FUNCTIONAL MATERIAL AND METHOD FOR MANUFACTURING THE SAME
20220145487 · 2022-05-12
Inventors
Cpc classification
B05D2601/24
PERFORMING OPERATIONS; TRANSPORTING
C09D147/00
CHEMISTRY; METALLURGY
D06M16/00
TEXTILES; PAPER
C09D125/18
CHEMISTRY; METALLURGY
C25D13/22
CHEMISTRY; METALLURGY
B05D5/12
PERFORMING OPERATIONS; TRANSPORTING
C09D5/14
CHEMISTRY; METALLURGY
B01D39/16
PERFORMING OPERATIONS; TRANSPORTING
B05D7/546
PERFORMING OPERATIONS; TRANSPORTING
D06M15/356
TEXTILES; PAPER
C09D5/4492
CHEMISTRY; METALLURGY
B05D2601/20
PERFORMING OPERATIONS; TRANSPORTING
International classification
C09D125/18
CHEMISTRY; METALLURGY
C09D147/00
CHEMISTRY; METALLURGY
C09D5/00
CHEMISTRY; METALLURGY
C09D5/14
CHEMISTRY; METALLURGY
Abstract
The present invention relates to a material having various functions such as antimicrobial function or waterproof function, as well as a method and an apparatus for manufacturing the same. The method for manufacturing a functional material according to the present invention includes coating a surface of conductive or non-conductive material with an electrically charged microfine material having a size of nano- or micro-units, thereby imparting functionality to the material simultaneously with maintaining intrinsic properties thereof.
In addition, the method for manufacturing a functional material, according to the present invention, had advantages in which: repeating a process of coating the surface of the conductive or non-conductive material with a functional substance can impart a plurality of desired functions to the material, in addition, a thickness of the functional material may be easily adjusted, and a large area/large quantity may be produced by a simplified process using a general material in a short period.
Claims
1. A method for manufacturing a functional material, comprising: preparing a material to be coated, wherein the material is a conductive material or a non-conductive material present on a conductive substrate; immersing the material in a polymer suspension having an electric charge to form a first coating layer on the surface of the material; and immersing the polymer-coated material in an electrolyte in which particles having functional properties (“functionality”) are dispersed, and then, forming a second layer by applying power a DC voltage to two electrodes, wherein the electrodes are consist of the polymer-coated material or the conductive substrate as a first electrode, and a second electrode as a conductive substrate facing to the first electrode, so as to form a second coating layer above the first coating layer.
2. The method according to claim 1, wherein the non-conductive material is a material to absorb the electrolyte or a material having a porous structure.
3. The method according to claim 1, wherein the formation of the first coating layer includes forming two or more layers by a lamination method (“layer-by-layer assembly”), wherein adjacent deposited layers are formed by immersing the same in a polymer suspension having opposite charges from the layers.
4. The method according to claim 1, wherein formation of the first coating layer includes: immersing the material having a positively charged surface in a poly(sodium 4-styrene sulfonate) (PSS) solution having a negative charge to form a first polymer coating layer; and immersing the material having the first polymer coating layer formed thereon in a poly(diallyldimethyl diammonium chloride) (PDDA) solution having a positive charge to form a second polymer coating layer.
5. The method according to claim 4, further comprising: forming a plurality of polymer coating layers by repeatedly conducting the formation of the first polymer coating layer and the formation of the second polymer coating layer.
6. The method according to claim 1, wherein the formation of the second coating layer includes forming two or more layers by treating the particles having different functionalities through electrophoretic deposition (EPD).
7. The method according to claim 6, wherein, if the non-conductive material is a fabric, the formation of the second coating layer includes: forming a first functional coating layer by immersing the fabric in the electrolyte in which first particles having antimicrobial properties are dispersed; and forming a second functional coating layer by immersing the fabric in the electrolyte in which second particles having hydrophobicity are dispersed.
8. The method according to claim 7, wherein formation of the first functional coating layer uses a polyethylenimine solution as a dispersant.
