step 3 for the growth of micro/nanorods of ZnO (possibly doped with metals) with desired morphology, three different growth techniques (static HT growth, dynamic HT growth, and growth by PS) are, instead, proposed in order to be able to control the morphological characteristics of the structures produced (i.e., diameter and length).
- three different growth techniques static HT growth, dynamic HT growth, and growth by PS are, instead, proposed in order to be able to control the morphological characteristics of the structures produced (i.e., diameter and length).
- the following techniques are proposed:
- Step 1 Production of aqueous suspension of GNPs
- the GNPs are produced using the thermochemical exfoliation technique starting from intercalated graphite compounds according to the prior art [13, 14, 15] .
- the methods of deposition of the seed layer and of the ZnO nano/microstructures work in a similar way on graphenes obtained from epitaxial growth, chemical vapour deposition, mechanical exfoliation, and reduced graphene oxide (rGO).
- the advantage of using GNPs as starting graphene material lies in the better properties of electrical conductivity of GNPs as compared to rGO [14] and in the process of production of GNPs, which is economically advantageous, suitable for mass production, and does not make use of toxic substances.
- Step 2 Deposition of seed layer on non-supported GNPs in aqueous solution
- the seed layer for the growth of ZnO nano/microrods is deposited on GNPs in aqueous suspension, which is constituted by a mixture of water and isopropanol, dissolved in which is an appropriate amount of zinc acetate dihydrate (Zn(CH3COO)2-2H2O) in a concentration lying in the 1 mM
- the process of deposition of the seed layer consists in the substeps described below.
- Step 1 The GNPs obtained in Step 1 (or GO or rGO or graphene nanoplatelets of a commercial type) are rinsed with isopropanol, and the solvent is removed by centrifugation. The GNPs are then dispersed in the aqueous solution containing zinc acetate dihydrate via vigorous stirring in a centrifuge tube. The suspension is then transferred into a glass beaker and subjected to one of the two different treatments described hereinafter:
- the sediment obtained is thermally treated in an oven at a temperature of between 200°C and 400°C, for a time of between 10 min and 60 min, to obtain GNPs coated with nanoparticles that constitute the seed layer, of which it is possible to control the dimensions and coating density (over GNPs) by choosing the technique of mechanical/magnetic stirring or else the sonication technique and by appropriately fixing the process temperature and times.
- Step 3 Growth of ZnO nanorods/microrods on nonsupported GNPs in aqueous suspension
- aqueous solution for the growth of ZnO nano/microrods is prepared by dissolving equimolar amounts of zinc nitrate hexahydrate and hexamethylenetetramine (HMTA) in double-distilled (DI) water, in a concentration ranging from 2 mM to 0.5 M.
- DI double-distilled
- a metal nitrate hexahydrate or anhydrous metal nitrate is further added to the growth solution .
- the resulting solution is then magnetically stirred for a time between 20 min and 60 min at a rate in the 300 rpm ⁇ 700 rpm range at room temperature, thus obtaining a turbidity-free solution.
- the GNPs coated with the seed layer are rinsed again with DI H 2 0, and the water is removed by centrifugation.
- the GNPs recovered from the sediment are then homogeneously dispersed in the growth aqueous solution via vigorous stirring in a centrifuge tube.
- Hydrothermal growth in static conditions the suspension of GNPs in the aqueous growth solution (transferred into a glass beaker) is put into an oven preheated at a temperature between 70°C and 150°C for a time ranging between 1 h and 10 h.
- Probe sonication the suspension of GNPs in the aqueous growth solution (transferred into a glass beaker) is subjected to probe sonication for a timef between 5 min and 60 min, fixing the amplitude of oscillation of the probe between 20% and 100% (of its maximum value).
- the suspension is centrifuged to remove the growth solution and washed twice with double-distilled water.
- the precipitate obtained is dried in an oven at a temperature between 70°C and 180°C for a time between 10 and 30 min.
- the end product is constituted by GNPs coated with ZnO nano/microrods.
