Metal article, method for manufacturing the metal article, and metal composite
11629428 · 2023-04-18
Assignee
Inventors
- Kar-Wai Hon (New Taipei, TW)
- Ching-Hao Yang (New Taipei, TW)
- HAO ZHOU (Shenzhen, CN)
- Dong-Xu Zhang (Shenzhen, CN)
Cpc classification
C25D11/12
CHEMISTRY; METALLURGY
C23F17/00
CHEMISTRY; METALLURGY
B32B15/012
PERFORMING OPERATIONS; TRANSPORTING
International classification
C23F17/00
CHEMISTRY; METALLURGY
Abstract
A metal article comprises two metals, and a first hole and an oxide layer are set correspondingly on the surfaces of the two metals. To avoid the electrolytic corrosion on the interface between the two metals during the formation of the first hole, the disclosure provides a method of manufacturing the metal article. By putting a metal substrate in a first electrolyte including an etching agent and a passivating agent and applying electricity on the metal substrate, the metal article with the first hole is formed without electrolytic corrosion. The disclosure also provides a metal composite, which is formed by setting a material part in the first hole of the metal article.
Claims
1. A method for manufacturing a metal article, comprising: putting a metal substrate into a first electrolyte, wherein the first electrolyte comprises an etching agent and a passivating agent; the metal substrate comprises a first metal layer and a second metal layer, and the second metal layer is set on a surface of the first metal layer; and applying electricity on the metal substrate to form a first hole on the surface of the first metal layer, and to form an oxide layer on the surface of a second metal layer, thereby obtaining the metal article.
2. The method of claim 1, wherein the etching agent is at least one selected from the group consisting of sulfuric acid, nitric acid, sulfate and nitrate; the passivating agent is at least one selected from the group consisting of sulfuric acid, nitric acid, oxalic acid, phosphoric acid, citric acid, sulfate, nitrate, oxalate, phosphate and citrate; an acid radical of the etching agent is different from an acid radical of the passivating agent; and at least one of the etching agents and passivating agents comprise hydrogen ion.
3. The method of claim 1, further comprising: putting the metal article with the first hole into an alkaline solution to remove the oxide layer; and putting the metal article with the oxide layer removed into a second electrolyte, to form a second hole on a surface of the second metal layer.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) Implementations of the present disclosure will now be described, by way of example only, with reference to the attached figures.
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DETAILED DESCRIPTION
(14) It will be appreciated that for simplicity and clarity of illustration, where appropriate, reference numerals have been repeated among the different figures to indicate corresponding or analogous elements. In addition, numerous specific details are set forth in order to provide a thorough understanding of the embodiments described herein. However, it will be understood by those of ordinary skill in the art that the embodiments described herein can be practiced without these specific details. In other instances, methods, procedures, and components have not been described in detail so as not to obscure the related relevant feature being described. Also, the description is not to be considered as limiting the scope of the embodiments described herein. The drawings are not necessarily to scale, and the proportions of certain parts may be exaggerated to better illustrate details and features of the present disclosure.
(15) The term “comprising,” when utilized, means “including, but not necessarily limited to”; it specifically indicates open-ended inclusion or membership in the so-described combination, group, series, and the like.
(16) In some embodiments illustrated in
(17) According to some embodiments, the first metal layer 20 includes a first metal. The first metal is at least one selected from the group consisting of stainless steel, carbon steel and iron.
(18) In some embodiments illustrated in
(19) A periphery of the opening 42 of each of the first holes 40 is defined as R. M and N are two different points on the periphery R, and a distance between the two points M and N is a length of a first line segment MN. The length of the first line segment MN is equal to a longest straight-line distance between any two points on the periphery R. The first line segment MN is with a length A. L is a point on the periphery R, and L is different from the points M and N. A plane P of the opening 42 is where the three points M, N, and L are located. A cross-sectional plane Q of the first holes 40 is parallel to the plane P. A periphery S is where the plane Q and an inner wall of each of the first holes 40 intersect. E and F are two different points on the periphery S, and a distance between the two points E and F is a length of a second line segment EF. The length of the second line segment EF is the longest straight-line distance between any two points on the periphery S. The second line segment EF is with a length B. A depth of each of the first holes 40 is defined as H.
