• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    Process for the production of magnetic cork particles, particles thus obtained and uses thereof. The present invention relates to a process for producing magnetic cork particles comprising the steps of providing a composition of an alkaline solution and cork particles, with a size comprised between 1 nm and 2 mm, and stirring; add an acid solution containing Fe3 + and Fe2 + cations to the composition to cause the magnetization of the cork particles and maintain agitation; filter the obtained solution to obtain a precipitate of magnetized cork particles and wash the precipitate with water until the washing solution reaches a pH comprised between 4 and 7, and allow to dry until obtaining stabilized magnetized cork particles, in which the magnetization of the cork particles is due to the formation of a magnetite coating on the particles, the magnetite adsorbing on the surface of the particle. It also refers to magnetized cork particles thus obtained and their uses. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2698153A1
    申请号:ES201730993
    申请日:2017-07-31
    公开日:2019-01-31
    发明作者:Buendía Juana Abenójar；Queirós Ferreira Barbosa Ana Sofía Oliveira；Casanova Miguel Angel Martínez；Carbas Ricardo Joâo Camilo；López Francisco Javier Velasco；Da Silva Lucas Filipe Martins；Real Romero Juan Carlos Del
    申请人:PONTIFICIA COMILLAS, University of；Universidad Carlos III de Madrid；Universidad Pontificia Comillas；Inst De Ciencia E Inovacao Em Engenharia Mecanica E Engenharia Industrial；Universidade do Porto；
    IPC主号:
    专利说明:

    [0001]
    [0002] Procedure for the production of magnetic cork particles, particles thus obtained and uses thereof
    [0003]
    [0004] Field of the invention
    [0005]
    [0006] The present invention relates to a process for producing magnetic particles. In particular, it relates to a process for obtaining magnetic cork particles, to the particles obtained by this process and to their uses in the manufacture of adhesives, paints or composite materials of polymeric matrix or to form small magnetic pieces that will be applied in different industries .
    [0007]
    [0008] BACKGROUND OF THE INVENTION
    [0009]
    [0010] The demand for new materials with customized properties increases every day, and it is necessary to combine different groups of materials, such as composite materials. Due to these requirements, polymers, paints or adhesives are being developed with improved electrical, thermal, mechanical properties (fatigue, tenacity, impact or wear). A combination of properties is also required, along with the need to obtain lighter materials.
    [0011]
    [0012] In response to this demand, the inventors of the present invention have developed a new method for obtaining magnetized cork particles. In 1981, Massart ( R.Massart, Preparation of aqueous magnetic liquids in alkaline and acidic media, IEEE transactions on magnetics, 17/2 ( 1981) 1247-1248) obtained an aqueous solution of magnetite. By a similar procedure, in 2004, Oliveira et al. They manufactured a composite material of activated magnetic carbon in solution to absorb water contaminants, such as oil ( LCA Oliveira, RVRA Rios, JD Fabris, RM Lake, K. Sapag Magnetic particle technology: A simple preparation of magnetic composites for the adsorption of water contaminants, Journal of Chemical Education, 82 ( 2004) 248-250). Magnetic wood has also been obtained ( B. Hui, G. Li, G. Han, Y. Li, L. Wang, J. Li. Fabrication of magnetic response composite based on wood veneers by a simple in situ synthesis method. and Technology 49 ( 2015) 755-767). With the purpose of To produce the magnetic wood, a coating of chitosan is required followed by a magnetization treatment. Chitosan acts as a bridge that joins the magnetite coating and the wood substrates, which is the key factor for the formation of its strong bonding forces. Another procedure for obtaining magnetic wood was proposed by Dong et al. ( Y. Dong, Yutao Y., Y. Zhang, S. Zhan, J. Li. Combined treatment for fast-growing conversion of poplar wood to magnetic wood with high dimensional stability Wood Science and Technology 50 ( 2016) 503-517) , with magnetization of poplar wood by coprecipitation of ferrous and ferrous ions and subsequent in situ polymerization by impregnation with a solution of furfuryl alcohol.
