CN115141500A - Non-stick material and preparation method thereof - Google Patents
Non-stick material and preparation method thereof Download PDFInfo
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- CN115141500A CN115141500A CN202111048681.5A CN202111048681A CN115141500A CN 115141500 A CN115141500 A CN 115141500A CN 202111048681 A CN202111048681 A CN 202111048681A CN 115141500 A CN115141500 A CN 115141500A
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- DHKVCYCWBUNNQH-UHFFFAOYSA-N 2-[5-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]-1-(1,4,5,7-tetrahydropyrazolo[3,4-c]pyridin-6-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1=NN=C(O1)CC(=O)N1CC2=C(CC1)C=NN2 DHKVCYCWBUNNQH-UHFFFAOYSA-N 0.000 description 1
- BSWXAWQTMPECAK-UHFFFAOYSA-N 6,6-diethyloctyl dihydrogen phosphate Chemical compound CCC(CC)(CC)CCCCCOP(O)(O)=O BSWXAWQTMPECAK-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 1
- 240000002853 Nelumbo nucifera Species 0.000 description 1
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 1
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
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- 239000008367 deionised water Substances 0.000 description 1
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- 239000008157 edible vegetable oil Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
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- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
-
- A—HUMAN NECESSITIES
- A47—FURNITURE; DOMESTIC ARTICLES OR APPLIANCES; COFFEE MILLS; SPICE MILLS; SUCTION CLEANERS IN GENERAL
- A47J—KITCHEN EQUIPMENT; COFFEE MILLS; SPICE MILLS; APPARATUS FOR MAKING BEVERAGES
- A47J36/00—Parts, details or accessories of cooking-vessels
- A47J36/02—Selection of specific materials, e.g. heavy bottoms with copper inlay or with insulating inlay
- A47J36/025—Vessels with non-stick features, e.g. coatings
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Food Science & Technology (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention provides a non-stick material and a preparation method thereof. The non-stick material includes a plurality of non-stick particles as units of non-stick material, the non-stick particles including a core material and an amorphous alloy material disposed on at least a portion of a surface of the core material. The non-stick material according to the present inventive concept can provide excellent non-stick effect and a long service life.
Description
Technical Field
The invention relates to the technical field of kitchen utensils, in particular to a non-stick material arranged on a base material of a cooker and a preparation method thereof.
Background
In the prior art, the realization of the non-stick technology mainly has three directions: 1) Low surface energy of itself; 2) Forming a hydrophobic and oleophobic surface similar to a lotus leaf surface through a microscopic concave-convex structure; 3) The porous oil storage forms a stable oil film so as to realize non-sticking by using oil as a medium.
The non-stick materials for the current cookers mainly comprise fluorine paint, ceramic paint and organic silicon resin, and the three non-stick materials form a non-stick coating on the inner surface of the cooker mainly in a spraying mode so as to achieve the aim of non-stick when heating food. The fluorine paint mainly comprises PTFE (polytetrafluoroethylene), PFOA (perfluorooctanoic acid ammonium), PFA (copolymer of perfluoropropyl perfluorovinyl ether and polytetrafluoroethylene), FEP (fluorinated ethylene propylene copolymer), ETFE (ethylene-tetrafluoroethylene copolymer) and the like, and the non-stick principle of the fluorine paint is that the fluorine-containing polymer has extremely low surface free energy. The ceramic coating is mainly a coating which takes inorganic silicon with a silicon-oxygen bond structure as a main component, and the non-stick effect is achieved mainly by forming a nano structure on the surface of a cooker. The organic silicon resin achieves the effect of non-stick mainly by utilizing the characteristic of low surface energy. Although these three coatings have a non-stick effect, they all have significant drawbacks: the fluorine coating non-stick coating is not wear-resistant, so that an iron shovel cannot be used during cooking, a steel wire ball and scouring pad cannot be used for cleaning, harmful substances can be generated by decomposition at high temperature, and the non-stick property is reduced after the coating is worn; the ceramic coating has a poor non-stick effect compared with a fluorine coating, is non-stick by mainly utilizing silicone oil in a coating system, but has poor lasting non-stick property, and the coating can easily fall off after being generally used for 3-6 months; the non-stick effect of the organic silicon coating is poorer than that of the fluorine coating, the color of the organic silicon coating is easy to yellow or gray after the organic silicon coating is contacted with high temperature or open fire, the hardness is reduced at high temperature, and the phenomenon of 'back sticking' is easy to generate.
Therefore, the non-stick material generally has the phenomenon of poor permanent non-stick property. Therefore, a surface protection technology capable of making the pot have good durability, non-stick property and wear resistance is needed.