9. The method according to claim 6, wherein, if the non-conductive material is a fabric, formation of the second coating layer includes: immersing the fabric in the electrolyte in which first particles having antimicrobial properties- and second particles having hydrophobicity are dispersed; and conducting electrophoretic deposition (EPD) to form the second coating layer having antimicrobial properties and hydrophobicity.
10. The method according to claim 7, wherein the first particles are at least one selected from the group consisting of zinc oxide (ZnO), silver (Ag), gold (Au), copper oxide (CuO), titanium oxide (TiO.sub.2) and magnesium oxide (MgO).
11. The method according to claim 7, wherein the second particles are at least one selected from the group consisting of silicon dioxide (SiO.sub.2), zinc oxide (ZnO), titanium oxide (TiO.sub.2), cadmium sulfide (CdS) and strontium titanate (SrTiO.sub.3).
12. The method according to claim 1, further comprising heat treatment of the above material after the formation of the second coating layer.
13. The method according to claim 12, wherein the first coating layer includes a thermosetting polymer layer formed by immersing the material in the suspension in which the thermosetting polymer is dispersed, wherein the thermosetting polymer includes polyamide or polyvinylidene fluoride.
14. The method according to claim 12, wherein the formation of the second coating layer includes immersing the material in the electrolyte in which a thermosetting polymer is dispersed, wherein the thermosetting polymer includes polyamide or polyvinylidene fluoride.
15. A functional material, comprising: a conductive material or a non-conductive material which is prepared on a conductive substrate, to be coated; and first and second coating layers successively formed on the surface of the material, wherein the first coating layer is formed by immersing the material in a charged polymer suspension, and the second coating layer is formed by immersing the material having the first coating layer in an electrolyte in which functional particles are dispersed, and then applying a DC voltage to the substrate as a first electrode and a second electrode which is another electrode opposite to the above first electrode, thereby forming the second coating layer above the first coating layer.
16. The method according to claim 9, wherein the first particles are at least one selected from the group consisting of zinc oxide (ZnO), silver (Ag), gold (Au), copper oxide (CuO), titanium oxide (TiO.sub.2) and magnesium oxide (MgO).
17. The method according to claim 9, wherein the second particles are at least one selected from the group consisting of silicon dioxide (SiO.sub.2), zinc oxide (ZnO), titanium oxide (TiO.sub.2), cadmium sulfide (CdS) and strontium titanate (SrTiO.sub.3).
Description
BRIEF DESCRIPTION OF DRAWINGS
[0025]
[0026]
[0027]
[0028]
[0029]
[0030]
[0031]
[0032]
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS OF INVENTION
[0033] Various modifications may be added to the present invention and different embodiments may be included. Therefore, specific embodiments will be illustrated in the drawings and described in detail in the description.
[0034] However, this is not intended to limit the present invention to specific embodiments, and it is to be understood that the present invention includes all changes, equivalents, and substitutes within the spirit and scope of the present invention.
[0035]
[0036] As shown in
[0037] In other words, in order to overcome a problem of difficulty in depositing a charged material present in an electrolyte on an electrode made of a typical non-conductive material by electrophoretic deposition (EPD), the method for manufacturing a functional material according an embodiment of the present invention may firstly form a first coating layer using a charged polymer and then form a second coating layer above the first coating layer by EPD.
[0038] Further, the material to be coated may be conductive and, in order to overcome non-uniformity of coating occurring when the above conductive material as an electrode is coated with functional microparticles by EPD, the first coating layer may be firstly formed using the charged polymer, followed by forming the second coating layer above the first coating layer by EPD.
[0039] At this time, if the second coating layer is formed on the surface of a non-conductive material by EPD using an electrolyte in which functional microparticles having a nano- or micro-scale size are dispersed, the functionality may be imparted while maintaining inherent characteristics of the material.
[0040] Meanwhile, in order to manufacture a functional material, firstly, a material to be coated may be prepared (S10).
