Removal solution of metal oxide layer and preparation method and removal method thereof

Abstract

The invention discloses a solution for removing a metal oxide layer and a preparation method and a removal method thereof, and the solution for removing the metal oxide layer comprises 3 to 5 parts of sodium tetraborate, 8 to 15 parts of allyl alcohol polyoxyalkylene ether, 3 to 7 parts of propylene glycol monomethyl ether, 2.5 to 4.5 parts of 2-bromo-2-nitropropane-1, 3-diol, 2 to 3 parts of sodium phytate, 4 to 6 parts of potassium oxalate, 5 to 6 parts of sodium gluconate and 10 to 15 parts of triethanolamine. 1-5 parts of hydrazine sulfate, 10-20 parts of dimethyl sulfoxide and the balance of water. According to the invention, the bond energy of Fe-O, Fe-S and the like is broken by utilizing the synergistic effect of unsaturated compounds, namely allyl alcohol polyoxyalkylene ether alkene and 2-bromo-2-nitropropane-1, 3-diol, and reducing components, namely sodium gluconate and hydrazine sulfate. According to the invention, a penetrating agent sodium tetraborate and a surfactant allyl alcohol polyoxyalkylene ether are used for uniformly accelerating bond breaking, and chelating agents potassium oxalate, sodium phytate and triethanolamine are used for stabilizing a solution and slowly corroding a base material. The hydrogen-absorbing coating has no corrosion to a base material, is close to zero hydrogen absorption, keeps the original mechanical properties unchanged, and has better practicability.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of metal surface protection, and particularly relates to a metal oxide layer removal solution and a preparation method and removal method thereof. BACKGROUND

[0002] A layer of oxide is formed on the surface of a metal part in a natural environment or during machining and heat treatment, and the main components include any one or more of ferric oxide, ferrous oxide, chromium oxide, silicon oxide, manganese oxide, calcium oxide, magnesium oxide, zinc oxide, copper oxide, phosphorus oxide, and sulfur oxide. Before surface treatment such as electroplating, anodizing, oxidation, or passivation, the naturally formed oxide or the scale produced during heat treatment needs to be removed from the surface of the part to obtain a fresh substrate and improve the adhesion of the surface treatment layer.

[0003] Currently, existing processes usually use sandblasting and / or pickling to remove the oxide / scale. However, sandblasting has the disadvantages of high noise, much dust, and unevenness for special-shaped parts. The pickling solution mainly includes hydrochloric acid, sulfuric acid, phosphoric acid, and corrosion inhibitors and surfactants, which have the disadvantages of large smoke, poor safety, strong corrosion, and hydrogen permeation, which destroys the mechanical properties of the substrate. Especially for high-strength steel (heat treatment strength > 1300 MPa), hydrogen embrittlement is easily produced in an acidic environment. Therefore, the use of pickling methods to remove oxides is not allowed, and only sandblasting can be used. However, for high-strength precision-sized parts, sandblasting easily leads to part rejection due to over-dimensioning, which restricts the manufacturing of parts and cannot meet the use requirements.

[0004] The existing Chinese patent CN201910680837.8 discloses a neutral remover for high-temperature scale and a preparation method thereof. The remover includes alkyne alcohol 5-9 parts, plant surfactant dispersant 9-12 parts, reducing agent 10-18 parts, chelating agent 17-34 parts, pH adjuster 2-3 parts, and the rest is deionized water. The alkyne alcohol, plant surfactant, reducing agent, and chelating agent synergistically act. However, the oxide removal rate of this method is slow, the applicable range is narrow, and it is only suitable for the scale produced by high-strength steel at high temperature.

[0005] The existing Chinese patent CN200910094920.3 discloses an acid pickling method before steel electroplating, which removes the rust layer and scale on the surface of steel before electroplating. The weight percentage composition of the pickling solution is: urea 1-20%, ammonium salt 1-10%, HCl 1-20%, H2SO4 1-15%, HNO3 0.1-10%, surfactant 0.001-1%, and the rest is water; the pickling temperature is 10-90℃; and the pickling time is 0.5-30 min. However, this method mainly removes by acid pickling mechanism, and hydrogen is precipitated during the pickling process, which has the risk of hydrogen embrittlement for high-strength steel, and hydrogen removal treatment is required after removal. SUMMARY

[0006] The present application aims to provide a metal oxide layer removal solution and a preparation method and removal method thereof, and aims to solve the above problems.