Disclosure of Invention
The inventive concept provides a non-stick particle and a method of making the same. The non-stick particles realized by the conception of the invention can have low surface energy and a porous structure, and the coating prepared by the non-stick particles has the characteristics of high wear resistance, excellent non-stick property and the like, thereby achieving the effect of durable non-stick of the cooker.
According to an exemplary embodiment, a non-stick material includes a plurality of non-stick particles as a unit of non-stick material, the non-stick particles including a core material and an amorphous alloy material disposed on at least a portion of a surface of the core material.
According to an exemplary embodiment, the core material may include a porous ceramic material, and the amorphous alloy material may include at least one of an iron-based amorphous alloy, a zirconium-based amorphous alloy material, a copper-based amorphous alloy material, an aluminum-based amorphous alloy material, a magnesium-based amorphous alloy material, and a titanium-based amorphous alloy material.
According to an exemplary embodiment, the porous ceramic powder may include at least one of diatomite, zeolite powder, and bentonite.
According to an exemplary embodiment, a high entropy alloy material may be further provided on a surface of the core material.
According to an exemplary embodiment, a fluorine resin may be further provided on a surface of the core material.
According to an exemplary embodiment, the amorphous alloy material may be attached in the form of particles on at least a portion of a surface of the core material.
According to an exemplary embodiment, the mass of the core material included in each non-stick particle may be 5% to 30% of the mass of the non-stick particle.
According to an exemplary embodiment, the grain size of the amorphous alloy material is in a range of 10 μm to 25 μm.
According to example embodiments, the core material may be in the form of particles, and the particle size of the core material may be in the range of 35 μm to 60 μm.
According to an exemplary embodiment, the amorphous alloy material may be wrapped on at least a portion of a surface of the core material in a layer, and the amorphous alloy material layer may have a thickness in a range of 10 μm to 25 μm.
According to an exemplary embodiment, the non-stick particles may range in size from 60 μm to 100 μm.
The present inventive concept also provides a method of making a non-stick material comprising a plurality of non-stick particles, the method comprising: respectively providing a core material and an amorphous alloy material; mixing the amorphous alloy material and the core material with a binder; atomizing the mixture comprising the core material, the amorphous alloy material and the binder at a certain temperature to obtain the non-stick material comprising the non-stick particles.
The above briefly describes the concept according to the present invention. The present invention contemplates that non-stick particles having high non-stick properties and long service life can be realized by using a core layer having a high non-stick reinforcing material and a metal material having low surface energy attached to at least a part of the surface thereof, so that when the non-stick particles are applied to the surface of a cooker, the cooker having characteristics of high wear resistance and excellent non-stick properties can be provided.
Detailed Description
The inventive concept will now be described more fully hereinafter. The inventive concept may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, should be interpreted as having a meaning that is consistent with their meaning in the context of the relevant art and the present disclosure and will not be interpreted in an idealized or overly formal sense unless expressly so defined herein.
In the application research of the non-stick coating, the amorphous alloy coating has very wide application prospect due to the amorphous structure. The amorphous alloy is also called as liquid metal, and has no structural defects such as grain boundaries, twin crystals, lattice defects, dislocation, stacking faults and the like a crystal alloy, and has no heterogeneous phase, precipitate, segregation and other component fluctuation, and is a disordered structure, so the amorphous alloy has high uniformity chemically, has no plastic deformation modes such as grain boundary slippage and the like when being subjected to external force, and has higher strength. In addition, since the amorphous alloy has no crystal grains and grain boundaries, the amorphous alloy is more resistant to corrosion than crystalline metals, partial corrosion does not generally occur, and pitting corrosion is suppressed. Therefore, the applicant considers that the wear resistance and the corrosion resistance of the cookware are improved by arranging the amorphous alloy coating on the surface of the cookware. In addition, the applicant also finds that the material with the porous structure can store the edible oil to form an oil film, and the formed oil film can realize the non-sticking property of the pot.
Generally, the higher the amorphous content and the lower the porosity of the amorphous alloy coating, the better the corrosion resistance of the amorphous alloy coating. However, many problems exist in the process of preparing the amorphous alloy coating, which cause that the prepared amorphous alloy coating has structural defects such as grain boundary, segregation and the like, or has loose structure, high porosity and the like, thereby influencing the quality of the amorphous alloy coating. Therefore, even if the amorphous alloy coating is arranged on the surface of the pot, the pot has the characteristics of high wear resistance and high corrosion resistance.