[0041] Herein, the material may be conductive or may be non-conductive and provided on a conductive substrate. The material to be coated (“coating object”) having imparted functionality may be conductive or non-conductive.
[0042] The conductive material or the conductive substrate is not particularly limited in terms of shape or substance thereof as long as it is intended to transfer electricity and, as shown in Table 1 below, may include, for example, a non-metallic substance such as carbon-containing vinyl, felt, etc., or at least one selected from the metal group consisting of stainless steel, titanium, nickel, silver, gold, platinum, etc.
TABLE-US-00001 TABLE 1 Materials Conductive Conductive yarn (carbon felt, graphite, Teflon), alloy (aluminum, copper, magnesium, duralumin . . .), titanium, stainless steel, nickel, silver, gold, platinum
[0043] Further, the non-conductive material provided on the conductive substrate is also not particularly limited in terms of shape and substance thereof and, as shown in Table 2 below, may include, for example, at least one selected from the group consisting of synthetic resin such as polyester, cotton, fabric, paper, filter, membrane, etc.
TABLE-US-00002 TABLE 2 Materials Non-conductive Synthetic resin, fabric (cotton, polyester, nylon . . .), filter, paper, membrane
[0044] However, the non-conductive material provided on the conductive substrate, according to an embodiment of the present invention, preferably has a porous structure or can absorb an electrolyte.
[0045] This is because an electric field can be easily generated across the non-conductive surface existing between two electrodes.
[0046] According to an embodiment of the present invention, in order to provide the non-conductive material on the conductive substrate, the non-conductive material may be attached to the conductive substrate. Alternatively, the conductive substrate may be rolled in the form of a rod, and the non-conductive material may be wrapped around the rolled conductive substrate. According to a specific embodiment, a thin titanium plate may be rolled and a fabric (for example, cotton fabric, polyester fabric, etc.) may be wrapped around the same and provided.
[0047] Such prepared material as the coating object may be immersed in a polymer suspension having a charged surface in order to form a first coating layer on the surface of the material (S20).
[0048] According to an embodiment of the present invention, in order to form the first coating layer on the non-conductive material, a lamination method (layer-by-layer assembly) may be used.
[0049] According to the lamination method, the surface of the non-conductive material may be modified and a thin film coating may be formed using a substance charged opposite to the above surface of the non-conductive material.
[0050] According to an embodiment of the present invention, polymers having positive or negative charges may be repeatedly laminated on the surface of the non-conductive material by turns according to electrostatic attraction. If the first coating layer is provided in plural, adjacent deposited layers may have opposite charges from each other. As such, repeatedly laminating the polymers may desirably adjust the thickness of the first coating layer as necessary.
[0051] Specifically, when the prepared non-conductive material has a positively or negatively charged surface, the material may be firstly immersed in a negatively or positively charged polymer suspension, followed by secondly immersing the material in another positively or negatively charged polymer suspension, thereby providing a first coating layer having two layers. Of course, repeating the above immersion process may produce a first coating layer having three or more layers. Alternatively, using a suspension including a mixture of different particles having various functions may prepare a first coating layer including the mixture of different particles by EPD at one time.
[0052] At this time, after each immersion process is finished, the remaining polymer is preferably removed by washing the surface of the non-conductive material with deionized water.
[0053] According to an embodiment of the present invention, a surface of titanium wrapped with fabric may be positively charged, and the positively charged material may be immersed in a negatively charged poly(sodium 4-styrene sulfonate) (PSS) solution for 2 to 4 minutes, preferably 3 minutes, to form a first polymer coating layer. Then, after washing the product for 10 seconds, the first polymer coating layer may be immersed in a positively charged poly(diallyldimethyl diammonium chloride) (PDDA) solution for 2 to 4 minutes, preferably 3 minutes, to form a second polymer coating layer, thereby providing a first coating layer composed of multiple layers.
[0054] Herein, the PSS solution may be prepared by dissolving 30% by weight (“wt. %”) of PSS in deionized water, while the PDDA solution may be prepared by dissolving 35 wt. % of PDDA in deionized water.