(20) There is a plurality of plane Q and a plurality of periphery S, and the length B is the maximum value of the longest straight-line distances in all of the peripheries S, each of the longest straight-line distances is defined between two points on each periphery S. That is, if a longest straight-line distance between two points on a periphery S1 is B1, a longest straight-line distance between two points on a periphery S2 is B2, a longest straight-line distance between two points on a periphery S3 is B3, . . . and a longest straight-line distance between two points on a periphery Sn is Bn (n is an integer value), a value of B is the maximum value of B1, B2, B3 . . . and Bn.
(21) The longest distance A between two points on the periphery R is less than the longest distance B between two points on the periphery S. The opening 42 of each of the first holes 40 is narrower than an interior space 44, so that the first holes 40 each form a hook towards an axis of the first holes 40. The hook enhances a bonding strength between the metal article 100 and a material part 210 on a surface of the metal article 100.
(22) According to some embodiments, the longest distance A between two points on the periphery R is about 10 μm to 50 μm, that is, 10 μm≤A≤50 μm. According to some embodiments, a lower limit of the longest distance A of the first line segment MN is one of 10 μm, 16 μm, 24 μm, 28 μm, 34 μm, 38 μm, 45 μm, and 50 μm. An upper limit of the longest distance A of the first line segment MN is one of 12 μm, 14 μm, 20 μm, 26 μm, 30 μm, 35 μm, 40 μm, 45 μM, and 50 μm. The lower limit must be not greater than the upper limit.
(23) According to some embodiments, the longest distance B between two points on the periphery S is about 10 μm to 100 μm, that is, 10 μm≤B≤100 μm. According to some embodiments, a lower limit of the longest distance B of the second line segment EF is one of 10 μm, 16 μm, 24 μm, 28 μm, 34 μm, 38 μm, 45 μm, 50 μm, 55 μm, 62 μm, 68 μm, 75 μm, 83 μm, 88 μm, 93 μm, and 99 μm. An upper limit of the longest distance B of the second line segment EF is one of 12 μm, 14 μm, 20 μm, 26 μm, 30 μm, 35 μm, 40 μm, 45 μm, 50 μm, 16 μm, 64 μm, 70 μm, 76 μm, 80 μm, 87 μm, 95 μm, 98 μm, and 100 μm. The lower limit must be not greater than the upper limit.
(24) According to some embodiments, a depth H of each of the first holes 40 is about 30 μm to 120 μm, that is, 30 μm≤H≤120 μm. According to some embodiments, a lower limit of the depth H of each of the first holes 40 is one of 30 μm, 36 μm, 40 μm, 47 μm, 58 μm, 61 μm, 72 μm, 80 μm, 88 μm, 93 μm, 101 μm, 105 μm, 112 μm, and 120 μm. An upper limit of the depth H of each of the first holes 40 is one of 32 μm, 39 μm, 48 μm, 50 μm, 66 μm, 76 μm, 80 μm, 87 μm, 95 μm, 100 μm, 108 μm, 116 μm, and 120 μm. The lower limit must be not greater than the upper limit.
(25) An oxide layer 30 is set on the second outer surface 14 of the second metal layer 10. The oxide layer 30 covers the second outer surface 14. The oxide layer 30 is a passivation layer formed by metal oxidation reaction of the second metal layer 10.
(26) According to some embodiments, the second metal layer 10 includes a second metal. The second metal is at least one selected from the group consisting of aluminum and aluminum alloys. In an embodiment, the second metal is aluminum, and the oxide layer 30 is alumina.