In contrast, the applicant firstly tries to mix the amorphous alloy material and the porous ceramic material and then directly spray the mixture on the inner surface of the cooker substrate in a hot manner to form a non-stick coating on the inner surface of the cooker substrate, the non-stick coating utilizes the characteristic that the amorphous alloy material has low surface energy and the characteristic that the porous ceramic material absorbs oil to form an oil film to realize the non-stick property of the cookware, and the cookware has the non-stick effect through testing. However, upon further analysis of the non-stick coating, the applicant found that the content of the porous ceramic material in the non-stick coating was low; and although the amorphous alloy material and the porous ceramic material are mixed according to the same mass ratio during spraying, the content of the porous ceramic material in the non-stick coating formed by each spraying is different. The reason for this is that the density and melting point of the porous ceramic material and the amorphous alloy material are different, and if the two materials are mixed and then directly thermally sprayed, the porous ceramic material having the characteristics of low density and higher melting point has a low deposition rate in the thermal spraying process, while the amorphous alloy material having a high density and a low melting point has a high deposition rate, and finally, the ratio of the amorphous alloy material to the porous ceramic material in the coating cannot be controlled.
Based on the above, the applicant tries to coat the amorphous alloy material on the outer surface of the porous ceramic material to form the composite material with the core-shell structure, and by utilizing the characteristics that the amorphous alloy material has higher density and lower melting point than the porous ceramic material, the porous ceramic material is deposited on the inner surface of the cooker substrate along with the molten amorphous alloy material during thermal spraying, so that the deposition rate of the porous material is improved, the mass ratio of the liquid metal and the porous material in the non-stick coating is controllable, and the non-stick coating on the surface of the cooker has better non-stick effect and durable non-stick property through tests.
The inventive concept will be described in detail below with reference to specific examples.
The non-stick material applicable to the surface of the base material of cookware according to the present inventive concept may include a plurality of non-stick particles, and each non-stick particle may serve as a unit of non-stick material according to the present inventive concept.
Non-stick particles according to the present concepts may include a core material and an amorphous alloy material having a low surface energy disposed on at least a portion of a surface of the core material. In other words, the non-stick particles according to the present inventive concept may have a composite structure similar to a core-shell structure. The core in the core-shell structure described herein corresponds to a core material of the non-stick particles, whereas the shell in the core-shell structure described herein corresponds to an amorphous alloy material having a low surface energy provided on at least a portion of the surface of the core material. As used herein, the term "at least partially" may mean partially or fully.
According to the inventive concept, the core material provides support properties to the entire non-stick particle, and thus needs to have a certain strength to support the metal material having a low surface energy attached to the surface thereof. In addition, the core material can also have a certain porosity, so that the effects of oil absorption and storage can be generated, and the non-stick performance can be further improved. According to an exemplary embodiment, the core material may include a porous ceramic powder. Here, the porous ceramic powder may be a material known in the art, and the porous ceramic powder structure has porosity, so that the porous ceramic powder structure can play a role in absorbing and storing oil, and increase the non-stickiness of the material. Here, the inventive concept does not limit the kind of the porous ceramic powder. For example, according to an exemplary embodiment, the porous ceramic powder may include diatomaceous earth, zeolite powder, bentonite, and the like. The core material according to the inventive concept may include at least one ceramic powder among a plurality of porous ceramic powders.
The core material according to the inventive concept may be provided in the form of particles, and may have a particle size of 35 μm to 60 μm. The particle size here refers to the largest radial dimension of the particles. In addition, the quality of the core material according to the inventive concept may affect the strength of the overall non-stick particle as well as the non-stick properties, strength, etc. of the non-stick coating formed on the surface of the cookware substrate using the material comprising the particle. Thus, the mass of the core material included in each non-stick particle may be controlled to be 5wt% to 30wt% of the mass of the non-stick particle. When the mass ratio of the core material is too low (less than 5wt% of the mass of the non-stick particles), the non-stick reinforcing effect is not significant; conversely, when the mass ratio is too high (more than 30wt% of the mass of the non-stick particles), the strength of the non-stick particles and subsequent construction are affected (when a thermal spray process is used to make coatings from the non-stick particles, the non-stick particles need to be thermally deformed to create a mechanical and metallurgical bond with the substrate, in which case the non-metallic phase will affect the coating plastically to much, resulting in the non-stick particles breaking up, resulting in increased coating defects).
