Manufacturing method of a cold-sprayed high-performance physically non-stick composite cookware

Abstract

The present invention discloses a manufacturing method of a cold-sprayed high-performance physically non-stick composite cookware. The inner surface of the round disc cookware material undergoes steps such as sandblasting - cold spraying of titanium alloy composite powder - screen printing - acid etching - alkali solution for removing ink - femtosecond laser ablation - acid pore etching treatment, etc. Finally, stretching and edge trimming treatments are carried out to obtain the non-stick cookware required by the design. The cookware prepared by the present invention realizes physical non-stick property due to its porous structure, and the inner surface of the cookware is a layer of titanium alloy composite powder. Metallic titanium cannot be absorbed by the human body and cannot be absorbed through the skin either. Therefore, even if the coating falls off and is ingested by the human body, it is harmless to the human body.

Description

Technical Field

[0001] The present invention relates to the technical field of cookware production, and particularly relates to a manufacturing method of a cold-sprayed high-performance physically non-stick composite cookware. Background Art

[0002] At present, the non-stick property of honeycomb cookware in the market relies on the non-stick property of Teflon, which belongs to chemical non-stick. Teflon is polytetrafluoroethylene. According to the preliminary list of carcinogens published by the International Agency for Research on Cancer of the World Health Organization, polytetrafluoroethylene is in the list of Group 3 carcinogens. Although the existing evidence fails to prove the carcinogenicity of Teflon to humans, the use of Teflon in cookware should be avoided as much as possible. Summary of the Invention

[0003] In order to overcome the disadvantages and deficiencies of the prior art, the present invention provides a manufacturing method of a cold-sprayed high-performance physically non-stick composite cookware. The cookware manufactured by this method has physical non-stick performance, and there is no need to worry about food sticking to the pan and burning at the bottom during cooking, nor the potential carcinogenic risk brought by the Teflon coating, which is healthy and safe.

[0004] The purpose of the present invention is achieved by the following technical solutions:

[0005] In the first aspect, the present invention provides a manufacturing method of a cold-sprayed high-performance physically non-stick composite cookware, which specifically includes the following steps:

[0006] S1: Perform sandblasting treatment on the inner surface of the pre-cut round cookware blank.

[0007] S2: Cold-spray a titanium alloy composite powder on the inner surface of the round cookware blank after the sandblasting treatment in step S1 to form a titanium alloy composite coating on the inner surface of the round cookware blank.

[0008] S3: Print a pattern formed by anti-etching ink on the inner surface of the round cookware blank using screen anti-etching ink and then dry it to expose the titanium alloy composite coating at the position covered by the screen.

[0009] S4: Spray an acidic etching solution on the inner surface of the round cookware blank to etch away at least part of the thickness of the titanium alloy composite coating without the coverage of anti-etching ink to form a concave surface, and wash away the acidic etching solution after the etching is completed.

[0010] S5: Wash away the anti-etching ink using an alkaline solution.

[0011] S6: After washing away the alkaline solution, ablate the concave surface using femtosecond laser.

[0012] S7: Perform pore etching treatment on the entire inner surface of the round cookware blank using an acidic etching solution, and wash away the acidic etching solution after the etching is completed.

[0013] S8: Then, the round pan material is stretched and trimmed to obtain the non-stick pan required by the design.

[0014] The titanium alloy composite powder consists of 40 - 60% titanium, 10 - 25% hydroxyapatite, 5 - 15% titanium oxide, 4 - 12% titanium nitride, and 1 - 5% copper - silver alloy, and the synthesis ratio is 100%.

[0015] The particle size of the titanium alloy composite powder is 10 - 50 microns.

[0016] In step S3, a 100 - 300 - mesh screen is used for screen printing, and screen printing is carried out more than 2 times.

[0017] In step S3, the drying time is 14 - 16 minutes, and the drying temperature is 60 - 160 °C.

[0018] In step S3, the anti - etching ink consists of a photopolymer resin, a photo - crosslinking agent, an active diluent, and a photo - initiator.

[0019] Preferably, the anti - etching ink consists of components with a total volume percentage of 100%: 30 - 55% phenolic epoxy acrylate resin, 15 - 35% acid anhydride, 6 - 13% hydroquinone diglycidyl ether, 3 - 8% trimethylolpropane triacrylate, and 2 - 9% homolytic initiator.

