CN210420166U - Non-cyanide cadmium titanium alloy and trivalent chromium passivation coating structure of aluminum alloy matrix - Google Patents
Non-cyanide cadmium titanium alloy and trivalent chromium passivation coating structure of aluminum alloy matrix Download PDFInfo
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- CN210420166U CN210420166U CN201920686485.2U CN201920686485U CN210420166U CN 210420166 U CN210420166 U CN 210420166U CN 201920686485 U CN201920686485 U CN 201920686485U CN 210420166 U CN210420166 U CN 210420166U
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Abstract
The utility model discloses an aluminum alloy base member's no cyanogen cadmium titanium alloy and trivalent chromium passivation coating structure, including aluminum alloy base member and the zinc dipping layer, alkaline chemistry nickel coating, low-phosphorus chemistry nickel coating, no cyanogen cadmium titanium alloy cladding material, trivalent chromium passivation layer, the nanometer hydroxyl graphite alkene confining layer that prepare in proper order from inside to outside on aluminum alloy base member surface, no cyanogen cadmium titanium alloy cladding material adopts potassium chloride no cyanogen cadmium titanium alloy electroplating process preparation, and the graphite alkene confining layer adopts the modified sealant preparation of nanometer hydroxyl graphite alkene. The utility model provides a cladding material structure carries out neutral salt fog test 3500h according to GB/T10125 + 2012 "artificial atmosphere corrosion test salt fog test", and the piece surface that plates does not have white corrosive substance and generates, has excellent corrosion resistance, cladding material structure has replaced the hexavalent chromium passivation layer of high toxicity with the trivalent chromium passivation layer, accords with cleaner production's requirement, has better market prospect.
Description
Technical Field
The utility model belongs to the field of metal plating, in particular to a cyanide-free cadmium titanium alloy and trivalent chromium passivation coating structure of an aluminum alloy matrix.
Background
The plating interlayer has excellent corrosion resistance, and is widely applied to aerospace and navigation parts and some electronic products with special requirements. At present, cyanide cadmium plating and/or cyanide-free cadmium plating are adopted to prepare the protective layer for the aerospace aluminum alloy parts, and the white corrosive does not appear in 96h of a neutral salt spray test of a plated interlayer according to the requirements of the original aerospace industry ministry standard QJ 453 and 1988 cadmium plating technical conditions.
The cadmium-titanium alloy coating has the characteristic of low hydrogen brittleness, and is currently used for preparing protective layers of aerospace high-strength steel parts. Compared with the plating of the interlayer, the cadmium-titanium alloy plating layer has higher corrosion resistance, and the application field of the cadmium-titanium alloy plating layer is to be further developed. In the prior art, a cadmium-titanium alloy plating layer is prepared by adopting a cyanide cadmium-titanium alloy electroplating process and a nitrilotriacetic acid-ammonium salt cyanide-free cadmium-titanium alloy electroplating process, and because the two processes are unstable, the plating solution is difficult to maintain and the plating layer is not compact enough, the application of the cadmium-titanium alloy plating layer is limited.
The corrosion resistance of the plating interlayer prepared by the prior art is relatively low, and with the rapid development of the aerospace industry, the corrosion resistance of the prior plating interlayer can not meet the increasing technical requirements of aerospace products.
The passivation layer of the plating interlayer prepared by the prior art adopts a highly toxic hexavalent chromium passivation process, and has the problem of high pollution.
SUMMERY OF THE UTILITY MODEL
An object of the utility model is to provide an aluminum alloy base member's cyanide-free cadmium titanium alloy and trivalent chromium passivation coating structure to solve the cladding material corrosion resistance that prior art prepared and can not satisfy modern national defense industry demand, cladding material production is not friendly scheduling problem to the environment.
In order to achieve the purpose, the utility model adopts the following technical scheme:
a cyanide-free cadmium-titanium alloy and trivalent chromium passivation coating structure of an aluminum alloy matrix comprises the aluminum alloy matrix, and a zinc dipping layer, an alkaline chemical nickel coating layer, a low-phosphorus chemical nickel coating layer, a cyanide-free cadmium-titanium alloy coating layer, a trivalent chromium passivation layer and a nano-hydroxyl graphene sealing layer are sequentially prepared on the surface of the aluminum alloy matrix from inside to outside.
Further, the thickness of the alkaline chemical nickel plating layer is 0.5-3 μm.
Further, the thickness of the alkaline chemical nickel plating layer is 1-2 μm.
Further, the alkaline chemical nickel plating layer is prepared by an alkaline chemical nickel plating process.