According to the inventive concept, the amorphous alloy material may be an amorphous alloy commonly used in the art, and may be attached on at least a portion of the surface of the core material in various forms (e.g., a layer, a film, a bulk, particles having a specific shape or an amorphous shape), and its main element composition may include Fe, zr, cu, al, mg, ti, sn, ni, pb, zn, nd, ga, mo, hf, cr, ca, Y, si, P, B, C, etc., but is not limited thereto. According to a specific example, the amorphous alloy material may be attached in the form of particles on at least a portion of the surface of the core material.
The amorphous alloy material according to the inventive concept may be one or more selected from iron (Fe) -based amorphous alloy materials, zirconium (Zr) -based amorphous alloy materials, copper (Cu) -based amorphous alloy materials, aluminum (Al) -based amorphous alloy materials, magnesium (Mg) -based amorphous alloy materials, titanium (Ti) -based amorphous alloy materials. For example, the components of the amorphous alloy material can be Zr60-Cr20-Al13-Ni5-Hf2, zr65- (Ti) -Ni10-Al10-C mu 15, fe80-Cr5-Mo6-B4-Si5, fe50-Zr20-Cr9-B6-C mu 10-Y5, fe87.4-Si6.7-B2.4-Cr2.7-C0.8, fe90-B3-Si7 and the like in atomic percentage.
In addition, according to exemplary embodiments of the inventive concept, at least one of materials that may provide non-stick properties, such as fluorine resin, high-entropy alloy, and the like, may be attached on at least a portion of a surface of the core material in various forms (e.g., a layer, a film, a block, particles having a certain shape or an amorphous shape) together with the amorphous alloy material. The fluororesin may be a fluororesin commonly used in the art, such as Polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), polyvinylidene fluoride (PVDF), ethylene-tetrafluoroethylene copolymer (ETFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), polyvinyl fluoride (PVF), etc., and since the fluororesin has a low surface energy, the addition of the fluororesin can enhance the non-tackiness of the composite powder. Further, the high entropy alloys described herein refer to alloys known in the art that contain five or more alloying elements and that have equal or substantially equal atomic percentages of the various alloying constituents. For example, the high entropy alloy may be Fe20-Sn20-Pb20-P20-C20, etc. Therefore, the inventive concept does not describe the high-entropy alloy and the fluororesin in detail, and the inventive concept is not limited thereto. Further, the high-entropy alloy and the fluororesin according to the present inventive concept may include the same size range as that of the amorphous alloy material, respectively.
When the low surface energy metallic material is provided in the form of particles, the particle size of the low surface energy metallic material is in the range of 10 μm to 25 μm, preferably in the range of 10 μm to 20 μm. However, the inventive concept is not limited thereto, that is, a low surface energy metal material may be formed to wrap at least a portion of the surface of the core material in the form of a layer instead of particles, according to the choice of process. In this case, the layer of the low surface energy metal material may have a thickness in the range of 10 to 25 μm, preferably 10 to 20 μm.
When an amorphous alloy material, a fluororesin material, a high-entropy alloy material, or the like having the above-described dimensions in the form of particles or layers is attached to the core material, non-sticking particles having dimensions in the range of 60 μm to 100 μm can be formed. Within this range, a non-stick material including non-stick particles may have better workability.
In addition, the non-stick material including the non-stick particles according to the exemplary embodiments of the inventive concept may be applied in various environments. For example, the non-stick material according to the concepts of the present invention can be formed directly on the cookware substrate using existing techniques (e.g., deposition, coating, etc.) to form a non-stick coating, or can be added to, dispersed in, other materials that form the non-stick coating of cookware to prepare the coating for the non-stick cookware. The inventive concept is not limited to the use of non-stick materials. For example, when the non-stick material contemplated by the present invention is directly applied to the surface of the base material of the cooker, the particle size of the non-stick particles may be 60 μm to 80 μm, preferably 60 μm to 70 μm, and when the particle size of the particles is within this range, the non-stick material has good fluidity and is convenient for construction. When the non-stick material of the present invention is added to a non-stick paint, the non-stick particles may have a particle size of 60 to 100 μm, preferably 60 to 80 μm, and when the particle size of the non-stick particles is within this range, they can be uniformly dispersed in the paint, and the surface of the non-stick paint formed finally is smooth and has no granular feel.
The non-stick particles in the non-stick material according to the inventive concept are described in detail above with reference to examples, and in the following, a method of preparing the non-stick particles according to the inventive concept will be exemplarily described with reference to specific processes.
In accordance with the present inventive concept, a granulation process may be employed to produce non-stick particles.
First, a core material and an amorphous alloy material may be separately provided.