- Figures la and lb show SEM images at two different magnifications of GNPs coated by seed layer obtained through magnetic stirring;
- Figures 2a and 2b show SEM images at two different magnifications of GNPs coated by seed layer obtained through probe sonication
- Figures 3a and 3b show SEM images at two different magnifications of GNPs coated with ZnO micro/nanorods obtained by producing the seed layer via mechanical stirring, followed by hydrothermal growth under static condition;
- Figures 4a and 4b show SEM images at two different magnifications of GNPs coated with ZnO nanorods obtained by producing the seed layer by means of mechanical stirring, followed by hydrothermal growth under dynamic conditions;
- Figures 5a and 5b show SEM images at two different magnifications of GNPs coated with ZnO nanorods obtained by producing the seed layer by means of probe sonication, followed by hydrothermal growth under dynamic conditions;
- Figures 6a and 6b show SEM images at two different magnifications of GNPs coated with ZnO nanorods obtained, by producing the seed layer by means of probe sonication, followed by growth at room temperature via probe sonication;
- Figures 7a and 7b show SEM images of ZnO microrods doped with magnesium at two different magnifications.
- Example 1 - Preparation of the GNPs The GNPs are produced using a graphite intercalated compound (GIC) as precursor, according to a method similar to the one reported in [13-15]. In brief, the GICs are thermally expanded in a muffle furnace at 1150°C for 5 s.
- GIC graphite intercalated compound
- An amount of 20 mg of expanded graphite is then immersed in ethanol (instead of acetone, or an acetone-DMF mixture or an acetone-NMP mixture as described in [13-15]) and exfoliated in liquid phase via probe sonication in pulsed regime for a total time between 15 min and 30 min, fixing the amplitude of oscillation of the probe at 70% and controlling the temperature of the suspension at 15°C, through the use of a recirculation bath connected to a thermocryostat.
- the sonication process produces a colloidal suspension of GNPs with lateral size of 1 pm to 5 pm and a thickness of 1 nm to 20 nm.
- the solvent is then removed by centrifugation.
- Example 2 Deposition of the seed layer on GNPs via magnetic stirring
- the solution for the deposition is prepared by dissolving zinc acetate dihydrate (with a concentration between 0.001 M and 0.010 M) in isopropanol via magnetic stirring for 20 ⁇ 60 min at a rate of 400-600 rpm.
- the GNPs obtained in the previous step are rinsed with isopropanol, and the solvent is removed by centrifugation.
- the GNPs are then dispersed in the solution for formation of the seed layer via vigorous stirring in a centrifuge tube.
- the suspension is then transferred into a glass beaker and magnetically stirred at 250 rpm for 30 min to obtain a uniform coating of GNPs by the seed layer.
- the suspension is then further centrifugated (at 3095 g for 30 min) to remove the seed-layer growth solution.
- the sediment obtained is then thermally treated in a muffle furnace at a temperature between 200°C and 400°C for a time between 10 min and 60 min, to obtain GNPs coated with ZnO nanoparticles, which constitute the seed layer.
- Figure 1 shows the SEM images at different magnifications of GNPs with seed layer obtained by means of magnetic stirring.
- the nanoparticles have a size usually between 10 nm and 30 nm.
- Example 3 Deposition of the seed layer on GNPs via probe sonication
- the solution for the deposition of the seed layer is obtained as described in Example 2.
- the suspension of GNPs is prepared as described in Example 2.
- the suspension is then transferred into a glass beaker and sonicated by means of a sonication probe for a time between 5 min and 30 min, fixing the amplitude of oscillation of the probe between 20% and 80% of the maximum value.
- the suspension is then further centrifugated (at 3095 g for 30 min) to remove the seed-layer growth solution.
- the sediment obtained is then thermally treated in a muffle furnace at a temperature between 200°C and 400°C for a time between 10 min and 60 min to obtain GNPs coated with ZnO nanoparticles, which constitute the seed layer.
- Figure 2 shows images obtained under the scanning electron microscope of GNPs coated with seed layer obtained by means of probe sonication.
- the nanoparticles that provide the seed layer are of a size generally smaller than 10 ⁇ 20 nm and uniformly coat the surface of the GNPs.
- the coating density of the surface of the GNPs is higher in the case of sonication as compared to the case of magnetic stirring.
- Example 4 Growth of ZnO nanorods on GNPs, from a seed layer produced via mechanical stirring, using a hydrothermal method under static conditions ZnO micro/nanorods are grown on GNPs previously coated with seed layer produced by mechanical stirring, as described in Example 2.
- the aqueous growth solution is prepared as described on page 15, Phase 3, step / ' ).
- the resulting solution is then mechanically mixed via magnetic stiring at room temperature to obtain a turbidity-free solution.
- the GNPs coated with the seed layer are rinsed again with double-distilled water, and the water is removed by centrifugation.
- the GNPs recovered from the sediment are then homogeneously dispersed in the growth solution via vigorous stirring in a centrifuge tube.