    [0013]
    [0014] The procedure proposed by the authors of the present invention starts from the same concepts, that is to say, a coprecipitation of ferric and ferrous ions in an alkaline solution, but, in this case, without the need to introduce the iron ions from the solution to the component under vacuum and furfurilation conditions ( Dong et al., 2016), as demonstrated in the wood. It also allows working directly with the particles, without needing them to be in the solution (as Massart et al., 1981, and Oliveira et al., 2004) and it is not necessary to insert nitrogen groups on the surface as in Hui, et. al., 2015. Advantageously, in the process of the present invention, magnetite is adsorbed on the surface of the particles.
    [0015]
    [0016] With the magnetization process proposed in the present invention, cork particles with magnetic properties have been obtained. In composite materials, these particles can be used to modify the final properties. For example, cork modifies the mechanical properties of epoxy adhesives, increasing their resistance to impact and their tenacity ( Barbosa, AQ, da Silva, LF, Ochsner, A., Abenojar, J., & del Real, JC ( 2012) Influence of the size and quantity of cork particles on the toughness of a structural adhesive The Journal of Adhesion, 88 ( 4-6), 452-470). The methodology proposed in the present invention allows to manufacture magnetic cork particles and uses them to reinforce a polymeric matrix, so that the particles can be moved to specific places inside the material before the curing process, thus being able to modify the mechanical properties in locations specific to composite materials.
    [0017]
    [0018] All types of relays contain an electroconductive material and can be moved freely under the effect of an external magnetic field. During their life cycle, the free ends of the plates, directed towards each other, overlap and form a basis for a new type of switching device with a "germ magnetically controlled contact"("germ magnetically controlled contact") ( in Russian) or '' reed switch '' (in English). This contact is called "magnetically controlled contact" because it closes under the influence of an external magnetic field, unlike the contacts of ordinary relays that are commuted with the help of mechanical force applied directly on them ( Reed Switches and Reed Relays in Electric Relays: Principies and applications, Taylor & Francis Group, LLC, 2006). The contact elements of the reed switches are made of ferromagnetic materials with linear expansion coefficients similar to glass. The most frequently used material is Permalloy, an alloy of iron and nickel ( H. Shokrollahi, K. Janghorban, Soft magnetic composite materials ( SMCs), Journal of Materials Processing Technology, 189 ( 2007) 1-12, H. Shokrollah. magnetic and structural properties of the most important alloys of rum produced by mechanical alloying Materials & Design, 30 ( 2009) 3374-3387) (usually 25% nickel in the alloy). Sometimes Kovar (iron alloy, nickel and cobalt) is used for high temperature applications ( Shankar B. Dalavi, J. Theerthagiri, M. Raja Man, RN Panda, Synthesis, characterization and magnetic properties of nanocrystalline FexNi80-xCo20 ternary alloys Journal of Magnetism and Magnetic Materials, 344 ( 2013) 30-34).
    [0019]
    [0020] There are many patents claiming magnetic sensors, but in all cases metal alloys are used (for example, US 6201259 B1 or US 6636391 B2). Advantageously, the natural magnetic particles obtained by the process of the present invention could be shaped to form small magnetic pieces, such as sensors, relays or electromagnets lighter than the metallic ones (for example, iron alloys) currently used.
    [0021]
    [0022] Finally, the magnetized cork particles of the present invention can be used in the manufacture of composite materials, paints or adhesives, taking advantage of their mobility in the polymeric matrix before the curing process.
    [0023] BRIEF DESCRIPTION OF THE DRAWINGS
    [0024]
    [0025] The invention can adopt different physical and chemical forms, the preferred embodiments of which will be described in detail and illustrated in the figures attached to this document:
    [0026]
    [0027] Figure 1.- Low pressure plasma chamber: (left) on the outside and (right) on the inside.
    [0028] Figure 2.- Schematic of the manufacturing process of magnetic particles.
    [0029] Figure 3.- Density of cork particles measured with a helium pycnometer.
    [0030] Figure 4.- Untreated cork particles, in an interval of 250-500. ^ M.
    [0031] Figure 5.- Cork particles, in an interval of 250-500. ^ M, treated in a plasma chamber.
    [0032] Figure 6.- Cork particles, in an interval of 250-500. ^ M, washed.
    [0033] Figure 7.- Magnetic cork particles: (left) 53-38. ^ M (right) 250-125. ^ M.