As described above, the core material may include the porous ceramic powder, and may have a particle size of 35 μm to 60 μm. The inventive concept is not limited to a material forming method of the core material, that is, a commercially or self-made core material may be selected by those skilled in the art according to the inventive concept, and the particle size of the core material may be adjusted according to the prior art. For example, the size of the core material may be adjusted to a desired size using a grinding means such as ball milling, and the inventive concept is not limited thereto.
In addition, the amorphous alloy may include at least one of an iron (Fe) -based amorphous alloy, a zirconium (Zr) -based amorphous alloy, a copper (Cu) -based amorphous alloy, an aluminum (Al) -based amorphous alloy, a magnesium (Mg) -based amorphous alloy, and a titanium (Ti) -based amorphous alloy. When the amorphous alloy material is attached (e.g., adhered) in the form of particles on the surface of the core material, the amorphous alloy material particles may have a particle size (particle diameter) of 10 μm to 25 μm, preferably 10 μm to 20 μm. When the amorphous alloy material is attached (e.g., wrapped) in a layer on the surface of the core material, the amorphous alloy material may have a thickness of 10 to 25 μm, preferably 10 to 20 μm. Hereinafter, a method of forming a non-stick particle according to an exemplary embodiment of the inventive concept will be described with a metal material particle having a low surface energy as a specific example, however, the inventive concept is not limited thereto, that is, a person skilled in the art may form a metal material having a low surface energy on a surface of a core material in layers using an appropriate method according to the inventive concept to form a non-stick particle in which a metal material layer having a low surface energy wraps the core layer.
The preparation of the amorphous alloy material having low surface energy according to the exemplary embodiments of the inventive concept is not limited. According to an exemplary embodiment, after the amorphous alloy is determined, molten amorphous alloy material (e.g., molten iron-based amorphous alloy) particles may be provided to the cooling medium using, for example, an atomization powdering method to form amorphous alloy particles having different grain sizes using different cooling actions under different parameters of the cooling medium by adjusting respective parameters of the cooling medium. However, the inventive concept is not limited thereto, that is, one skilled in the art may adopt a method known in the art to prepare an amorphous alloy material having a low surface energy according to the inventive concept.
According to a specific example, a copper chill plate can be selected as a cooling medium for molten amorphous alloy material particles, and therefore, the molten amorphous alloy material can be ejected at a constant velocity toward the copper chill plate rotating at a high speed, and fine particles solidified by atomizing the alloy liquid are dispersed all around by the centrifugal force. In addition, inert gas is blown into the copper quenching disk through gas nozzles arranged on the periphery of the quenching disk to accelerate the cooling of molten alloy particles. By the method, the cooling rate can reach 106K/s, so that the alloy structure is not as early as crystallization and is solidified in a supercooled state, and the amorphous alloy material with various particle sizes and low surface energy, which is disclosed by the invention, is prepared. Then, the size of the amorphous alloy material particles having low surface energy may be adjusted using a milling process such as ball milling, etc., to adjust the size of the amorphous alloy material particles having low surface energy to 10 μm to 25 μm, preferably 10 μm to 20 μm. However, when the size of the provided or prepared amorphous alloy material particles having a low surface energy is within a suitable range, a size adjustment process such as grinding may be omitted. For example, alloy particles having a suitable particle size may be screened by a screening process.
In addition, when the non-stick particles according to the exemplary embodiments of the inventive concept include the high-entropy alloy, the above-described process of preparing the amorphous alloy is also applicable to the process of preparing the high-entropy alloy, and the high-entropy alloy may have the same particle size range as that of the amorphous alloy. Hereinafter, for brief description, the amorphous alloy material and the high-entropy alloy material may be collectively referred to as a metal material having a low surface energy.
After the core material and the metal material having the low surface energy are prepared, a bonding process of the core material and the metal material having the low surface energy may be performed. Here, the bonding process may be achieved by a granulation method. The granulation method is to add a certain amount of adhesive, plasticizer and the like into the fine powder to prepare the mixture into spheres with larger granularity, certain pseudo-granularity and good fluidity. This sphere, called pellet, can have a very significant quality impact on subsequent shaping and sintering.
Here, the coupling process will be described in detail by taking a spray granulation method as an example.