(27) According to some embodiments, a thickness D of the oxide layer 30 is about 0 μm to 1 μm, that is, 0 μm<D≤1 μm. According to some embodiments, a lower limit of the thickness D of the oxide layer 30 is one of 0.001 μm, 0.002 μm, 0.005 μm, 0.01 μm, 0.02 μm, 0.05 μm, 0.08 μm, 0.1 μm, 0.2 μm, 0.5 μm, 0.8 μm, and 0.9 μm. An upper limit of the thickness D of the oxide layer 30 is one of 0.003 μm, 0.006 μm, 0.008 μm, 0.015 μm, 0.025 μm, 0.06 μm, 0.09 μm, 0.15 μm, 0.3 μm, 0.6 μm, 0.85 μm, and 0.95 μm. The lower limit must be not greater than the upper limit.
(28) In some embodiments illustrated in
(29) In the present disclosure, the size (including length and depth) of the second holes 46 can be set as required and is not limited. For example, the size of the second holes 46 may be the same as the size of the first holes 40.
(30) In some embodiments illustrated in
(31) The material part 210 includes a plurality of bonding portions 220. At least some of the bonding portions 220 are in the interior space 44 of the first holes 40, to combine the material part 210 and the metal article 100. According to some embodiments, the bonding portions 220 completely fill the interior spaces 44 of the first holes 40.
(32) According to some embodiments, the first outer surface 24 is a surface of the first metal layer 20. That is, the first holes 40 are set on one surface of the first metal layer 20. According to other embodiments, the first outer surface 24 includes multiple surfaces of the first metal layer 20. That is, the first holes 40 are set on multiple surfaces of the first metal layer 20.
(33) According to some embodiments, the material part 210 may be made of a material selected from a group consisting of metal, polymer, ceramic, glass, and any combination thereof.
(34) In some embodiments illustrated in
(35) According to some embodiments, a method for manufacturing the metal article 100 is provided. In some embodiments illustrated in
(36) Step 1: putting a metal substrate into a first electrolyte. The first electrolyte includes an etching agent and a passivating agent. The metal substrate includes a first metal layer 20 and a second metal layer 10, and the second metal layer 10 is set on a surface of the first metal layer 20.
(37) Step 2: applying electricity on the metal substrate, forming a plurality of first holes 40 on the surface of the first metal layer 20, and an oxide layer 30 on the surface of a second metal layer 10. Then, the metal article 100 is obtained.
(38) In the step 1, the etching agent is at least one selected from the group consisting of sulfuric acid, nitric acid, sulfate and nitrate. The passivating agent is at least one selected from the group consisting of sulfuric acid, nitric acid, oxalic acid, phosphoric acid, citric acid, sulfate, nitrate, oxalate, phosphate and citrate. An acid radical of the etching agent is different from an acid radical of the passivating agent, and at least one of the etching agents and passivating agents include hydrogen ion. The acid radical is of the inorganic acid group except for the hydrogen ion. The acid radical of the etching agent and the acid radical of the passivating agent are different. For example, if sulfuric acid is the etching agent, then sulfuric acid and sulfate containing sulfate cannot be selected as the passivating agent, and at least one of nitric acid, oxalic acid, phosphoric acid, citric acid, nitrate, oxalate, phosphate and citrate must be selected as the passivating agent. At least one of the etching agents and passivating agents include hydrogen ion to maintain acidity of the system. Sulfuric acid and nitric acid can be used as both the etching agent and the passivating agent. The passivating agent can passivate the second outer surface 14 of the second metal layer 10 to form an oxide layer 30 during an electrolysis process. The etching agent can form the first holes 40 on the first outer surface 24 of the first metal layer 20 during the electrolysis process.
(39) A total volume ratio C of the etching agent and the passivating agent in the first electrolyte is about 0.01% to 10%, that is, 0.01%≤C≤10%. The volume ratio C of the electrolyte can be converted into a mass ratio according to actual conditions. According to some embodiments, a lower limit of the volume ratio C is one of 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, and 10%. An upper limit of the volume ratio C is one of 1.5%, 2.5%, 3.5%, 4.5%, 5.5%, 6.5%, 7.5%, 8.5%, 9.5%, and 10%. The lower limit must be not greater than the upper limit. The volume ratio C affects a pH value of the first electrolyte.