[0007] The present application is mainly realized by the following technical solutions: A metal oxide layer removal solution, according to weight parts, comprises: Sodium tetraborate: 3-5 parts, Propylene glycol: 8-15 parts, Propylene glycol methyl ether: 3-7 parts, 2-Bromo-2-nitropropane-1,3-diol: 2.5-4.5 parts, Sodium phytate: 2-3 parts, Potassium oxalate: 4-6 parts, Sodium gluconate: 5-6 parts, Triethanolamine: 10-15 parts, Hydrazine sulfate: 1-5 parts, Dimethyl sulfoxide: 10-20 parts, Water: the balance.

[0008] In order to better realize the present application, further, according to weight parts, comprising sodium tetraborate 3 parts, propylene glycol 8 parts, propylene glycol methyl ether 3 parts, 2-bromo-2-nitropropane-1,3-diol 2.5 parts, sodium phytate 2 parts, potassium oxalate 4 parts, sodium gluconate 5 parts, triethanolamine 10 parts, hydrazine sulfate 1 part, dimethyl sulfoxide 10 parts, water 51.5 parts.

[0009] In order to better realize the present application, further, according to weight parts, comprising sodium tetraborate 3 parts, propylene glycol 8 parts, propylene glycol methyl ether 3 parts, 2-bromo-2-nitropropane-1,3-diol 4.5 parts, sodium phytate 3 parts, potassium oxalate 6 parts, sodium gluconate 5 parts, triethanolamine 10 parts, hydrazine sulfate 1 part, dimethyl sulfoxide 10 parts, water 46.5 parts.

[0010] In order to better realize the present application, further, according to weight parts, comprising sodium tetraborate 3 parts, propylene glycol 8 parts, propylene glycol methyl ether 3 parts, 2-bromo-2-nitropropane-1,3-diol 4.5 parts, sodium phytate 3 parts, potassium oxalate 6 parts, sodium gluconate 5 parts, triethanolamine 10 parts, hydrazine sulfate 1 part, dimethyl sulfoxide 10 parts, water 46.5 parts.

[0011] In order to better realize the present application, further, according to weight parts, including sodium tetraborate 3 parts, propylene glycol polyoxyalkylene ether 8 parts, propylene glycol methyl ether 3 parts, 2-bromo-2-nitropropane-1,3-diol 2.5 parts, sodium phytate 2 parts, potassium oxalate 4 parts, sodium gluconate 6 parts, triethanolamine 10 parts, hydrazine sulfate 5 parts, dimethyl sulfoxide 20 parts, water 36.5 parts.

[0012] In order to better realize the present application, further, according to weight parts, including sodium tetraborate 3 parts, propylene glycol polyoxyalkylene ether 8 parts, propylene glycol methyl ether 7 parts, 2-bromo-2-nitropropane-1,3-diol 2.5 parts, sodium phytate 2 parts, potassium oxalate 6 parts, sodium gluconate 6 parts, triethanolamine 12 parts, hydrazine sulfate 5 parts, dimethyl sulfoxide 15 parts, water 33.5 parts.

[0013] The present application is mainly realized by the following technical solutions: A preparation method of a metal oxide layer removal solution, for preparing the metal oxide layer removal solution, characterized in that: pure water is injected into a container, and components are sequentially put into the container for stirring and dissolving, and mixed uniformly; the stirring speed is 300-350 rpm, and the dissolving temperature is 25-35 DEG C.

[0014] In order to better realize the present application, further, the conductivity of the pure water is 2-5 us / cm.

[0015] A metal oxide layer removal method, which is carried out by using the metal oxide layer removal solution, characterized in that: metal parts are soaked in the removal solution for treatment.