Further, the thickness of the low-phosphorus chemical nickel plating layer is 2-10 mu m.
Further, the thickness of the low-phosphorus chemical nickel plating layer is 5-8 mu m.
Further, the low-phosphorus chemical nickel-plating layer is prepared by adopting a low-phosphorus chemical nickel-plating process.
Furthermore, the thickness of the cyanide-free cadmium titanium alloy coating is 8-24 μm.
Furthermore, the thickness of the cyanide-free cadmium titanium alloy plating layer is 10-12 mu m.
Furthermore, the thickness of the cyanide-free cadmium titanium alloy plating layer is 12-14 mu m.
Furthermore, the cyanide-free cadmium titanium alloy plating layer is prepared by a potassium chloride cyanide-free cadmium titanium alloy electroplating process;
the plating solution used in the potassium chloride cyanide-free cadmium titanium alloy electroplating process comprises the following components: cadmium chloride, potassium chloride, a coordination agent, sodium fluoride, a titanium salt supply agent, a brightening agent, an auxiliary agent and a displacement agent.
Further, the trivalent chromium passivation layer is prepared by a trivalent chromium blue-white passivator or a trivalent chromium color passivator.
Further, the thickness of the nano-hydroxyl graphene sealing layer is 0.3-1.5 mu m.
Further, the thickness of the nano-hydroxyl graphene sealing layer is 0.5-1 μm.
Further, the nano-hydroxyl graphene sealing layer is prepared by adopting a nano-hydroxyl graphene sealing process;
the sealing liquid applied to the nano-hydroxyl graphene sealing process comprises the following components: silica sol, water-soluble silane polymer, nano-level hydroxyl graphene solution, an organic silicon defoaming agent, an organic silicon flatting agent and deionized water.
The utility model has the advantages that:
1. the alkaline chemical nickel plating layer is prepared by adopting an alkaline chemical nickel plating process, the alkaline chemical nickel plating solution has small corrosivity to a zinc dipping layer, and the prepared chemical nickel plating layer has good binding force;
2. the bottom layer of the cadmium-titanium alloy plating layer is prepared by adopting a low-phosphorus chemical nickel plating process, and the low-phosphorus chemical nickel plating layer is not easy to passivate and can form better bonding force with the cadmium-titanium alloy plating layer;
3. the cyanide-free cadmium-titanium alloy plating layer is prepared on the substrate, so that the compactness and corrosion resistance of the plating layer are improved, and the brightness of the plating layer is high;
4. the trivalent chromium passivation layer replaces a hexavalent chromium passivation layer, so that the pollution of the coating production to the environment is reduced;
5. the nano-hydroxyl graphene sealing layer is prepared on the trivalent chromium passivation layer, so that the wear resistance, corrosion resistance and scratch resistance of the coating can be obviously improved, and the nano-hydroxyl graphene sealing layer also has self-repairability and can make up for the technical defect that the trivalent chromium passivation layer is lack of self-repairability;
6. the potassium chloride cyanide-free cadmium titanium alloy electroplating process is newly developed by ultra-high chemical industry, has stable process performance, convenient maintenance of plating solution, high compactness of plating layer and excellent corrosion resistance.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this application, do not constitute a limitation of the invention, and in which:
FIG. 1 is a schematic diagram of the structure of the coating layer of the present invention.
Detailed Description
The present invention will be described in detail with reference to the drawings and specific embodiments, and the exemplary embodiments and descriptions of the present invention are used to explain the present invention, but not to limit the present invention.
Example 1:
as shown in fig. 1, a cyanide-free cadmium titanium alloy and trivalent chromium passivation coating structure of an aluminum alloy matrix comprises an aluminum alloy matrix 1, and a zinc dipping layer 2, an alkaline chemical nickel plating layer 3, a low-phosphorus chemical nickel plating layer 4, a cyanide-free cadmium titanium alloy coating 5, a trivalent chromium blue-white passivation layer 6 and a nano-hydroxyl graphene sealing layer 7 are sequentially prepared on the surface of the aluminum alloy matrix from inside to outside.
The zinc dipping layer 2 is prepared by adopting the existing secondary zinc dipping process.
The alkaline chemical nickel-plating layer 3 is prepared by an alkaline chemical nickel-plating process, and the thickness of the plating layer is 1-2 mu m.
The low-phosphorus chemical nickel-plating layer 4 is prepared by adopting a low-phosphorus chemical nickel-plating process, and the thickness of the plating layer is 6-8 mu m.
The thickness of the cyanide-free cadmium titanium alloy plating layer 5 is 12-14 mu m; it is prepared by adopting a potassium chloride cyanide-free cadmium titanium alloy process.