(40) The pH value of the first electrolyte is about 1 to 4, that is, 1≤pH≤4. According to some embodiments, a lower limit of the pH value of the first electrolyte is one of 1, 1.5, 1.8, 2, 2.4, 2.7, 3.2, 3.5, and 4. An upper limit of the pH value of the first electrolyte is one of 1, 1.6, 1.9, 2, 2.6, 2.9, 3.3, 3.6, and 4. The lower limit must be not greater than the upper limit. When the lower limit of the pH value of the first electrolyte is too small (for example, less than 1), an acidity of the first electrolyte is too strong, the length A of the first line segment, the length B of the second line segment, and the depth H of the first holes 40 are not easy to control during the electrolysis process with such acid. When the upper limit of the pH value of the first electrolyte is too high (for example, more than 4), the acidity of the first electrolyte is too weak, the thickness D of the oxide layer 30 formed by the second metal layer 10 in the first electrolyte is not thick enough, resulting in unexpected corrosion of the second metal layer 10 covered by the oxide layer 30.
(41) According to some embodiments, the pH value of the first electrolyte is about 1 to 2, that is, 1≤pH≤2.
(42) The metal substrate functions as a positive electrode in the first electrolyte. A negative electrode is also put into the first electrolyte.
(43) The first metal layer 20 of the metal substrate includes a first metal. The first metal is at least one selected from the group consisting of stainless steel, carbon steel and iron. The second metal layer 10 includes a second metal. The second metal is at least one selected from the group consisting of aluminum and aluminum alloys. Aluminum or aluminum alloy is passivated to form aluminum oxide, that is, the oxide layer 30.
(44) The negative electrode is made of a conductive inorganic material. The conductive inorganic material can be metal or non-metal. The metal can be selected from one of gold, silver, copper, zinc, tungsten, magnesium, brass, iron, platinum, calcium, molybdenum, cobalt, chromium, nickel, indium and tin. The non-metal can be selected from graphite.
(45) In the step 2, when there is electricity between the positive electrode and the negative electrode, the metal substrate is electrolyzed. The electricity may be generated by a DC power or an AC power.
(46) According to some embodiments, the voltage V.sub.1 is about 1 V to 5 V, that is, 1≤V.sub.1<5. According to some embodiments, a lower limit of the voltage V.sub.1 is one of 1 V, 1.5 V, 2 V, 2.5 V, 3 V, 3.5 V, 4 V, 4.5 V and 5 V. An upper limit of the voltage V.sub.1 is one of 1 V, 1.6 V, 2.2 V, 2.7 V, 3.2 V, 3.8 V, 4.2 V, 4.6 V and 5 V. The lower limit must be not greater than the upper limit. When the lower limit of the voltage V.sub.1 is too small (for example, less than 1V), a speed of forming the first holes 40 on the first outer surface 24 of the first metal layer 20 is slow, which increases the time cost. When the upper limit of the voltage V.sub.1 is too large (for example, more than 5V), the oxide layer 30 formed on the second metal layer 10 may be destroyed, resulting in an unexpected corrosion of the second metal layer 10 covered by the oxide layer 30. Also, the speed of forming the first holes 40 of the first metal layer 20 is too fast, and the length A of the first line segment, the length B of the second line segment of the first holes 40, and the depth H of the first holes 40 are not easy to control during the electrolysis process.
(47) According to some embodiments, the voltage V.sub.1 is about 3V to 3.5V, that is, 3≤V.sub.1≤3.5.
(48) According to some embodiments, a temperature T of the electrolysis process is about 15° C. to 50° C., that is, 15° C.≤T≤50° C. According to some embodiments, a lower limit of the temperature is one of 15° C., 20° C., 25° C., 30° C., 35° C., 40° C., 45° C. and 50° C. An upper limit of the temperature is one of 18° C., 22° C., 27° C., 32° C., 37° C., 43° C., 48° C. and 50° C. The lower limit must be not greater than the upper limit.
(49) According to some embodiments, the temperature T of the electrolysis process is about 20° C. to 30° C., that is, 20° C.≤T≤30° C.