[0016] The present application has the following advantages: (1) The main components of the present application are penetrants, reducing agents, chelating agents, surfactants and unsaturated organic matters, which are used for cleaning the metal oxide layer under the condition of pH value 7.5-8.5, have the advantages of safety and environmental protection, have no corrosion to the base material after the oxide is removed, have close to zero hydrogen absorption, have no change to the original mechanical properties, and completely replace sand blasting, strong acid pickling and other methods. The present application is simple to use, can quickly remove the metal oxide layer by room temperature immersion, can be used as a stock solution, can be used after dilution, automatically generates precipitates, is beneficial to recycling and utilization, and reduces the difficulty of sewage treatment. Specifically, the present application is a water-soluble solvent type, has the advantages of non-volatility and non-flammability, and solves the problems of hydrogen permeation and hydrogen embrittlement existing in the acid pickling before electroplating of high-strength steel, and the problems of part easy to be out of tolerance, deformation and the harm of solid waste to the environment and personnel caused by sand blasting of high-strength steel precision parts.

[0017] (2) The etching principle of the present application is different from acid etching, and no hydrogen is generated in the process of decomposing metal oxides, but the oxides are dissolved by destroying the chemical bonds of the oxides, without hydrogen permeation and corrosion of the substrate, eliminating the risk of hydrogen embrittlement caused by pickling, and can make up for the problem of part out-of-tolerance and deformation caused by sandblasting, solve the harm of solid waste caused by sandblasting to the environment and personnel, and has good practicability. The metal oxide layer mentioned in the present application includes metal oxides and metal oxide layers, and the metals include elemental metal substrates, ultrahigh strength steel alloys, copper alloys, aluminum alloys, magnesium alloys, titanium alloys and the like. The present application has wider applicability, higher speed and is suitable for various iron-based alloys, magnesium alloys, titanium alloys, aluminum alloys, copper alloys and other high-temperature oxides and ordinary oxide layers. DETAILED DESCRIPTION

[0018] Example 1 A metal oxide layer removal solution, comprising the following components by weight: Sodium tetraborate: 3-5 parts, Propylene glycol: 8-15 parts, Propylene glycol methyl ether: 3-7 parts, 2-Bromo-2-nitropropane-1,3-diol: 2.5-4.5 parts, Sodium phytate: 2-3 parts, Potassium oxalate: 4-6 parts, Sodium gluconate: 5-6 parts, Triethanolamine: 10-15 parts, Hydrazine sulfate: 1-5 parts, Dimethyl sulfoxide: 10-20 parts, Deionized water: the balance.

[0019] The main components of the present application are penetrants, reducing agents, chelating agents, surfactants, unsaturated organic compounds, and the present application utilizes the synergistic effect of the above unsaturated compounds propylene glycol, 2-bromo-2-nitropropane-1,3-diol, and the reducing components sodium gluconate and hydrazine sulfate to break the bond energy of Fe-O and Fe-S, and the penetrants, surfactants sodium tetraborate and propylene glycol, which can uniformly accelerate the dissolution of the oxides, and the chelating agents potassium oxalate, sodium phytate and triethanolamine, which have the functions of stabilizing the solution and the substrate, can maintain the original physical and mechanical properties of the substrate, and the present application is also effective for copper alloys, aluminum alloys, magnesium alloys and titanium alloys.

[0020] A preparation method of a removing solution for various alloy hot finishing, sequentially stirring, dissolving, putting and mixing the above components. Pour pure water into the container, and sequentially add the above components. The conductivity of the pure water is 2-5 us / cm, start the stirring motor, the stirring speed is 300-350 rpm, and the temperature is raised to 25-35℃. When used, the metal parts can be soaked in the removing solution at room temperature for treatment, and further assisted by ultrasonic wave for enhanced treatment.