The technological parameters of the potassium chloride cyanide-free cadmium titanium alloy electroplating process are as follows: 20g/L of cadmium chloride, 80-100 g/L of coordination agent, 160g/L of potassium chloride, 2g/L of sodium fluoride, 3mL/L of titanium salt replenishment agent, 2mL/L of brightening agent, 30mL/L of auxiliary agent, 10mL/L of displacement agent, 6.5-7.5 of pH value of plating solution, 20-35 ℃ of temperature of plating bath, and 1A/dm of cathode current density2The area ratio of the cathode to the anode is 1: 1, and the anode is a cadmium plate with the cadmium content being more than or equal to 99.97 percent.
The dislocation agent contains water-soluble propargylamide polymer with the mass concentration of 8-12 g/L, sodium dimethylbenzenesulfonate with the mass concentration of 50-80 g/L and polyethylene oxide ether phosphate with the product type of PE 600 of 80-120 mL/L. Adding 8-12 g of water-soluble propargylamide polymer, 50-80 g of sodium dimethylbenzenesulfonate and 80-120 mL of polyoxyethylene ether phosphate with the product model being PE 600 into 500mL of water, uniformly stirring, and adding water to 1000 mL.
The complexing agent consists of A, B, C components, wherein the component A is nitrilotriacetic acid, the component B is one or two of citric acid, tartaric acid, gluconic acid and malic acid, the component C is one or two of malonic acid, maleic acid, fumaric acid and oxalic acid, and the complexing agent is prepared according to the following proportion: A. 300-400 g, B350-450 g, C250-350 g, adding into a container, stirring and mixing evenly.
The brightener is prepared by adding 300mL of isopropanol into 400mL of water and uniformly mixing, dissolving D, E and F components into a mixed solution of isopropanol and water according to 50-60 g, 35-45 g and 70-90 g respectively, and adding water to 1000 mL.
The adjuvant is prepared by the following method: 60-70G of water-soluble polyacrylamide with the type of IC113, 30-40G of condensation compound consisting of ethylenediamine, dimethylpropylamine and epichlorohydrin, 50-60G of 2-ethylhexyl sulfate sodium salt, 15-25G N, N, N-tris (2-hydroxypropyl) -N' -hydroxyethyl ethylenediamine and 40-50G G components (the component G is consistent with the component F in the brightener) are added into 700G of water, stirred to be dissolved, and then the water is added to 1000 mL.
The titanium salt replenishing agent is an aqueous solution of potassium fluotitanate, 2g of potassium fluotitanate is dissolved in 800mL of water, and water is added to the solution until the volume is 1000 mL.
The trivalent chromium blue-white passivation layer 6 is prepared by adopting TRIROS TCP-185 trivalent chromium blue passivator in the super-bonding chemical industry through the conventional trivalent chromium passivation process.
The nano-graphene sealing layer 7 is prepared by adopting a nano-hydroxyl graphene sealing agent in the ultra-bonding chemical industry through the existing nano-hydroxyl graphene sealing process, and the thickness of the sealing layer is 0.5-1 mu m.
The nano-hydroxyl graphene sealant comprises the following components in parts by weight: 30 parts of silica sol, 20 parts of PU 113 water-soluble silane polymer, 4 parts of nano hydroxyl graphene with the mass fraction of 4%, 0.5 part of TANAOAMS (tamnafOAM) organic silicon defoaming agent produced by Dutch Tuona, 1 part of LA13-863 organic silicon leveling agent produced by Dutch Stall and 40 parts of deionized water.
And diluting the nano-hydroxyl graphene sealing agent by 3 times with deionized water to prepare nano-hydroxyl graphene sealing liquid, dipping the plated part in the sealing liquid, taking out and drying to form a sealing layer.
The operation of the embodiment is divided into the following steps:
1. pretreatment: performing a step of "alkaline chemical degreasing → washing → etching → washing → nitric acid light extraction → washing" on the aluminum alloy substrate 1;
2. and 2, zinc dipping layer 2: after the aluminum alloy matrix 1 is pretreated, preparing a zinc dipping layer 2 by performing 'first zinc dipping → washing → zinc removing → washing → second zinc dipping → washing';
3. alkaline electroless nickel plating layer 3: after the aluminum alloy matrix 1 is soaked with zinc, alkaline chemical nickel plating → water washing is carried out to prepare an alkaline chemical nickel plating layer 3;
4. low-phosphorus electroless nickel plating layer 4: after alkaline chemical nickel plating, the aluminum alloy matrix 1 is subjected to low-phosphorus chemical nickel plating → water washing to prepare a low-phosphorus chemical nickel plating layer 4;
5. the cyanide-free cadmium titanium alloy plating layer 5: after pre-plating nickel on a plated part, performing '10% sulfuric acid activation → cadmium titanium alloy plating → water washing' to prepare a cyanide-free cadmium titanium alloy plating layer 5;
6. trivalent chromium blue-white passivation layer 6: the cyanide-free cadmium titanium alloy plating layer 5 is subjected to '2% nitric acid light extraction → water washing → passivation → water washing' to prepare the trivalent chromium blue-white passivation layer 6.