[0020] The acidic etching solution consists of components with a total volume percentage of 100%: 30 - 60% hydrofluoric acid, 10 - 15% ammonium sulfate, 20 - 50% aminodicarboxylic acid, 10 - 15% hydrogen peroxide, 3 - 5% sodium gluconate, 1 - 3% disodium ethylenediaminetetraacetate, 0.5 - 2% potassium hydroxyethylidene diphosphonate, and the balance is deionized water.

[0021] In step S3, the etching time is 20 minutes.

[0022] In step S7, the etching time is 2 minutes.

[0023] In the second aspect, the present invention provides a cookware manufactured by using the manufacturing method of the cold - sprayed high - performance physical non - stick composite cookware.

[0024] The present invention has the following advantages and effects compared with the prior art:

[0025] The titanium alloy composite powder used in the present invention is a composite powder composed of metal and ceramic. After cold spraying, a titanium alloy composite coating will be formed on the inner layer of the pot. After screen printing the pattern, an ink-covered layer and a non-ink-covered layer will be formed on the inner surface of the pot material. Since the ink has anti-etching properties, when etching the inner surface of the pot material with an acidic etching solution and controlling the etching time, the titanium alloy composite coating covered by the ink will not be corroded, while some metals in the titanium alloy composite coating without ink coverage will be corroded by the acidic etching solution and the ceramic remains, thus forming grooves to facilitate subsequent femtosecond laser processing. Then, use an alkaline solution to wash off the anti-etching ink on the titanium alloy composite coating so that the entire inner surface of the pot material has no ink coverage. Use the femtosecond laser ablation method to ablate the concave surface to form an uneven oleophobic and hydrophobic structure. After the femtosecond laser is completed, use an acidic etching solution to corrode the entire inner surface of the pot material, control the etching time to corrode some metals in the entire titanium alloy composite coating, while the ceramic and some metals in the entire titanium alloy composite coating are retained, thus forming a porous structure. The porous structure can gather oil more and form an oil film to achieve physical non-stickiness.

[0026] In addition, generally, the pot body is made of aluminum alloy. By cold spraying a layer of titanium alloy composite powder on the inner surface of the pot body in the present invention, the aluminum alloy can be isolated to reduce the harm of aluminum to the human body; and the metallic titanium on the coating cannot be absorbed by the human body and cannot be absorbed through the skin either. Therefore, even if the coating falls off and is ingested into the human body, it is harmless to the human body. Brief Description of the Drawings

[0027] Figure 1 It is a schematic diagram showing white spaces when using traditional ink for screen printing.

[0028] Figure 2 It is a schematic diagram of the changes on the inner surface of the pot material of the present invention after etching treatment, femtosecond laser, and pore etching treatment.

[0029] Figure 3 It is a micrograph of the porous structure formed in Example 1.

[0030] Figure 4 a in it is a schematic diagram of sampling point 1 on the inner surface of the pot made in Example 1, Figure 4 b in it is Figure 4 an enlarged view of sampling point 1 in a of it.

[0031] Figure 5 It is a schematic diagram of the inner surface of the pot prepared in the example. Detailed Description of the Invention

[0032] The technical solutions in the embodiments will be described clearly and completely below. Obviously, the embodiments described below are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0033] It should be understood that when used in this specification and the appended claims, the terms "comprising" and "including" indicate the presence of the described features, wholes, steps, operations, elements and / or components, but do not exclude the presence or addition of one or more other features, wholes, steps, operations, elements, components and / or their combinations.

[0034] It should also be understood that the terms used in the specification of the embodiments of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the embodiments of the present invention. As used in the specification of the embodiments of the present invention and the appended claims, unless the context clearly indicates otherwise, the singular forms "a", "an" and "the" are intended to include the plural forms.

[0035] Embodiment 1

[0036] This embodiment provides a manufacturing method for a cold-sprayed high-performance physically non-stick composite cookware, specifically including the following steps:

[0037] a: Sandblast the inner surface of the pre-cut round aluminum alloy to increase the roughness of the inner surface of the aluminum alloy;

[0038] b: Cold-spray a titanium alloy composite powder on the inner surface of the round aluminum alloy after the sandblasting treatment in step S1 to form a titanium alloy composite coating;

[0039] The cold-sprayed titanium alloy composite powder is composed of 60% titanium, 20% hydroxyapatite, 10% titanium oxide, 7% titanium nitride, and 3% copper-silver alloy, and the particle size of the cold-sprayed titanium alloy composite powder is 10 - 50 microns.