[0021] Specifically, the dissolution conditions of each component are: The sodium tetraborate is of analytical grade, the stirring speed is 300-350 rpm, and it is completely dissolved in 10 minutes at a dissolution temperature of 25-35℃; The propylene glycol is of analytical grade, the stirring speed is 300-350 rpm, and it is completely dissolved in 10 minutes at a dissolution temperature of 25-35℃; The propylene glycol is of analytical grade, the stirring speed is 300-350 rpm, and it is completely dissolved in 10 minutes at a dissolution temperature of 25-35℃; The 2-bromo-2-nitropropane-1,3-diol is of analytical grade, the stirring speed is 300-350 rpm, and it is completely dissolved in 10 minutes at a dissolution temperature of 25-35℃; The sodium tetraborate is of analytical grade, the stirring speed is 300-350 rpm, and it is completely dissolved in 10 minutes at a dissolution temperature of 25-35℃; The potassium oxalate is of analytical grade, the stirring speed is 300-350 rpm, and it is completely dissolved in 10 minutes at a dissolution temperature of 25-35℃; The sodium tetraborate is of analytical grade, the stirring speed is 300-350 rpm, and it is completely dissolved in 10 minutes at a dissolution temperature of 25-35℃; The triethanolamine is of analytical grade, the stirring speed is 300-350 rpm, and it is completely dissolved in 10 minutes at a dissolution temperature of 25-35℃; The hydrazine sulfate is of analytical grade, the stirring speed is 300-350 rpm, and it is completely dissolved in 10 minutes at a dissolution temperature of 25-35℃; The dimethyl sulfoxide is of analytical grade, the stirring speed is 300-350 rpm, and it is completely dissolved in 10 minutes at a dissolution temperature of 25-35℃.

[0022] Example 2: A metal oxide layer removal solution, as shown in Table 1, includes, by weight, sodium tetraborate 3 parts, propylene glycol polyoxyalkylene ether 8 parts, propylene glycol methyl ether 3 parts, 2-bromo-2-nitropropane-1,3-diol 2.5 parts, sodium phytate 2 parts, potassium oxalate 4 parts, sodium gluconate 5 parts, triethanolamine 10 parts, hydrazine sulfate 1 part, dimethyl sulfoxide 10 parts, and pure water 51.5 parts. The prepared removal solution is uniform and transparent; the stability meets the requirements.

[0023] As shown in Table 1, under the condition of a dissolution temperature of 25℃, the same batch of heat-treated high-strength steel and titanium alloy test pieces are placed in 1 liter of the solution, and it is observed that the oxide of the high-strength steel and titanium alloy test pieces is completely removed in 75 minutes and 113 minutes, respectively, and the matrix is intact and qualified.

[0024] The present application utilizes the synergistic effect of unsaturated compounds propylene glycol polyoxyalkylene ether, 2-bromo-2-nitropropane-1,3-diol, and reducing components sodium gluconate and hydrazine sulfate to break the bond energy of Fe-O and Fe-S. The present application utilizes the penetrating agent sodium tetraborate and the surfactant propylene glycol polyoxyalkylene ether to uniformly accelerate the bond breaking, and utilizes the chelating agents potassium oxalate, sodium phytate, and triethanolamine to stabilize the solution and slow down the corrosion of the substrate. The present application has no corrosion to the substrate, close to zero hydrogen absorption, no change in the original mechanical properties, and good practicability.

[0025] Example 3 A metal oxide layer removal solution, as shown in Table 1, includes, by weight, sodium tetraborate 3 parts, propylene glycol polyoxyalkylene ether 8 parts, propylene glycol methyl ether 3 parts, 2-bromo-2-nitropropane-1,3-diol 4.5 parts, sodium phytate 3 parts, potassium oxalate 6 parts, sodium gluconate 5 parts, triethanolamine 10 parts, hydrazine sulfate 1 part, dimethyl sulfoxide 10 parts, and pure water 46.5 parts. The prepared removal solution is uniform and transparent; the stability meets the requirements.

[0026] As shown in Table 1, under the condition of a dissolution temperature of 25℃, the same batch of heat-treated high-strength steel and titanium alloy test pieces are placed in 1 liter of the solution, and it is observed that the oxide of the high-strength steel and titanium alloy test pieces is completely removed in 75 minutes and 113 minutes, respectively, and the matrix is intact and qualified.