7. Nano graphene sealing layer 7: and (3) after the trivalent chromium of the plated part is passivated, preparing a nano graphene sealing layer 7 by soaking graphene sealing liquid → dripping, blowing off the sealing liquid remained at the bottom of the plated part → baking at 70-90 ℃.
Example 2:
as shown in fig. 1, a cyanide-free cadmium titanium alloy and trivalent chromium passivation coating structure of an aluminum alloy matrix comprises an aluminum alloy matrix 1, and a zinc dipping layer 2, an alkaline chemical nickel plating layer 3, a low-phosphorus chemical nickel plating layer 4, a cyanide-free cadmium titanium alloy coating 5, a trivalent chromium color passivation layer 6 and a nano-hydroxyl graphene sealing layer 7 are sequentially prepared on the surface of the aluminum alloy matrix from inside to outside.
The zinc dipping layer 2 is prepared by adopting the existing secondary zinc dipping process.
The alkaline chemical nickel-plating layer 3 is prepared by an alkaline chemical nickel-plating process, and the thickness of the plating layer is 1-2 mu m.
The low-phosphorus chemical nickel-plating layer 4 is prepared by a low-phosphorus chemical nickel-plating process, and the thickness of the plating layer is 3-5 microns.
The thickness of the cyanide-free cadmium titanium alloy plating layer 5 is 10-12 mu m, the cyanide-free cadmium titanium alloy plating layer is prepared by adopting a potassium chloride cyanide-free cadmium titanium alloy process, and the process parameters are the same as those in the embodiment 1.
The trivalent chromium color passivation layer 6 is prepared by a TRIROS TR-177 trivalent chromium multicolor passivator in the super-nation chemical industry and is prepared by the existing trivalent chromium passivation process.
The nano-graphene sealing layer 7 is prepared by adopting a nano-hydroxyl graphene sealing agent in the ultra-bonding chemical industry and an existing nano-hydroxyl graphene sealing process, and the thickness of the sealing layer is 0.5-1 mu m.
The nano-hydroxyl graphene sealant comprises the following components in parts by weight: 25 parts of silica sol, 20 parts of PU 113 water-soluble silane polymer, 5 parts of hydroxyl graphene with the mass fraction of 4%, 0.5 part of TANAOAMS (tamnafOAM) organic silicon defoaming agent produced by Dutch Tuona, 1 part of LA13-863 organic silicon leveling agent produced by Dutch Stall and 40 parts of deionized water.
And diluting the hydroxyl graphene modified sealing agent by 3 times with deionized water to prepare graphene sealing liquid, dipping the plated part in the sealing liquid, taking out and drying to form a sealing layer.
The operation of the embodiment is divided into the following steps:
1. pretreatment: performing a step of "alkaline chemical degreasing → washing → etching → washing → nitric acid light extraction → washing" on the aluminum alloy substrate 1;
2. and 2, zinc dipping layer 2: after the aluminum alloy matrix 1 is pretreated, preparing a zinc dipping layer 2 by performing 'first zinc dipping → washing → zinc removing → washing → second zinc dipping → washing';
3. alkaline electroless nickel plating layer 3: after the aluminum alloy matrix 1 is soaked with zinc, alkaline chemical nickel plating → water washing is carried out to prepare an alkaline chemical nickel plating layer 3;
4. low-phosphorus electroless nickel plating layer 4: after alkaline chemical nickel plating, the aluminum alloy matrix 1 is subjected to low-phosphorus chemical nickel plating → water washing to prepare a low-phosphorus chemical nickel plating layer 4;
5. the cyanide-free cadmium titanium alloy plating layer 5: after pre-plating nickel on a plated part, performing '10% sulfuric acid activation → cadmium titanium alloy plating → water washing' to prepare a cyanide-free cadmium titanium alloy plating layer 5;
6. trivalent chromium color passivation layer 6: the cyanide-free cadmium-titanium alloy plating layer 5 is subjected to '2% nitric acid light extraction → water washing → passivation → water washing' to prepare the trivalent chromium color passivation layer 6.