[0040] Set the parameters of the cold spraying as follows: the carrier gas temperature is 210 - 750 °C, the carrier gas pressure is 2.8 - 3.8 MPa, the spraying distance is 15 - 40 mm, and the powder speed is 930 - 1180 m / s.

[0041] c: Use a screen anti-etching ink to print a honeycomb pattern formed by the anti-etching ink on the inner surface of the round aluminum alloy and then dry it;

[0042] When performing screen printing, a screen with a mesh size of 100 - 300 meshes is used for full - area printing. During printing, in order to ensure a uniform printing layer without blank spaces or broken lines, it is necessary to print two or more times. At the same time, the printing process has high requirements for the environment: since the anti - etching ink is a photosensitive material, there should be no strong light or direct sunlight indoors during use. Generally, yellow lights and yellow curtains are used; the indoor cleanliness requirement is relatively high. To reduce dust, it is best to use a purification workshop; in addition to meeting the above two conditions, attention should also be paid to the indoor temperature, humidity, and ventilation. The indoor temperature is maintained at 25 ± 1 °C, and the humidity is maintained at 40% - 60%; after printing, it needs to be dried. The drying temperature is generally in the range of 60 - 160 °C. Excessive temperature will affect development; the drying time is 15 ± 1 minute. When the film is dry and does not stick to the hand, the drying is completed; during drying, it is still necessary to pay attention to avoiding light and preventing dust.

[0043] After drying is completed, a honeycomb pattern is formed on the inner surface of the wafer aluminum alloy. The surface covered by the anti - etching ink after screen printing is protected from being corroded by the acidic etching solution.

[0044] The anti - etching ink is composed of components with a total volume percentage of 100%: 50% phenolic epoxy acrylate resin, 30% phosphoric anhydride, 10% hydroquinone diglycidyl ether, 5% trimethylolpropane triacrylate, and 5% homolytic initiator.

[0045] Among them, the phenolic epoxy acrylate resin is prepared by the method described in Zhou Liang, Yang Zhuoru, "Synthesis Research of Phenolic Epoxy Acrylate Resin" 2004(4)21 - 23.

[0046] The hydroquinone diglycidyl ether is prepared by the method described in Gao Chunlin, Fan Linlin, Wang Lei, Zhao Bing, "Synthesis Research of Hydroquinone Diglycidyl Ether" 2010(10)24 - 26.

[0047] The anti - etching ink prepared by the present invention has low requirements for the flatness of the inner surface of the wafer material. Even if the surface roughness is large, it can still be fully covered by the anti - etching ink, while traditional inks require a flat surface, otherwise there will be blank spaces or broken lines.

[0048] d: Based on the honeycomb pattern in step c, spray the acidic etching solution on the titanium alloy composite coating on the inner surface of the aluminum alloy for 20 minutes. Since the ink has anti - etching properties, when the acidic etching solution etches the inner surface of the aluminum alloy, the titanium alloy composite coating covered by the ink will not be corroded. And due to the control of the etching time, the titanium alloy composite coating without ink coverage is corroded by the acidic etching solution by 3 - 5 mm. Since the titanium alloy composite powder is composed of metal and ceramic, the acidic etching solution corrodes the metal component in the titanium alloy composite coating, and the ceramic component is retained. And because part of the metal is corroded, the titanium alloy composite coating without ink coverage forms a concave shape with a thickness of 3 - 5 mm relative to the titanium alloy composite coating with ink coverage.

[0049] Among them, the acidic etching solution contains 30 - 60% hydrofluoric acid, 10 - 15% ammonium sulfate, 20 - 50% aminodicarboxylic acid, 10 - 15% hydrogen peroxide, 3 - 5% sodium gluconate, 1 - 3% disodium ethylenediaminetetraacetate, 0.5 - 2% potassium hydroxyethylidene diphosphonate, and the balance is deionized water.

[0050] e: Wash off the acidic etching solution;

[0051] f: Alkaline wash to remove the anti-etching ink;

[0052] g: After washing off the alkaline solution, perform femtosecond laser ablation on the concave surface. Set the wavelength during femtosecond laser ablation to 355 - 532 nm, the spot size to 1 - 3 μm, the positioning accuracy to 0.5 - 1 μm, and the repeat accuracy to 0.2 - 0.6 μm;

[0053] h: After femtosecond laser ablation, use the acidic etching solution to perform pore etching on the inner surface of the entire wafer aluminum alloy. The acid etching time is 2 minutes. After acid etching, part of the metal in the titanium alloy composite coating on the inner surface of the entire wafer aluminum alloy is removed, and the remaining ceramic and part of the metal in the titanium alloy composite coating are retained, thereby forming a porous structure. The porous structure can hold oil better and form an oil film to achieve physical non-sticking.