[0055] An immersion time in the PSS or PDDA solution may be the optimum time induced by repetitive experiments so that charges are sufficiently deposited on the surface of a material. It is recommended to coat for at least 2 minutes, preferably 3 minutes or more. That is, a sufficiently long immersion time may be desirable for electrostatic deposition of the polymer. However, in order to form a uniform coating on the surface or to stably deposit the second coating layer on the surface, immersion is preferably conducted for at least 2 or 3 minutes. At this time, the immersion time may vary in consideration of characteristics of the surface to be coated and characteristics of particles.
[0056] Since the PSS solution and the PDDA solution have high surface charge, these may be deposited on the material according to stronger electrostatic attraction. Further, since the first coating layer made of a polymer substance is interposed between the above material and the second coating layer, mechanical bonding force therebetween may be improved. Specifically, the mechanical bonding force may further be improved through heat treatment.
[0057] Meanwhile, in order to impart functionality to the material on which the first coating layer is formed, the material may be immersed in an electrolyte in which microparticles having functionality are dispersed. Further, electric power may be applied to a conductive material or a conductive substrate as a first electrode, as well as a second electrode which is another electrode opposite to the first electrode, thereby forming a second coating layer on the first coating layer (S30).
[0058] In this regard, microparticles may have desired functions to be imparted to the material and are not specifically limited. For example, one or more substances having different functions such as antimicrobial, hydrophobic, hydrophilic, conductive, anti-inflammatory or pyrogenetic, heat resistance, flame resistance, and UV blocking properties may be used.
[0059] More specifically, the microparticles used for coating the material to impart functionality thereto may be any of the materials shown in Table 3 below or surface-treated with the same and, of course, the second coating layer may include a plurality of functional coating layers in order to impart different functions to the material.
TABLE-US-00003 TABLE 3 Materials Antimicrobial ZnO, Ag, Au, CuO, TiO.sub.2, MgO properties Hydrophobicity Superhydrophobic SiO.sub.2, Hydrophobic decanethiol-modified silver nanoparticles, Hydrophobic kaolin, PA-Ag, OA-Fe.sub.3O.sub.4 Hydrophilicity Superhydrophilic SiO.sub.2, ZnO, TiO.sub.2, CdS, SrTiO.sub.3 Conductivity Ni, Au, Cu, Ag Anti- Ceramics, urea, borax, guanidine sulfamate, antimony inflammatory trioxide properties UV blocking ZnO, TiO.sub.2, CeO.sub.2, CdS, SrTiO.sub.3 properties
[0060] Meanwhile, according to an embodiment of the present invention, electrophoretic deposition, that is, EPD may be used to form a second coating layer on the first coating layer.
[0061] When depositing the second coating layer above the first coating layer by EPD, deposition quality may be affected by the electrolyte in which microparticles are dispersed. Specifically, in the case of using a water-soluble electrolyte, even if the microparticles have a high surface charge when an electric field is generated bubbles and heat are generated due to electrolysis, thus causing poor deposition quality.
[0062] Therefore, according to an embodiment of the present invention, the electrolyte used for forming the second coating layer is preferably an organic solvent generally used in electrophoresis. Alternatively, an organic solvent and an aqueous solution may be mixed and used. Specifically, for dispersion of hydrophobic SiO.sub.2 particles, deionized water is preferably added to methanol. More particularly, an electrolyte in which 85 to 95% by volume (“vol. %”), preferably, 90 vol. % of methanol and 5 to 15 vol. %, preferably, 10 vol. % of deionized water are mixed may be prepared and provided to minimize effects of electrolysis or to acquire higher surface charge. Further, pH adjustment may be easily implemented when mixing the organic solvent and the aqueous solution, thereby effectively regulating the surface charge of the particles. Because of the functional particles proposed above, the organic solvent and the aqueous solution in a pure state may be used without pH adjustment.