    [0034] Figure 8.- EDX spectrum of a magnetic cork particle in the area marked in the micrograph .
    [0035] Figure 9.- Elemental mapping obtained from EDX spectra, on a magnetic particle of cork, measured in the area marked in figure 8.
    [0036] Figure 10.- Test with a magnet on the magnetic cork particles: (left) 53 38. ^ m and (right) 250-125. ^ M.
    [0037] Figure 11.- X-ray diffraction pattern of magnetic cork particles obtained with different alkaline solutions. JCPDS number 89-2355 for Fe3O4 (magnetite).
    [0038]
    [0039] Detailed description of the invention
    [0040]
    [0041] In response to the needs of the state of the art, in relation to the search for new materials with customized properties, together with the need to obtain lighter materials, the authors of the present invention have developed a new technique to obtain magnetic particles from of biological materials. In this procedure, the magnetization is produced by applying a coating of magnetite on the biological particle, magnetite adsorbing on the surface of the material.
    [0042]
    [0043] The proposed technique has been applied to cork, to obtain cork particles functionally modified.
    [0044]
    [0045] The present invention thus provides a method for producing magnetic cork particles comprising the steps of:
    [0046]
    [0047] a) Providing a composition comprising an alkaline solution and cork particles, said particles having a size between 1 nm and 2 mm, and shaking;
    [0048] b) Add an acidic solution containing Fe3 + and Fe2 + cations to the composition obtained in a) to cause the magnetization of the cork particles and maintain the agitation;
    [0049] c) Filter the solution obtained in b) to obtain a precipitate of magnetized cork particles, and
    [0050] d) Wash the precipitate with water until the washing solution reaches a pH between 4 and 7 and allow to dry until obtaining stabilized magnetized cork particles.
    [0051]
    [0052] The particles are dried until they reach constant weight; the time depends on the water absorbed by the cork.
    [0053]
    [0054] The magnetization of the cork particles in b) is due to the formation of a magnetite coating on the particles, the magnetite adsorbing on the surface of the particle.
    [0055]
    [0056] In a particular embodiment, the alkaline solution of step a) is NaOH or NH3. In a preferred embodiment, 8-15 grams of cork particles are used per liter of alkaline solution.
    [0057]
    [0058] The acid solution of step b), which contains Fe3 + and Fe2 + cations, has a pH between 1.5 and 2.5, and is obtained from ferric or ferrous chloride salts or sulfates. Both solutions are processed to produce magnetite. In a preferred embodiment, the Fe3 + / Fe2 + cations maintain a molar ratio of 5/3, according to the chemical reaction.
    [0059] In the process of the present invention, the control of the pH is essential for the formation of magnetite, since at a very acid pH a brownish quasi-gelatinous precipitate is formed and at a pH around 4 the magnetite begins to stabilize and settle on the cork particles. This stabilization ends with the neutral pH.
    [0060]
    [0061] In particles with low surface energy, it is necessary to increase their surface energy using mechanical treatments or chemical modifications, to increase their wettability and allow them to adhere to other materials. This group of materials includes polymers and most natural materials, such as cork. Surface treatments are used to increase surface energy, with surface energy being a measure of intermolecular forces. When a solid has high surface energy, it attracts liquids better and is said to be moistened by them.
    [0062]
    [0063] In the process of the present invention, the magnetite particles must be adsorbed on the surface by the particles to be treated. Therefore, it is necessary to have an adequate previous surface energy together with a surface cleaning.
    [0064]
    [0065] Accordingly, in particular embodiments of the method of the present invention, surface pretreatments of the cork particles may be necessary. These pretreatments include cleaning or surface activation treatments that promote the magnetization process.
    [0066]
    [0067] Therefore, in a particular embodiment of the process of the present invention, the pretreatment includes washing the cork particles with deionized water, acetone and ethanol, and allowing them to dry.
    [0068]
    [0069] In another particular embodiment, the pretreatment step includes treating and cleaning the cork particles in a low pressure plasma chamber with different gases (air, oxygen or other inert gases).