[0054] h: Stretch and trim the wafer aluminum alloy obtained in step g to obtain a pot with the designed size.

[0055] Example 2

[0056] This example provides a manufacturing method for a cold-sprayed high-performance physically non-sticking composite cookware. The manufacturing method and steps are the same as those in Example 1, except that the cold-sprayed titanium alloy composite powder in this example is composed of 50% titanium, 15% hydroxyapatite, 15% titanium oxide, 15% titanium nitride, and 5% copper-silver alloy. The anti-etching ink consists of components with a total volume percentage of 100%: 45% phenolic epoxy acrylate resin, 30% phosphoric anhydride, 8% hydroquinone diglycidyl ether, 8% trimethylolpropane triacrylate, and 9% homolytic initiator.

[0057] Example 3

[0058] This example provides a manufacturing method for a cold-sprayed high-performance physically non-sticking composite cookware. The manufacturing method and steps are the same as those in Example 1, except that the cold-sprayed titanium alloy composite powder in this example is composed of 45% titanium, 25% hydroxyapatite, 15% titanium oxide, 12% titanium nitride, and 3% copper-silver alloy. The anti-etching ink consists of components with a total volume percentage of 100%: 55% phenolic epoxy acrylate resin, 25% phosphoric anhydride, 10% hydroquinone diglycidyl ether, 5% trimethylolpropane triacrylate, and 5% homolytic initiator.

[0059] Example 4

[0060] This example provides a manufacturing method for a cold-sprayed high-performance physical non-stick composite cookware. The manufacturing method and steps are the same as those in Example 1, except that the cold-sprayed titanium alloy composite powder in this example is composed of 55% titanium, 18% hydroxyapatite, 14% titanium oxide, 12% titanium nitride, and 1% copper-silver alloy. The anti-etching ink consists of components with a total volume percentage of 100%: 40% phenolic epoxy acrylate resin, 35% phosphoric anhydride, 13% hydroquinone diglycidyl ether, 7% trimethylolpropane triacrylate, and 5% homolytic initiator.

[0061] Example 5

[0062] This example provides a manufacturing method for a cold-sprayed high-performance physical non-stick composite cookware. The manufacturing method and steps are the same as those in Example 1, except that the cold-sprayed titanium alloy composite powder in this example is composed of 60% titanium, 18% hydroxyapatite, 8% titanium oxide, 10% titanium nitride, and 4% copper-silver alloy. The anti-etching ink consists of components with a total volume percentage of 100%: 48% phenolic epoxy acrylate resin, 22% phosphoric anhydride, 13% hydroquinone diglycidyl ether, 8% trimethylolpropane triacrylate, and 9% homolytic initiator.

[0063] Comparative Example 1

[0064] This comparative example provides a traditional pure titanium pot. The manufacturing method of the traditional pure titanium pot is as follows: After the composite multi-layer titanium ring pieces are treated with oil coating, they are stretched, trimmed, cleaned, polished, and assembled to obtain the traditional pure titanium pot.

[0065] Comparative Example 2

[0066] This comparative example provides a clad titanium pot. The manufacturing method of the clad titanium pot is as follows: An aluminum round sheet with a thickness of 3.5 - 6 mm is used. After oil coating, stretching and forming, edge turning, cleaning, cladding (the cladding thickness is 15 - 35 μm), polishing, spraying a non-stick coating, and assembling, the clad titanium pot is obtained.

[0067] Test Example

[0068] The non-stick property of frying eggs was tested on the pots prepared in Example 1, Example 2, Comparative Example 1, and Comparative Example 2. The abrasion resistance and corrosion resistance tests were carried out on the pots prepared in Example 1, Example 2, and Comparative Example 2. Since Comparative Example 1 does not have a coating, the abrasion resistance and corrosion resistance tests were not carried out on it. The test results are shown in Table 1.