(50) According to some embodiments, the temperature T of the electrolysis process is 25° C., that is, T is room temperature. Thus, extra energy and cost is not needed to maintain the temperature of the electrolysis process.
(51) According to some embodiments, a time t of the electrolysis process is about 1 min to 30 min, that is, 1 min≤t≤30 min. According to some embodiments, a lower limit of the time t of the electrolysis process is one of 1 min, 5 min, 8 min, 10 min, 15 min, 18 min, 22 min, 25 min and 30 min. An upper limit of the time t of the electrolysis process is one of 1 min, 6 min, 9 min, 13 min, 16 min, 20 min, 23 min, 27 min, and 30 min. The lower limit must be not greater than the upper limit. When the lower limit of the time t is too short (for example, less than 1 min), the length A of the first line segment, the length B of the second line segment of the first holes 40 of the first metal layer 20 are too small, resulting in a weak bonding strength between the metal article 100 and the material part 210. When the upper limit of the time t is too long (for example, more than 30 min), the length A of the first line, the length B of the second line segment and the depth H of the first holes 40 are too large, resulting in a decreased number of the first holes 40, and the bonding strength of the metal article 100 and the material part 210 is reduced.
(52) According to some embodiments, the time t of the electrolysis process is about 10 min to 20 min, that is, 10 min≤t≤20 min.
(53) According to some embodiments, the time t of the electrolysis process is about 12 min to 15 min, that is, 10 min≤t≤20 min.
(54) During the electrolysis process, in a very short time, the second metal layer 10 on the second outer surface 14 is oxidized (that is, a passivation process), and the oxide layer 30 is formed to cover the second metal layer 10, so that the oxide the layer 30 can protect the second metal layer 10 from being corroded during subsequent electrolysis process. The first metal layer 20 set on the first outer surface 24 is etched to form the hook that extends towards the center axis of each of the first holes 40 (that is, the pitting process). The volume ratio C of the acidic electrolyte in the first electrolyte, the pH value of the first electrolyte, the voltage V1, the temperature T, and the time t are controlled to control the balance of the passivation process and the pitting process, thus the first metal layer 20 is etched in priority to prevent the second metal layer 10 from being corroded.
(55) The electrolysis process may include a single-step electrolytic etching, multi-step electrolytic etching, an electrolytic etching in which the etching electricity is first increased and then decreased, or repeated cycles of the electrolytic etching. The electricity, the temperature, and the time can be set according to actual requirements.
(56) According to some embodiments, the method further includes a step of cleaning the metal substrate to remove grease, oxide layer, and impurities on the surface of the metal substrate before step 1. The cleaning can be carried out by using a conventional simple cleaning method, such as solvent cleaning, chemical treatment, and mechanical treatment.
(57) According to some embodiments, the first electrolyte includes 0.01% sulfuric acid and 0.02% citric acid in volume ratio. The metal substrate is put into the first electrolyte for the electrolysis process. According to some embodiments, the second metal layer 10 of the metal substrate is aluminum, and the first metal layer 20 of the metal substrate is stainless steel. The applied electricity corresponding to a voltage V1 is 2V, the time of the electrolysis process is 3 min, and the electrolysis process was repeated 5 times. The metal substrate is taken out between each interval, washed with deionized water, and then subjected to the next electrolysis process. The metal substrate after the final electrolysis process is taken out, washed with deionized water, and dried to obtain the metal article 100.
(58)
(59) A method for manufacturing the metal article 100a in another embodiment is provided. In some embodiments illustrated in
(60) Step 3: putting the metal article 100 with the first holes 40 into an alkaline solution to remove the oxide layer 30.
(61) Step 4: putting the metal article 100 with the oxide layer 30 removed into a second electrolyte, so that the second holes 46 are formed on the surface of the second metal layer 10. The second electrolyte may be an acidic solution containing sulfuric acid or oxalic acid.