    [0070]
    [0071] Plasma is a strongly ionized gaseous material with an equal number of positive and negative free electric charges. When the plasma comes into contact with the surface of any material, its energy is released and transmitted to that surface. The principle of the process is based on the interactions between the plasma particles and the surface of the material ( FF Chen, MD Smith, Plasma in Van Nostrand's Scientific Encyclopedia, John Wiley & Sons, Inc. 2007, A. Schutze, JY Jeong, SE Babayan, J. Park, GS Selwyn, RF Hicks, The atmospheric-pressure plasma jet: a review and comparison to other plasma sources, IEEE Transactions on Plasma Science, 26/6 ( 1998) 1685-1694). The effects that can be obtained through plasma treatment are: cleaning, surface activation and surface erosion.
    [0072]
    [0073] The magnetization process was carried out in an aqueous solution and, after stabilization of this procedure, the magnetization of the particles was achieved. After the process of drying the particles in step d), the magnetization is maintained.
    [0074]
    [0075] In another main aspect of the present invention, those magnetized cork particles obtained by the process of the present invention are contemplated.
    [0076]
    [0077] The magnetic cork particles thus obtained can be introduced into a polymeric matrix and dispersed in such a way as to provide different mechanical, wear or electrical properties to the material. Once the particles are embedded or embedded in the resin matrix and the curing process is finished, the magnetic properties are no longer observed.
    [0078]
    [0079] Therefore, another aspect of the present invention relates to the use of magnetized cork particles thus obtained in the manufacture of polymer matrix composite materials. Particularly, the magnetized cork particles constitute between 0.01 and 70% of the total volume of the composition of the composite material.
    [0080]
    [0081] The main objective of the present invention is to develop a technique capable of obtaining functionally modified cork particles in order to provide magnetic properties, which can be moved by a magnet by means of attraction. Therefore, the particles can be embedded in a resin (adhesive or paint) in order to modify their mechanical, electrical, thermal or wear properties in specific areas where they could be demanded.
    [0082]
    [0083] Therefore, another aspect of the present invention relates to the use of the particles of magnetic corks obtained by the process of the present invention in the manufacture of adhesive or paint compositions. The magnetized cork particles constitute between 0.01 and 40% of the total volume of the composition.
    [0084]
    [0085] At the same time, in some cases, these magnetic particles can be used in the manufacture of small magnetic parts, such as sensors, relays or electromagnets lighter than the metal currently used and applied in a large number of industries.
    [0086]
    [0087] EXAMPLES
    [0088]
    [0089] Materials and pretreatments
    [0090]
    [0091] In this example, the cork particles were subjected to a pre-treatment to obtain a suitable previous surface energy together with a surface cleaning.
    [0092]
    [0093] Therefore, two alternative pretreatments of the cork particles in the magnetization process were carried out, which are detailed below:
    [0094]
    [0095] 1. 3-3.5 g of cork particles were washed progressively with 100 ml of deionized water, acetone and ethanol. The particles were allowed to dry until the next day to carry out the magnetization process; or
    [0096] 2. The particles were treated and cleaned in the plasma chamber at low pressure for 5 minutes at low power with air (figure 1). Several articles on the effect of plasma on particles have been published in relation to this topic ( J. Abenojar, AQBarbosa, Y. Ballesteros, JC del Real, LFM da Silva, MA Martínez.) Effect of surface treatments on cork: surface energy, adhesion and acoustic insulation, Wood Science and Technology 48/1 ( January 2014) 207-224; AQ Barbosa, M. Figueiredo, L. da Silva, A. Ochsner, J. Abenojar, Toughness of a brittle epoxy resin reinforced with micro cork particles: effect of size, amount and surface treatment Composites Part B, 114 ( 2017) 299-310, DOI: 10.1016 / j.compositesb.2016.10.072).
    [0097] Magnetization
    [0098]
    [0099] For the magnetization treatment, a solution of Fe3 + / Fe2 + cations obtained from ferric or ferrous chloride salts or sulfates was necessary. These cations, according to the chemical reaction of magnetite formation, should maintain a molar ratio of 5/3 in the solution of 20 g / l (maintaining the stoichiometry of the reaction, the volume can be changed). This solution of iron cations has an acidic pH of 2.0.
    [0100]
    [0101] A 1 M solution of ammonia (pH 12) was used as the alkaline solution. A solution of NaOH (5 M) could also be used as an alkaline solution. The control of the pH was essential for the formation of magnetite, since at a very acidic pH a brownish quasi-gelatinous precipitate formed and at a pH around 4 the magnetite began to stabilize and settle on the cork particles. This stabilization ended with neutral pH.