First, a selected core material and metal material particles having a low surface energy are mixed in a proportion that the mass of the core material accounts for 5% to 30% of the total mass of the mixture of the core material and the metal material particles, and a solution of an organic binder, an auxiliary (e.g., an antifoaming agent, a dispersing agent), a filler (e.g., graphite, carbon black, etc.), a solvent (e.g., alcohol, acetone, deionized water, etc.) and the mixed particles are mixed to make a slurry. Here, the organic binder may be an organic binder known in the art for use in a granulation process or the like, and may include polyvinyl alcohol, polyvinyl pyrrolidone, sodium carboxymethyl cellulose, or the like. The auxiliary generally includes an antifoaming agent mainly for eliminating foam or bubbles in the slurry and may include silicone oil, polyether-modified silicone oil, and the like, and a dispersing agent which may uniformly disperse the components in the slurry and may include citric acid, triethylhexylphosphoric acid, and the like. The filler is used to adjust the viscosity of the slurry while slowing down the settling of the metal powder in the slurry, and may include graphite, carbon black, and the like. However, it should be understood that various materials used in the slurry preparation process herein may be arbitrarily selected and omitted according to actual circumstances, and the inventive concept is not limited thereto.
Here, the step of preparing the slurry may include the following steps.
A: a solution of the organic binder is prepared. The organic binder is placed in a beaker containing a certain amount of solvent, heated in a water bath furnace, and stirred with a glass rod while being heated until the liquid formed in the beaker becomes transparent, at which time the binder is fully dissolved. The adhesive can be used after impurities in the dissolved adhesive are removed and the adhesive is cooled. Here, the organic binder to solvent volume ratio may be 1.
B: and (4) preparing slurry. The mixed particles may be added into water, and stirred uniformly, and then the organic binder, the auxiliary agent, the filler and the like prepared in step a are added, and the mixture is stirred uniformly, wherein the stirring time may be 30min to 50min, wherein the content of the mixed particles is 30% to 60%, preferably 40% to 50%, of the total mass of the obtained slurry, the content of the organic binder may be 1% to 10%, preferably 3% to 8%, of the total mass of the obtained slurry, the content of the filler may be 5% to 20%, preferably 8% to 15%, of the total mass of the obtained slurry, the content of the auxiliary agent may be 0.2% to 1%, and the content of water may be 20% to 60%, preferably 40% to 55%, of the total mass of the obtained slurry.
Secondly, after the slurry is prepared, the slurry may be atomized. Here, the atomization conditions may be: the atomization pressure is 0.3MPa to 0.6MPa, preferably 0.4MPa to 0.5MPa; the flow rate of the atomized air flow is 0.5m 3 /h～5m 3 H, preferably 1m 3 /h～3m 3 H; the atomization temperature is 80 ℃ to 150 ℃, preferably 100 ℃ to 140 ℃. After atomization, the resulting particles may be sintered. The sintering temperature is increased according to the physical property curve of the particle material, the low temperature region is 50-200 ℃, and the heat preservation time is 15-30 min; the high temperature zone is 200-600 ℃, preferably 300-400 ℃, and the heat preservation time is 2-4 h.
Finally, the resulting granules were sieved to obtain non-stick granules according to exemplary embodiments of the inventive concept.
In addition, when the fluororesin is included according to an exemplary embodiment of the inventive concept, the fluororesin may be added to the slurry in the form of particles of a certain particle size during the preparation of the slurry to achieve the adhesion of the fluororesin and the metal material particles having a low surface energy described above on the surface of the core material.
Here, although the method of forming the nonstick particles of the exemplary embodiment of the inventive concept is described in connection with the atomization granulation method, the inventive concept is not limited thereto. That is, a suitable core material may be added to a metal material having a bottom surface energy in a molten state, and non-stick particles of the metal material having a bottom surface energy in which the core material is located, externally wrapped with a predetermined thickness, may be formed by an ultra-cold atomization process or the like. Here, one skilled in the art, knowing the inventive concept, can select an appropriate process to form the non-stick particles of the inventive concept.
The non-stick particles and methods of forming the same contemplated by the present invention are described above in connection with exemplary embodiments. The non-stick particles according to the present inventive concept may include a core material and a metal material having a low surface energy on a surface of the core material and may further include a fluororesin, and such a composite material may improve the life span and non-stick property of a non-stick coating when applied to the non-stick coating on the surface of cookware. In addition, the deposition of particles on a base material is more uniform when the particles formed by granulation are sprayed on the base material, compared to the case where a core material and a metal material having a low surface energy on the surface of the core material are directly mixed and sprayed on the surface of the base material of a cooker. In contrast, since the density and melting point of the metal material having low surface energy are different from those of the core material, the deposition rate of the lighter and higher melting point core material (e.g., porous ceramic powder particles) is low, while the deposition rate of the metal material having low surface energy (e.g., amorphous alloy powder particles) is high in the direct spray process using their mixture, and the ratio between the metal material having low surface energy and the core material in the final coating layer cannot be controlled, resulting in poor performance of the finally formed non-stick coating layer.