(62) According to some embodiments, the metal article 100 is put into a sodium hydroxide solution. The oxide layer 30 is dissolved in the sodium hydroxide solution, and the first metal of the first metal layer 20 is not dissolved in the sodium hydroxide solution, thus the sodium hydroxide solution will not affect the first metal layer 20.
(63) Then, second holes 46 are formed on the second metal layer 10 by anodizing. Specifically, the metal article 100 with the oxide layer 30 has been removed is used as an anode, and phosphoric acid with a mass ratio of 5 g/L is put in, and a lead plate is selected as a cathode to the electrolysis process. The electrolysis process is performed at a temperature of 15° C., a voltage corresponding to the electricity is 10V. The second metal layer 10 on the surface is etched to form the second holes 46, and at the same time, it is oxidized to form an oxide layer 30a.
(64) There are many ways to form the second holes 46, and the above embodiments are only examples.
(65) In some embodiments illustrated in
(66) Step 11, providing a metal article 100.
(67) Step 12, applying a material of a material part 210 on a surface of the metal article 100.
(68) Step 13, curing the material of the material part 210 to form a metal composite 200.
(69) In step 11, the metal article 100 is manufactured by the method for manufacturing the metal article 100.
(70) In step 12, the material of the material part includes one or more of metal, polymer, ceramic and glass.
(71) In step 13, the material part 210 is applied to at least the first outer surface 24 of the first metal layer 20, and at least a part of the material part 210 enters the first holes 40. After the material part 210 is cured, the material part 210 is set in the first holes 40 forms the bonding portions 220 to combine the material part 210 and the metal article 100, thus the metal composite 200 is obtained.
(72) The material of the material part 210 can be processed by methods which are set according to properties or a status of the material part material.
(73) For example, the material of the material part 210 is metal and in a particle state, the material of the material part 210 may be processed by a laser melting method to form the material part 210.
(74) For example, the material of the material part 210 is polymer, when the material is in a liquid/solution state, the material may be processed by evaporating a solvent of the liquid/solution to form the material part 210. When the material is in a particle state, the material may be processed by a heating to melt the material part 210. When the material is in a molten state, the material may be molded to form the material part 210. When the material is in a gas state, the material may be formed by a gas in-situ polymerization method.
(75) For example, the material of the material part is a ceramic and is in a particle state, the material may be processed by a sintering method or a bonding method with a bonding agent to form the material part 210.
(76) For example, the material of the material part 210 is glass, when the material is in a particle state, the material may be processed by a heat melting method to form the material part 210; when the material is in a molten state, the material may be processed by a cooling method to form the material part 210.
(77) The materials and processing methods of the material of the material part 210 are not limited to the above examples.
(78) According to some embodiments, the metal article 100 is put in a heated mold, a molten plastic is injected into the first holes 40 of the metal article 100, and the metal composite 200 is obtained by injection molding.
(79) According to other embodiments, a method for manufacturing the metal composite 200a is further provided. Differences from the method for preparing the metal composite 200 are: the material of the material part 210 is applied to the metal article 100a with the second holes 46, and the material of the material part 210 is cured. Then the metal composite 200a is obtained. At least a portion of the material part 210 is set in the first holes 40 and the second holes 46.
(80) In the method for manufacturing the metal article 100 and the method for manufacturing the metal composite 200, the etching agent and the passivating agent are added into the first electrolyte to form the oxide layer 30 on the surface of the second metal layer 10 in the first place. The oxide layer 30 on the surface of the second metal layer 10 prevents the unexpected corrosion of the second metal layer 10 during the electrolysis process. In the second place, the first holes 40 are formed on the surface of the first metal layer 20 within a few minutes, and the time of the electrolysis process is short. The composition of the first electrolyte does not contain fluorine and chlorine elements, so that the first electrolyte is environmentally friendly and safe.
(81) It is to be understood, even though information and advantages of the present embodiments have been set forth in the foregoing description, together with details of the structures and functions of the present embodiments, the disclosure is illustrative only; changes may be made in detail, especially in matters of shape, size, and arrangement of parts within the principles of the present embodiments to the full extent indicated by the plain meaning of the terms in which the appended claims are expressed.