    [0102]
    [0103] The magnetization process follows the scheme presented in figure 2. 12 grams of particles were added per liter of ammonia solution. With the help of a magnetic plate and a magnet, the particles were agitated in the ammonia (1). From a burette, the solution of Fe cations was added dropwise onto the ammonia with the particles to be magnetized (2), maintaining a gentle agitation.
    [0104]
    [0105] After adding all the solution, it was kept under gentle agitation for about 5 minutes and then another 5 minutes at rest. The resulting solution had a pH of about 9.5. The solution was then filtered and the precipitate had to be washed with deionized water (3) to a pH of 6.5. Once the desired pH was obtained, it was allowed to dry for about 6 hours in an oven at 60 ° C, until a constant mass was reached.
    [0106]
    [0107] Characterization
    [0108]
    [0109] In order to study the effect of magnetization, the powder density was measured using a helium pycnometer. The morphology of the material was also studied with scanning electron microscopy (SEM) and X-ray diffraction tests were performed.
    [0110]
    [0111] To prove that the magnetic particles had been magnetized, the samples were tested with neodymium magnets (disc magnets 0 60 mm, height 5 mm and 0 30 mm, height 15 mm, neodymium, N42, nickel-plated by Supermagnetec).
    [0112]
    [0113] Results
    [0114]
    [0115] Figure 3 shows the density results measured with the helium pycnometer for different particle sizes of cork. An increase of 13.5% was observed for smaller particles (38-53 ^ m) and of 17.5% for larger particles (125 and 250 ^ m), which leads to the conclusion that magnetite It was present in the particles. The larger particles had more cavities in which magnetite could be deposited. Although the smallest particles have more surface available for the deposition of magnetite, they also present less quantity of cavities, so a difference between the densities is observed.
    [0116]
    [0117] The amount (by volume) of cork particles added to the polymer matrix is, therefore, intrinsically bound to the density; There is a need to recalculate its value taking into account this increase in density.
    [0118]
    [0119] Figure 4 shows the cork particles without any treatment, where the honeycomb structure, characteristic of the cork, is clearly identified. In the particles analyzed, the thickness of the cell wall was between 1.5 and 2 ^ m. When the plasma treatment is carried out, a decrease in the cell wall size of up to 0.4 ^ m and a deformation in the particle is apparently observed ( FIG. 5 ). However, this effect was not detected when the particles were washed ( figure 6 ).
    [0120]
    [0121] In the particles treated in a plasma chamber an improved union between cork and magnetite is observed, compared to the washed particles. However, the cork particles can be magnetized with the two pretreatments. In figure 7 it can be seen how the particles are completely coated independently of their size, and the honeycomb structure of the cork particles is not perceived.
    [0122]
    [0123] When the cork particles were analyzed by EDX (X-ray spectra of dispersive energy), the present elements and their quantity were revealed and the presence of iron in the particles was confirmed. According to figure 8 , in the area analyzed, found carbon, peak K (7.88% by weight), oxygen, peak K (56.49% by weight) and iron, peak L (35.63% by weight). Figure 9 shows an elementary mapping obtained in the same area as Figure 8 . Although the lack of flatness of the particles does not allow an elementary mapping over the entire area, it is possible to observe the presence of the three elements in the analyzed zone.
    [0124]
    [0125] Using a magnet, it showed how all the particles were attracted, regardless of their size (see Figure 10 ). The presence of magnetite in the cork particles was also studied by X-ray diffraction. The cork, which is an amorphous material, presents the characteristic diffractogram of any amorphous material. When the magnetic cork was studied by X-ray diffraction (figure 11 ), the presence of magnetite can be observed by coincidence with the pattern of magnetite n ° 89-2355. In this analysis, the test was carried out in parts where the alkaline solution of ammonium hydroxide or dissociated ammonia (NH4OH) was changed to sodium hydroxide (NaOH). The results are the same, coinciding the magnetite with the same pattern.