Hereinafter, advantages of the inventive concept will be comparatively described with reference to specific embodiments.
Example 1:
providing iron-based amorphous alloy powder (Fe 80-Cr5-Mo6-B4-Si 5) with the granularity of 10-20 microns and diatomite with the granularity of 35-60 microns;
mixing the above powder with polyvinyl alcohol, organic silicon oil, citric acid, graphite, acetone and water at a certain proportion, stirring for 40min, and making into slurry. Here, the mass of the diatomaceous earth accounts for 6% of the total mass of the iron-based amorphous alloy powder and the diatomaceous earth, the mass of the mixed particle material accounts for 40% of the total mass of the obtained slurry, the volume ratio of the polyvinyl alcohol to the acetone is 1;
spray drying the slurry at an atomization pressure of 0.4MPa and an atomization flow rate of 2m 3 H, the atomization temperature is 100 ℃;
after the atomization drying, sintering the powder particles obtained after the atomization drying: the low temperature zone is 150 ℃, and the heat preservation time is 15min; the high-temperature zone is in the temperature range of 400 ℃, and the heat preservation time is 3 hours;
and screening the sintered particles to obtain powder with the required particle size of 60-100 microns.
Example 2:
the difference from the example 1 is that the diatomite accounts for 15% of the total mass of the iron-based amorphous alloy powder and the porous ceramic powder.
Example 3:
the difference from the example 1 is that the weight of the diatomite accounts for 25% of the total weight of the iron-based amorphous alloy powder and the diatomite.
Example 4:
the difference from example 1 is that a nickel-based amorphous alloy (Ni 40-Fe20-Cr25-B5-Si 10) is used.
Example 5:
the difference from example 1 is that a zirconium based amorphous alloy (Zr 60-Cr20-Al13-Ni5-Hf 2) was used.
Example 6:
the difference from the embodiment 1 is that a part of high entropy alloy (Fe 20-Sn20-Pb 20-P20-C20) is added into iron-based amorphous alloy (Fe 80-Cr5-Mo6-B4-Si 5), wherein the mass of the iron-based amorphous alloy accounts for 70% of the total mass of the iron-based amorphous alloy and the high entropy alloy, and the mass of the high entropy alloy accounts for 30% of the total mass of the iron-based amorphous alloy and the high entropy alloy.
Comparative example 1:
the difference from the example 1 is that the weight of the diatomite accounts for 2% of the total weight of the iron-based amorphous alloy powder and the diatomite.
Comparative example 2:
the difference from the example 1 is that the weight of the diatomite accounts for 50% of the total weight of the iron-based amorphous alloy powder and the diatomite.
Comparative example 3:
only mixing iron-based amorphous alloy powder with the granularity of 10-20 mu m and diatomite with the granularity of 35-60 mu m without a granulation process, wherein the mass of the diatomite accounts for 6 percent of the total mass of the iron-based amorphous alloy powder and the diatomite.
Comparative example 4:
only 10-20 μm of Fe-based amorphous alloy powder is used.
Comparative example 5:
only 35-60 μm of diatomite is used.
The materials of examples 1 to 6 and comparative examples 1 to 5 were respectively subjected to plasma spraying to form coatings, and the performance of the coatings was tested, and the test results are shown in the following table.
| Scheme(s) | Porosity of coating | Strength of coating | Wear resistance/time of coating | Permanent tack-free property |
| Example 1 | 13％ | Qualified | 49000 | 54000 |
| Example 2 | 22％ | Qualified | 55000 | 60000 |
| Example 3 | 31％ | Qualified | 58000 | 62000 |
| Example 4 | 13％ | Qualified | 51000 | 52000 |
| Example 5 | 15％ | Qualified | 50000 | 52000 |
| Example 6 | 12％ | Qualified | 46000 | 48000 |
| Comparative example 1 | 6％ | Qualified | 38000 | 38000 |
| Comparative example 2 | 45％ | Fail to be qualified | 72000 | 65000 |
| Comparative example 3 | 5％ | Qualified | 42000 | 40000 |
| Comparative example 4 | 2.5％ | Qualified | 35000 | 35000 |
| Comparative example 5 | 60％ | Fail to be qualified | —— | 0 |
The test method of each property in the table is as follows:
1) The method for testing the porosity of the coating comprises the following steps: observing the section of the sample by a metallographic microscope, and setting different contrasts by IQmetric software to measure the porosity;
2) Testing the strength of the coating: adopting 500g of steel balls to vertically fall from a height of 50cm and hit the surface of the coating, wherein the coating is qualified if no crack, damage or drop occurs, and is not qualified otherwise;
3) Abrasion resistance and durable tack resistance test of the coating: the permanent tack-free property is increased by one 1000 omelette tests per 1000 omelette tests in the test method referred to in GB/T32095.2-2015, relative to the abrasion resistance test.