[0027] Example 4 A metal oxide layer removal solution, as shown in Table 1, includes, by weight, sodium tetraborate 3 parts, propylene glycol polyoxyalkylene ether 15 parts, propylene glycol methyl ether 3 parts, 2-bromo-2-nitropropane-1,3-diol 2.5 parts, sodium phytate 2 parts, potassium oxalate 4 parts, sodium gluconate 6 parts, triethanolamine 15 parts, hydrazine sulfate 5 parts, dimethyl sulfoxide 10 parts, and pure water 34.5 parts. The prepared removal solution is uniform and transparent; the stability meets the requirements.

[0028] As shown in Table 1, under the condition of a dissolving temperature of 25℃, the same batch of high-strength steel and titanium alloy test pieces were placed in 1 liter of the solution, and it was observed that the high-strength steel and titanium alloy test pieces were completely removed of the oxides in 84 minutes and 136 minutes respectively, and the substrates were intact and qualified.

[0029] Example 5 A metal oxide layer removal solution, as shown in Table 1, included, by weight, 3 parts of sodium tetraborate, 8 parts of propylene glycol, 3 parts of propylene glycol methyl ether, 2.5 parts of 2-bromo-2-nitropropane-1,3-diol, 2 parts of sodium phytate, 4 parts of potassium oxalate, 6 parts of sodium gluconate, 10 parts of triethanolamine, 5 parts of hydrazine sulfate, 20 parts of dimethyl sulfoxide, and 36.5 parts of pure water. The prepared removal solution was uniform and transparent, and the stability met the requirements.

[0030] As shown in Table 1, under the condition of a dissolving temperature of 25℃, the same batch of high-strength steel and titanium alloy test pieces were placed in 1 liter of the solution, and it was observed that the high-strength steel and titanium alloy test pieces were completely removed of the oxides in 68 minutes and 106 minutes respectively, and the substrates were intact and qualified.

[0031] Example 6 A metal oxide layer removal solution, as shown in Table 1, included, by weight, 3 parts of sodium tetraborate, 8 parts of propylene glycol, 7 parts of propylene glycol methyl ether, 2.5 parts of 2-bromo-2-nitropropane-1,3-diol, 2 parts of sodium phytate, 6 parts of potassium oxalate, 6 parts of sodium gluconate, 12 parts of triethanolamine, 5 parts of hydrazine sulfate, 15 parts of dimethyl sulfoxide, and 33.5 parts of pure water. The prepared removal solution was uniform and transparent, and the stability met the requirements.

[0032] As shown in Table 1, under the condition of a dissolving temperature of 25℃, the same batch of high-strength steel and titanium alloy test pieces were placed in 1 liter of the solution, and it was observed that the high-strength steel and titanium alloy test pieces were completely removed of the oxides in 75 minutes and 111 minutes respectively, and the substrates were intact and qualified.

[0033] Example 7 A metal oxide layer removal solution, as shown in Table 1, included, by weight, 3 parts of sodium tetraborate, 15 parts of propylene glycol, 3 parts of propylene glycol methyl ether, 4.5 parts of 2-bromo-2-nitropropane-1,3-diol, 2 parts of sodium phytate, 4 parts of potassium oxalate, 6 parts of sodium gluconate, 10 parts of triethanolamine, 5 parts of hydrazine sulfate, 10 parts of dimethyl sulfoxide, and 37.5 parts of pure water. The prepared removal solution was uniform and transparent, and the stability met the requirements.

[0034] As shown in Table 1, under the condition that the dissolving temperature is 25℃, the same batch of high-strength steel and titanium alloy test pieces are placed in 1 liter of solution, and it is observed that the high-strength steel and titanium alloy test pieces are completely removed of oxides in 58 minutes and 91 minutes respectively, and the substrates are intact and qualified.

[0035] Table 1 The above is only the preferred embodiment of the present application, and does not limit the present application in any form. Any simple modification or equivalent change of the above embodiment according to the technical essence of the present application falls within the protection scope of the present application.