    权利要求:
    Claims (16)
    [1]
    A process for the production of magnetic cork particles, the method comprising the steps of:
    a) Providing a composition comprising an alkaline solution containing cork particles, said particles having a size between 1 nm and 2 mm, and shaking;
    b) Add an acidic solution containing Fe3 + and Fe2 + cations to the composition obtained in a) to cause the magnetization of the cork particles and maintain the agitation;
    c) Filter the solution obtained in b) to obtain a precipitate of magnetized cork particles, and
    d) Wash the precipitate with water until the washing solution reaches a pH between 4 and 7 and allow to dry until obtaining stabilized magnetized cork particles.
    in which the magnetization of the cork particles in b) is due to the formation of a magnetite coating on the particles, the magnetite adsorbing on the surface of the particle.
    [2]
    2. Process according to claim 1, wherein the alkaline solution of step a) is NaOH or NH3.
    [3]
    3. Process according to claim 1 or 2, wherein the acid solution has a pH between 1.5 and 2.5.
    [4]
    4. Process according to claim 3, wherein the acid solution of step b), which contains Fe3 + and Fe2 + cations, is obtained from ferrous or ferric chloride salts or sulfates.
    [5]
    5. Process according to any of claims 1-4, wherein the Fe3 + / Fe2 + cations maintain a molar ratio of 5/3.
    [6]
    The process according to any of the preceding claims, wherein the cork particles are subjected to a surface pretreatment before step a).
    [7]
    The method according to claim 6, wherein the pretreatment is a surface cleaning or activation treatment.
    [8]
    The process according to claim 7, wherein the pretreatment includes washing the cork particles with deionized water, acetone and ethanol, and allowing them to dry.
    [9]
    The method according to claim 7, wherein the pretreatment includes treating and cleaning the cork particles in a low pressure plasma chamber with a gas.
    [10]
    10. Magnetized cork particles obtained by the method according to claims 1-9.
    [11]
    11. Use of magnetized cork particles, according to claim 10, for the manufacture of adhesive or paint compositions.
    [12]
    12. Use according to claim 11, wherein the magnetized cork particles constitute between 0.01 and 40% of the total volume of the composition.
    [13]
    13. Use of magnetized cork particles, according to claim 10, for the manufacture of polymer matrix composite materials.
    [14]
    14. Use according to claim 13, wherein the magnetized cork particles constitute between 0.01 and 70% of the total volume of the composition of the composite material.
    [15]
    15. Use of magnetized cork particles, according to claim 10, for the manufacture of small magnetic particles.
    [16]
    16. Use according to claim 15, wherein the small magnetic particles are sensors, relays or electromagnets.
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    同族专利:
    公开号 | 公开日
    US20210139707A1|2021-05-13|
    WO2019025651A1|2019-02-07|
    EP3663060A1|2020-06-10|
    ES2698153B2|2019-06-07|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    JP3646508B2|1998-03-18|2005-05-11|株式会社日立製作所|Tunnel magnetoresistive element, magnetic sensor and magnetic head using the same|
    JP3462832B2|2000-04-06|2003-11-05|株式会社日立製作所|Magnetic resistance sensor, magnetic head and magnetic recording / reproducing apparatus using the same|
    KR100790580B1|2006-12-04|2008-01-03|장상준|Cork sheet having adhesinveness|
    EP2258899A1|2009-06-02|2010-12-08|Tarkett GDL S.A.|Magnetic layered structure|
    CN105964231B|2016-05-24|2018-09-14|东北林业大学|It is a kind of using wood powder as the preparation method of the recyclable super-hydrophobic super-oleophylic adsorbent of magnetism of raw material|
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    ES201730993A|ES2698153B2|2017-07-31|2017-07-31|Procedure for the production of magnetic cork particles, particles thus obtained and uses thereof|ES201730993A| ES2698153B2|2017-07-31|2017-07-31|Procedure for the production of magnetic cork particles, particles thus obtained and uses thereof|
    EP18795693.3A| EP3663060A1|2017-07-31|2018-07-23|Method for producing magnetic cork particles, particles thus obtained, and uses thereof|
    PCT/ES2018/070519| WO2019025651A1|2017-07-31|2018-07-23|Method for producing magnetic cork particles, particles thus obtained, and uses thereof|
    US16/635,947| US20210139707A1|2017-07-31|2018-07-23|Method for producing magnetic cork particles|
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