From the above tests, it can be seen that: the coatings formed by comparative examples 1, 3 and 4, although having acceptable strength, have low abrasion resistance and long-lasting non-tackiness; the porous ceramic in the comparative example 2 has a large proportion, so the porosity is relatively large, and although the comparative example 2 has large wear resistance and long-lasting non-stick property of the coating, the strength of the coating is low; comparative example 5 since only the porous ceramic powder was sprayed, the deposition efficiency was low and the coating bonding force was low. It is difficult to form a coating layer efficiently. Therefore, no wear data exists, and the strength and the durability and the non-stick property of the coating are not qualified.
The non-stick coating formed by using the non-stick material according to the present inventive concept has a long-lasting non-stick property, high strength, and high wear resistance.
While one or more embodiments of the present invention have been described with reference to specific examples, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims.
Claims (11)
1. A non-stick material comprising a plurality of non-stick particles as units of non-stick material, the non-stick particles comprising a core material and an amorphous alloy material disposed on at least a portion of a surface of the core material.
2. The non-stick material of claim 1, wherein the core material comprises a porous ceramic material, and the amorphous alloy material comprises at least one of an iron-based amorphous alloy, a zirconium-based amorphous alloy material, a copper-based amorphous alloy material, an aluminum-based amorphous alloy material, a magnesium-based amorphous alloy material, and a titanium-based amorphous alloy material.
3. The non-stick material of claim 2, wherein the porous ceramic material comprises at least one of diatomaceous earth, zeolite powder, and bentonite.
4. The non-stick material according to claim 2, wherein at least one of a high-entropy alloy material and a fluorine resin is further provided on a surface of the core material.
5. The non-stick material of any of claims 1-4, wherein the amorphous alloy material is attached to at least a portion of a surface of a core material in the form of particles.
6. The non-stick material of claim 6, wherein the grain size of the amorphous alloy material is in the range of 10 μm to 25 μm.
7. The non-stick material of any of claims 1-4, wherein the core material is in the form of particles and has a particle size in the range of 35 μm to 60 μm.
8. The non-stick material of any of claims 1-4, wherein the mass of core material included in each non-stick particle is 5% to 30% of the mass of the non-stick particle.
9. The non-stick material of any of claims 1-4, wherein the amorphous alloy material is wrapped in a layer over at least a portion of a surface of a core material.
10. The non-stick material of any of claims 1-4, wherein the non-stick particles range in size from 60 μm to 100 μm.
11. A method of making a non-stick material comprising a plurality of non-stick particles, the method comprising:
respectively providing a core material and an amorphous alloy material;
mixing the amorphous alloy material and the core material with a binder;
atomizing a mixture comprising a core material, an amorphous alloy material and a binder at a temperature to obtain a nonstick material comprising nonstick particles,
wherein the non-stick particles comprise a core material and an amorphous alloy material disposed on at least a portion of a surface of the core material.
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| CN115595025A (en) * | 2021-07-08 | 2023-01-13 | 武汉苏泊尔炊具有限公司（Cn） | Non-stick material, preparation method thereof, non-stick coating and cooking utensil |
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| CN112137422A (en) * | 2019-06-28 | 2020-12-29 | 武汉苏泊尔炊具有限公司 | Non-stick master batch, manufacturing method of non-stick master batch, non-stick material and cooking utensil |
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| CN109706419A (en) * | 2017-10-25 | 2019-05-03 | 佛山市顺德区美的电热电器制造有限公司 | Non-sticking lining and preparation method thereof and cookware and equipment of cooking |
| CN112137422A (en) * | 2019-06-28 | 2020-12-29 | 武汉苏泊尔炊具有限公司 | Non-stick master batch, manufacturing method of non-stick master batch, non-stick material and cooking utensil |
| CN112137419A (en) * | 2019-06-28 | 2020-12-29 | 武汉苏泊尔炊具有限公司 | Non-stick master batch, manufacturing method of non-stick master batch, non-stick material and cooking utensil |
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| CN115595025B (en) * | 2021-07-08 | 2023-09-08 | 武汉苏泊尔炊具有限公司 | Non-stick material, preparation method thereof, non-stick coating and cooking utensil |
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