- the suspension is then transferred into a glass beaker and put in an appropriately preheated oven between 70°C and 150°C for a time between 1 h and 10 h (hydrothermal technique under static conditions).
- the suspension is centrifugated (at 3095 g for 30 min) for removal of the growth solution and washed twice with double-distilled water.
- the precipitate obtained is dried in an oven at a temperature between 70°C and 180°C for a time between 10 min and 60 min.
- the end product is constituted by GNPs coated by ZnO nano/microrods. As may be noted from SEM micrographs shown in Figure 3, they have a diameter between approximately 40 nm and 150 nm and a length in the 500 nm ⁇ 2 pm range.
- Example 5 Growth of ZnO nanorods on GNPs from a seed layer produced via mechanical stirring, using the hydrothermal methodunder dynamic conditions
- ZnO nanorods are grown on GNPs previously coated with a seed layer produced by means of mechanical stirring, as described in Example 2.
- the growth aqueous solution is prepared as described on page 15, Phase 3, Step / ' ).
- the resulting solution is then mixed mechanically using a mechanical stirrer at room temperature to obtain a turbidity-free solution.
- GNPs coated by the seed layer are rinsed again with double-distilled water, and the water is removed by centrifugation.
- the GNPs recovered from the sediment are then homogeneously dispersed in the growth solution via vigorous stirring in a centrifuge tube.
- the suspension is then transferred into a glass beaker, positioned on a hot plate heated between 40°C and 100°C and mixed continuously by means of a magnetic stirrer for a time between 1 h and 10 h. During the reaction, the solution is kept at constant temperature.
- the suspension is centrifugated (at 3095 g for 30 min) to remove the growth solution and washed twice with double-distilled water.
- the precipitate obtained is dried in oven at a temperature between 70°C and 180°C for a time between 10 min and 60 min.
- the end product is constituted by GNPs coated with ZnO nanorods. As may be noted from the SEM micrographs shown in Figure 4, they have a diameter ranging between approximately 20 nm and 30 nm and a length of between approximately 400 nm and 600 nm.
- Example 6 Growth of ZnO nanorods on GNPs from a seed layer produced by probe sonication, using the hydrothermal method under dynamic conditions
- ZnO nanorods are grown on GNPs previously coated with a seed layer produced by probe sonication, as described in Example 3.
- the aqueous growth solution is prepared as described on page 15, Phase 3, Step / ' .
- the resulting solution is then stirred via magnetic stirring at room temperature to obtain a turbidity-free solution.
- GNPs coated with the seed layer are rinsed again with double-distilled water, and the water is removed by centrifugation.
- the GNPs recovered from the sediment are then homogeneously dispersed in the growth solution via vigorous stirring in a centrifuge tube.
- the suspension is then transferred into a glass beaker, positioned on a hot plate heated between 40°C and 100°C and mixed continuously by means of a magnetic stirrer for a time between 1 h and 10 h. During the reaction the solution is kept at constant temperature.
- the suspension is centrifugated (at 3095 g for 30 min) to remove the growth solution, and washed twice with double-distilled water.
- the precipitate obtained is dried in an oven at a temperature between 70°C and 180°C for a time between 10 min and 60 min.
- the end product is constituted by GNPs coated with ZnO nanorods.
- Example 7 Growth of ZnO nanorods on GNPs, from a seed layer produced by probe sonication, using probe sonication
- ZnO nanorods are grown on GNPs previously coated with a seed layer produced by probe sonication, as described in Example 3.
- the growth aqueous solution is prepared as described on page 15, Phase 3, Step / ' ).
- the resulting solution is then magnetically stirred to obtain a turbidity-free solution.
- GNPs coated with the seed layer are rinsed again with double-distilled water, and the water is removed by centrifugation.
- the GNPs recovered from the sediment are then homogeneously dispersed in the growth solution via vigorous stirring in a centrifuge tube.
- the suspension is then transferred into a glass beaker and subjected to probe sonication for a time between 5 min and 60 min at room temperature, fixing the amplitude of oscillation of the probe between 20% and 100% (of its maximum value).
- the suspension is centrifugated (at 3095 g for 30 min) to remove the growth solution and washed twice with double-distilled water.
- the precipitate obtained is dried in an oven between 70°C and 180°C for a time between 10 min and 60 min.
- the end product is constituted by GNPs coated with ZnO nanorods. As may be noted from the micrographs represented in Figure 6, they present a state of flower-like aggregation shape.