[0069] Define the test method:

[0070] 1. High-temperature non-stick fried egg test: Test the non-stick property of non-stick cookware by frying eggs. The frying temperature is above 260 degrees Celsius. Fry 100 eggs for the test. After every 10,000 abrasion tests, fry 10 eggs. The non-stick effect level of frying eggs is set to 5 levels, which are as follows:

[0071] Level 1 is very poor: The egg can only be moved and broken under the action of the spatula.

[0072] Level 2 is poor: A certain degree of force is required to move the egg, but it can be moved as a whole without being broken under the action of the spatula, leaving a medium degree of residue.

[0073] Level 3 is average: There is a medium degree of adhesion at the edge of the egg and slight adhesion in the center.

[0074] Level 4 is good: There is slight adhesion at the edge of the egg.

[0075] Level 5 is very good: There is no adhesion at all, and no trace residue is left when moving the center.

[0076] 2. Abrasion test: Through the back-and-forth friction test with a scouring pad, the effect is excellent if it is more than 500,000 times, good if it is greater than or equal to 200,000 times, and poor if it is less than 100,000 times.

[0077] 3. Brine test: Test with 5% brine, gently boil for 24 hours, without defects such as peeling, foaming, cracking, shrinkage holes, etc.

[0078] Table 1 Results of various tests

[0079]

[0080]

[0081] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited by the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in the protection scope of the present invention.

Claims

1. A manufacturing method of a cold-sprayed high-performance physically non-stick composite cookware, characterized in that, It includes the following steps: S1: Sandblast the inner surface of the pre-cut round pot material; S2: Cold-spray a titanium alloy composite powder on the inner surface of the round pot material after the sandblasting in step S1 to form a layer of titanium alloy composite coating on the inner surface of the round pot material; the titanium alloy composite powder is composed of 40 - 60% titanium, 10 - 25% hydroxyapatite, 5 - 15% titanium oxide, 4 - 12% titanium nitride, and 1 - 5% copper-silver alloy, and the synthesis ratio is 100%; S3: Print a pattern formed by anti-etching ink on the inner surface of the round pot material using screen anti-etching ink and then dry it to expose the titanium alloy composite coating at the covered positions of the screen; S4: Spray an acidic etching solution on the inner surface of the round pot material to etch away at least part of the thickness of the titanium alloy composite coating without the coverage of anti-etching ink to form a concave surface, and wash away the acidic etching solution after the etching is completed; S5: Wash away the anti-etching ink using an alkaline solution; S6: After washing away the alkaline solution, ablate the concave surface using femtosecond laser; S7: Use an acidic etching solution to perform hole etching on the entire inner surface of the round pot material, and wash away the acidic etching solution after the etching is completed; S8: Then perform stretching and edge trimming on the round pot material to obtain the non-stick pot required by the design.

2. The manufacturing method according to claim 1, characterized in that, The particle size of the titanium alloy composite powder is 10 - 50 microns.

3. The manufacturing method according to claim 1, characterized in that, In step S3, a 100 - 300 mesh screen is used for screen printing, and screen printing is performed more than 2 times.

4. The manufacturing method according to claim 1, characterized in that, In step S3, the drying time is 14 - 16 minutes, and the drying temperature is 60 - 160 °C.

5. The manufacturing method according to claim 1, characterized in that, In step S3, the anti-etching ink is composed of a photopolymer resin, a photo-crosslinking agent, an active diluent, and a photoinitiator.

6. The manufacturing method according to claim 1, characterized in that, The anti-etching ink is composed of components with a total volume percentage of 100%: 30 - 55% phenolic epoxy acrylate resin, 15 - 35% acid anhydride, 6 - 13% hydroquinone diglycidyl ether, 3 - 8% trimethylolpropane triacrylate, 2 - 9% homolytic initiator.

7. The manufacturing method according to claim 1, characterized in that, The acidic etching solution is composed of components with a total volume percentage of 100%: 30 - 60% hydrofluoric acid, 10 - 15% ammonium sulfate, 20 - 50% aminodicarboxylic acid, 10 - 15% hydrogen peroxide, 3 - 5% sodium gluconate, 1 - 3% disodium ethylenediaminetetraacetate, 0.5 - 2% potassium hydroxyethylidene diphosphonate, and the balance is deionized water.

8. The manufacturing method according to claim 1, characterized in that, In step S3, the etching time is 20 minutes; in step S7, the etching time is 2 minutes.

9. A cookware, characterized in that, It is manufactured by using the manufacturing method of the cold-sprayed high-performance physical non-stick composite cookware according to any one of claims 1 to 8.

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