[0063] Further, adjusting the intensity of the electric field formed by the power applied to the first and second electrodes may control a deposition rate and enable the deposition of microparticles having different levels of surface charge. That is, increasing the electric field intensity may improve the deposition rate and enable the deposition of microparticles having a low level of surface charge.
[0064] Further, the thickness of the second coating layer may be adjusted by altering a time for application of the electric field. Herein, the electric field intensity, a size of the electrode, a concentration of microparticles in the electrolyte, etc. are preferably constant.
[0065] Specifically, according to an embodiment of the present invention, if the material is a fabric, the material having the first coating layer formed thereon may be firstly immersed in an electrolyte, in which first microparticles having antimicrobial properties are dispersed, to form a first functional coating layer, followed by immersing the material having the first functional coating layer formed thereon in another electrolyte, in which second microparticles having hydrophobicity are dispersed, to form a second functional coating layer, whereby antimicrobial properties and hydrophobicity are imparted to the fabric. Of course, it is possible to form the second functional coating layer having hydrophobicity only without formation of the first functional coating layer having antimicrobial properties or, otherwise, to form the first functional coating layer having antimicrobial properties only without formation of the second functional coating layer having hydrophobicity.
[0066] According to an embodiment of the present invention, in order to form the first functional coating layer having antimicrobial properties, the material having the first coating layer formed thereon may be immersed in an electrolyte in which ZnO microparticles are dispersed.
[0067] In this regard, a dispersant may be added to the electrolyte, and the dispersant is preferably a polyethylenimine (PEI) solution. Since the size and surface charge of ZnO microparticles depend on pH value and strong acidic or basic electrolytes may damage the fabric, PEI is recommended to minimize a particle size while having high surface charge in the neutral pH range.
[0068] For instance, an electrolyte was prepared by dispersing 5 g/L of PEI solution and 2 g/L of ZnO microparticles in methanol. Herein, the PEI solution was prepared by dissolving 50 wt. % of PEI in water.
[0069] In this regard, a time for immersing the material in the electrolyte mixed with ZnO-PEI solution to form the first functional coating layer is not particularly limited, but, preferably in the range of 3 to 4 minutes at an electric field intensity of 5 V/cm to 10 V/cm, specifically, when an electric field of 7.5 V/cm is formed by applying a DC voltage of 30V between two electrodes at an interval of 4 cm.
[0070] As shown in
[0071] Further, in order to form a second functional coating layer having hydrophobicity, the material having the first functional coating layer formed thereon may be immersed in an electrolyte, in which SiO.sub.2 microparticles, specifically polydimethylsiloxane (PDMS)—SiO.sub.2 microparticles are dispersed.
[0072] For instance, another electrolyte was prepared by dispersing 1 g/L of hydrophobic silica (SiO.sub.2) microparticles in the above electrolyte. At this time, the hydrophobic silica (SiO.sub.2) used herein is a microparticle having a size of 14 nm.
[0073] In this regard, the second functional coating layer having hydrophobicity is formed. In fact, in order to impart super-hydrophobic function with a contact angle of 150° or more to water droplets, as shown in
[0074] However, in this case, since SiO.sub.2 dispersed in the electrolyte is negatively charged, the previously power-applied electrode to form the first functional coating layer should be power-applied in opposite directions (see
[0075] Meanwhile, according to an embodiment of the present invention, after the formation of the second coating layer (S30), heat treatment of the material may be further included.
[0076] The first coating layer may be a polymer material, and mechanical bonding force between the non-conductive material and the second coating layer having functionality may be improved through heat treatment.
[0077] Therefore, the first coating layer preferably includes a thermosetting polymer layer. That is, the thermosetting polymer layer may be formed by immersing the material in a suspension in which the thermosetting polymer is dispersed. Herein, the thermosetting polymer may be at least one selected from the group consisting of polyamide, polyvinylidene fluoride, and the like.
[0078] Specifically, after the formation of the second polymer coating layer, the thermosetting polymer layer may be formed by immersing the coating layer in the suspension in which the thermosetting polymer is dispersed for a predetermined time, so as to form a thermosetting polymer layer. Of course, it is recommended to wash the surface of the second polymer coating layer with purified water before immersion in the suspension in which the thermosetting polymer is dispersed.