Claims

1. A solution for removing a metal oxide layer, characterized in that: Calculated by weight, including: Sodium tetraborate: 3-5 parts, Propylene alcohol polyoxyalkylene ether: 8-15 parts, Propylene glycol methyl ether: 3-7 parts, 2-Bromo-2-nitropropane-1,3-diol: 2.5-4.5 parts, Sodium phytate: 2-3 parts, Potassium oxalate: 4-6 parts, Sodium gluconate: 5-6 parts, Triethanolamine: 10-15 parts, Hydrazine sulfate: 1-5 parts, Dimethyl sulfoxide: 10-20 parts, Water: Balance.

2. The metal oxide layer removal solution according to claim 1, characterized in that: Calculated by weight, it includes 3 parts of sodium tetraborate, 8 parts of propylene glycol polyoxyethylene ether, 3 parts of propylene glycol methyl ether, 2.5 parts of 2-bromo-2-nitropropane-1,3-diol, 2 parts of sodium phytate, 4 parts of potassium oxalate, 5 parts of sodium gluconate, 10 parts of triethanolamine, 1 part of hydrazine sulfate, 10 parts of dimethyl sulfoxide, and 51.5 parts of water.

3. The metal oxide layer removal solution according to claim 1, characterized in that: Calculated by weight, it includes 3 parts of sodium tetraborate, 8 parts of propylene glycol polyoxyethylene ether, 3 parts of propylene glycol methyl ether, 4.5 parts of 2-bromo-2-nitropropane-1,3-diol, 3 parts of sodium phytate, 6 parts of potassium oxalate, 5 parts of sodium gluconate, 10 parts of triethanolamine, 1 part of hydrazine sulfate, 10 parts of dimethyl sulfoxide, and 46.5 parts of water.

4. The metal oxide layer removal solution according to claim 1, characterized in that: Calculated by weight, it includes 3 parts of sodium tetraborate, 15 parts of propylene glycol polyoxyethylene ether, 3 parts of propylene glycol methyl ether, 2.5 parts of 2-bromo-2-nitropropane-1,3-diol, 2 parts of sodium phytate, 4 parts of potassium oxalate, 6 parts of sodium gluconate, 15 parts of triethanolamine, 5 parts of hydrazine sulfate, 10 parts of dimethyl sulfoxide, and 34.5 parts of water.

5. The metal oxide layer removal solution according to claim 1, characterized in that: Calculated by weight, it includes 3 parts of sodium tetraborate, 8 parts of propylene glycol polyoxyethylene ether, 3 parts of propylene glycol methyl ether, 2.5 parts of 2-bromo-2-nitropropane-1,3-diol, 2 parts of sodium phytate, 4 parts of potassium oxalate, 6 parts of sodium gluconate, 10 parts of triethanolamine, 5 parts of hydrazine sulfate, 20 parts of dimethyl sulfoxide, and 36.5 parts of water.

6. The metal oxide layer removal solution according to claim 1, characterized in that: Calculated by weight, it includes 3 parts of sodium tetraborate, 8 parts of propylene glycol polyoxyethylene ether, 7 parts of propylene glycol methyl ether, 2.5 parts of 2-bromo-2-nitropropane-1,3-diol, 2 parts of sodium phytate, 6 parts of potassium oxalate, 6 parts of sodium gluconate, 12 parts of triethanolamine, 5 parts of hydrazine sulfate, 15 parts of dimethyl sulfoxide, and 33.5 parts of water.

7. A method for preparing a solution for removing a metal oxide layer, for preparing the solution for removing a metal oxide layer according to any one of claims 1 to 6, characterized in that: Pour pure water into the container, and put the components into the container in sequence, stir and dissolve, and mix evenly; the stirring speed is 300-350 rpm, and the dissolution temperature is 25-35℃.

8. The method for preparing a solution for removing a metal oxide layer according to claim 7, characterized in that: The conductivity of the pure water is 2-5 us / cm.

9. A method for removing a metal oxide layer, using the metal oxide layer removal solution according to any one of claims 1 to 6, characterized in that: Treat the metal parts by soaking them in the removal solution.

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