7. Nano graphene sealing layer 7: and (3) after the trivalent chromium of the plated part is passivated, preparing a nano graphene sealing layer 7 by soaking graphene sealing liquid → dripping, blowing off the sealing liquid remained at the bottom of the plated part → baking at 70-90 ℃.
By using the plating layer structures prepared in the embodiments 1 and 2, a neutral salt spray test is carried out for 3500h according to GB/T10125-. The plating layer structure has excellent corrosion resistance.
The coating structure prepared in example 1 and example 2 was used, and the coating adhesion was measured by thermal shock test method according to JB 2111-1977 method for testing the adhesion strength of metal coatings, and the coated article was heated to 190 ℃ in a heating furnace, and was taken out and placed in room temperature water for sudden cooling, and no bubbling or peeling occurred in the coating. The coating structure has good binding force.
The technical solutions provided by the embodiments of the present invention are described in detail above, and the principles and embodiments of the present invention are explained herein by using specific examples, and the descriptions of the above embodiments are only applicable to help understand the principles of the embodiments of the present invention; meanwhile, for a person skilled in the art, according to the embodiments of the present invention, there may be variations in the specific implementation manners and application ranges, and in summary, the content of the description should not be construed as a limitation to the present invention.
Claims (10)
1. A cyanide-free cadmium titanium alloy and trivalent chromium passivation coating structure of an aluminum alloy matrix is characterized in that:
the aluminum alloy substrate is sequentially provided with a zinc dipping layer, an alkaline chemical nickel plating layer, a low-phosphorus chemical nickel plating layer, a cyanide-free cadmium-titanium alloy plating layer, a trivalent chromium passivation layer and a nano hydroxyl graphene sealing layer from inside to outside on the surface of the aluminum alloy substrate.
2. The cyanide-free cadmium titanium alloy and trivalent chromium passivation coating structure of the aluminum alloy matrix according to claim 1, characterized in that:
the thickness of the alkaline chemical nickel plating layer is 0.5-3 μm.
3. The cyanide-free cadmium titanium alloy and trivalent chromium passivation coating structure of the aluminum alloy matrix according to claim 1, characterized in that:
the alkaline chemical nickel plating layer is a plating layer prepared by an alkaline chemical nickel plating process.
4. The cyanide-free cadmium titanium alloy and trivalent chromium passivation coating structure of the aluminum alloy matrix according to claim 1, characterized in that:
the thickness of the low-phosphorus chemical nickel plating layer is 2-10 mu m.
5. The cyanide-free cadmium titanium alloy and trivalent chromium passivation coating structure of the aluminum alloy matrix according to claim 1, characterized in that:
the low-phosphorus chemical nickel-plating layer is a plating layer prepared by adopting a low-phosphorus chemical nickel-plating process.
6. The cyanide-free cadmium titanium alloy and trivalent chromium passivation coating structure of the aluminum alloy matrix according to claim 1, characterized in that:
the thickness of the cyanide-free cadmium-titanium alloy coating is 8-24 mu m.
7. The cyanide-free cadmium titanium alloy and trivalent chromium passivation coating structure of the aluminum alloy matrix according to claim 1 or 6, characterized in that:
the cyanide-free cadmium titanium alloy plating layer is prepared by a potassium chloride cyanide-free cadmium titanium alloy electroplating process.
8. The cyanide-free cadmium titanium alloy and trivalent chromium passivation coating structure of the aluminum alloy matrix according to claim 1, characterized in that:
the trivalent chromium passivation layer is prepared by a trivalent chromium blue-white passivator or a trivalent chromium color passivator.
9. The cyanide-free cadmium titanium alloy and trivalent chromium passivation coating structure of the aluminum alloy matrix according to claim 1 or 4, characterized in that:
the thickness of the nano-hydroxyl graphene sealing layer is 0.3-1.5 mu m.
10. The cyanide-free cadmium titanium alloy and trivalent chromium passivation coating structure of the aluminum alloy matrix according to claim 9, characterized in that:
the nano-hydroxyl graphene sealing layer is prepared by adopting a nano-hydroxyl graphene sealing process.
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| CN113373442A (en) * | 2021-06-11 | 2021-09-10 | 广州超邦化工有限公司 | Zinc-cadmium alloy composite coating of aerospace electrical appliance accessory and preparation method thereof |
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| CN113373442A (en) * | 2021-06-11 | 2021-09-10 | 广州超邦化工有限公司 | Zinc-cadmium alloy composite coating of aerospace electrical appliance accessory and preparation method thereof |
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