[0079] According to another embodiment, when forming the second coating layer (S30), a thermosetting polymer may also be added to the electrolyte and dispersed therewith, followed by immersing the material in the above electrolyte so that a thermosetting function may be imparted when the second coating layer (for example, the first or second functional coating layer) through EPD. Likewise, the thermosetting polymer may be at least one selected from the group consisting of polyamide or polyvinylidene fluoride, and the like.
[0080] Heat treatment in the heat treatment process may be performed by drying the material having the first and second coating layers formed thereon at room temperature to evaporate the residual electrolyte, and then, applying heat to the material at 100° C. or higher, preferably 140° C. to 160° C. using a hot press, thereby improving mechanical bonding force between the non-conductive material and the first coating layer, and/or between the first coating layer and the second coating layer.
[0081] Hereinafter, the present invention will be described in more detail through examples according to the present invention, but the scope of the present invention is not limited by the examples presented below.
Example 1
[0082] As shown in
[0083] To an electrolyte prepared by mixing 90 vol. % methanol and 10 vol. % purified water, a PEI solution in which 50% by weight of polyethylenimine (PEI) is dissolved in water, followed by dispersing ZnO microparticles therein (that is, 2 g/L of ZnO microparticles dispersed in 1 g/L of PEI solution) was added to prepare a desired electrolyte. As shown in
Example 2
[0084] In the same manner as described in Example 1 above, the antimicrobial coating layer was formed. Thereafter, an electrolyte was prepared by mixing 90 vol. % of methanol and 10 vol. % of purified water, followed by dispersing 1 g/L of polydimethylsiloxane (PDMS)—SiO.sub.2 microparticles (with a particle diameter of 14 nm) in the above electrolyte, thereby preparing a desired electrolyte. Then, as shown in
[0085] Consequently, as shown in
Example 3
[0086] As shown in
[0087] In an electrolyte prepared by mixing 90 vol. % methanol and 10 vol. % purified water, 1 g/L of polydimethylsiloxane (PDMS)—SiO.sub.2 microparticles (with a particle diameter of 14 nm) were dispersed to prepare a desired electrolyte. As shown in
Experimental Example 1
[0088] The antimicrobial properties of the commercially available polyester fabric and the functional fabric coated with only ZnO microparticles before applying the SiO.sub.2 microparticles according to Example 1 were compared.
[0089]
[0090] In this regard, each E. coli cell culture experiment was conducted for 120 minutes under the condition of applying 1 ml of E. coli culture solution having an absorbance of 0.01 A (ODE 600 nm), which was measured using a spectrometer. Specifically, states of the functional fabric were photographed at intervals of 60 minutes, 90 minutes and 120 minutes.
[0091] Referring to
[0092] On the other hand, referring to
[0093] Consequently, it could be confirmed that the functional fabric manufactured in Example 1 had better antimicrobial effects than the conventional polyester fabric.
Experimental Example 2
[0094] According to Example 2, 6 μl of deionized water was dropped on the surface of the functional material manufactured by further coating SiO.sub.2 functional microparticles, and the results are shown in
[0095] Referring to
Experimental Example 3
[0096] With regard to the functional fabric manufactured by coating the material with both ZnO microparticles and SiO.sub.2 microparticles according to Example 2, as well as the functional fabric manufactured by applying only SiO.sub.2 microparticles without application of ZnO microparticles according to Example 3, E. coli cell culture experiments were implemented, and the results are shown in
[0097] As shown in
[0098] Further, as shown in
[0099] Consequently, the functional fabric manufactured by coating the material with both ZnO microparticles and SiO.sub.2 microparticles does not lose antimicrobial properties but exhibits both hydrophobicity and antimicrobial properties.
Example 4
[0100]
[0101] More particularly,
[0102] Further,
[0103] Consequently, when using EPD only as shown in