- the diameter of the nanostructures ranges between approximately 20 nm and 40 nm, and the length is between approximately 150 nm and 300 nm.
- the coating density is lower than in the case reported in Example 6 as a result of probe sonication during the growth step of the nanostructures.
- Microrods of ZnO doped with magnesium are grown according to the procedure described on page 15 (Phase 3), adding magnesium nitrate hexahydrate, in the preparation step of the micro/nanostructure-growth solution,.
- the structures thus obtained present a perfectly hexagonal cross section, with a diameter up to 500 nm and a length up to 2 ⁇ 3 pm.
- Control of the size of the ZnO nanostructures and of their coating density on the GNPs is obtained by appropriate definition of the process of deposition of the seed layer and the creation of a system for the hydrothermal growth under dynamic conditions.
- the modality of mixing of the suspension of growth enables control of the morphologies of the structures. This aspect is not found in the existing literature, including the patent literature, and represents a substantial improvement introduced by the present invention as compared to existing techniques.
- the sector of interest of the present invention is that of nanostructured and nanocomposite materials with enhanced electrical, electronic, electromagnetic, mechanical, and catalytic properties.
- Possible subjects interested in the invention are firms that operate in the sector of advanced materials and composite materials and piezoresistive and piezoelectric materials, in the sensors field, and in the production of water-based paints for providing radar-absorbent thin coatings or coatings with sensing properties.
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Application Number | Priority Date | Filing Date | Title |
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ITUB2015A009348A ITUB20159348A1 (en) | 2015-12-21 | 2015-12-21 | PRODUCTION OF GRAPHEN-BASED COMPOSITE NANOSTRUCTURES OBTAINED BY SUSPENSION GROWTH OF NANOROD AND ZnO MICROROD ON UNSUPPORTED GNP FLAKES |
PCT/IB2016/057818 WO2017109693A1 (en) | 2015-12-21 | 2016-12-20 | Production of graphene based composite nanostructures obtained through the growth of zinc-oxide nanorods or microrods on unsupported graphene nanoplatelets in suspension |
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MX2017013705A (en) * | 2017-10-25 | 2019-04-26 | Centro De Investigacion En Quim Aplicada | Nanocomposites of graphene-metals and transition metal oxides and manufacturing methods. |
KR102035553B1 (en) * | 2018-02-12 | 2019-10-23 | 경희대학교 산학협력단 | Method for Patterned Metal Oxide Nanorods |
TWI715142B (en) * | 2019-08-07 | 2021-01-01 | 瑞昱半導體股份有限公司 | Image sensing device and method for auto white balance therefor |
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CN111437834B (en) * | 2020-05-19 | 2022-07-12 | 福州大学 | Method for constructing in-situ heterojunction based on sulfur indium zinc nanosheets and application |
CN111874939A (en) * | 2020-08-14 | 2020-11-03 | 山东理工大学 | Rapid batch preparation method of nano metal oxide |
CN112374528B (en) * | 2020-09-30 | 2023-03-17 | 中国科学院苏州纳米技术与纳米仿生研究所广东(佛山)研究院 | Graphene surface-loaded zinc oxide nanoparticle composite material and preparation method and application thereof |
IT202100000848A1 (en) * | 2021-01-19 | 2022-07-19 | Univ Degli Studi Roma La Sapienza | WATER RESISTANT REMOVABLE MULTILAYER ANTIMICROBIAL COATING FOR CONTACT SURFACES AND ITS PREPARATION METHOD |
CN112885964B (en) * | 2021-01-28 | 2022-11-01 | 北京航空航天大学合肥创新研究院(北京航空航天大学合肥研究生院) | Multi-field regulation memristor and preparation method thereof |
CN113055573A (en) * | 2021-03-26 | 2021-06-29 | 平安开诚智能安全装备有限责任公司 | Mining ann's type intelligent recognition appearance of making a video recording |
CN115504501B (en) * | 2021-06-22 | 2023-10-24 | 中国科学院理化技术研究所 | Microwave heating element zinc oxide and preparation method and application thereof |
CN114864297B (en) * | 2022-05-25 | 2023-03-24 | 河南工业大学 | Preparation method of MXene/zinc oxide/graphene composite material |
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2015
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2016
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CN108698849A (en) | 2018-10-23 |
ITUB20159348A1 (en) | 2017-06-21 |
WO2017109693A1 (en) | 2017-06-29 |
CN108698849B (en) | 2021-04-13 |
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