Environmentally friendly cold-rolled titanium and titanium alloy plate surface cleaner and preparation method thereof

Abstract

The present invention relates to the field of C23G1 / 00, specifically to an environmentally friendly surface cleaner for cold-rolled titanium and titanium alloy plates and a preparation method thereof. The present invention adopts 5-10 parts of modified organic materials, 0.1-1 parts of passivators, 1-3 parts of corrosion inhibitors, 3-8 parts of complexing agents, 10-20 parts of nonionic surfactants, and 50-70 parts of water, and develops a new generation of green, environmentally friendly, excellent in performance, and convenient to use metal surface cleaning new materials through optimized combination. The product is non-toxic and harmless, does not contain heavy metals, toluene, and strong acids such as hydrochloric acid, sulfuric acid, and hydrofluoric acid, meets RoHS test requirements, is a green and environmentally friendly product, the entire cleaning process is green and environmentally friendly, no strong acid, no waste acid is generated, no dust, no pollution, meets the national industrial development direction, and the cleaned coil surface is bright, suitable for processing high-end titanium and titanium alloy products.

Description

Technical Field

[0001] The invention relates to the field of C23G1 / 00, in particular to an environmentally friendly surface cleaner for cold-rolled titanium and titanium alloy plates and a preparation method thereof. Background Art

[0002] In recent years, the demand for high-end materials in the fields of aerospace, shipbuilding, marine engineering, transportation, and military has continued to grow, and the production of high-end titanium alloys is of great strategic significance. Traditional cold-rolled titanium and titanium alloy plates are washed with a combination of alkali washing and inorganic strong acid (sulfuric acid, hydrochloric acid, etc.) after rolling. Strong alkali is highly corrosive, and inorganic acid is highly polluting, producing waste acid, acid mist, waste residue, and acid-containing wastewater, which cause serious pollution to water, soil, and the atmosphere, and will also cause long-term damage to the human body, seriously harming the health of operators, and also causing safety hazards.

[0003] Chinese patent CN106048630A discloses a strong water-based metal surface oil cleaning agent and its preparation method, which uses polyoxyethylene hexadecyl ether, modified sodium lignosulfonate, sodium citrate, carboxymethyl cellulose, ethylene glycol and the like as main raw materials to provide a cleaning agent with strong cleaning and decontamination ability, but when used for cleaning the surface of cold-rolled titanium and titanium alloy plates, it is not possible to effectively clean the plates while protecting the metal surface. Chinese patent discloses a cleaning agent for cleaning impurities on the surface of titanium alloy and its application method, which mainly uses sodium citrate, triethanolamine, surfactant, phenol and water as raw materials, and solves the problem of waste of titanium alloy caused by impurities on the surface of titanium alloy, but it is easy to leave a large amount of foam on the surface of titanium alloy, affecting the appearance of the product.

[0004] Therefore, the present invention provides an environmentally friendly surface cleaner for cold-rolled titanium and titanium alloy plates, which adopts environmentally friendly special structure organic materials as the main components, and after modification, it is supplemented with appropriately matched passivators, corrosion inhibitors, chelating agents, and surfactants to develop a new generation of green, environmentally friendly, excellent performance, and easy-to-use new metal surface cleaning materials through optimized combination. It is especially suitable for the surface cleaning of titanium plates and their alloys, which has important market application and promotion value. Summary of the invention

[0005] On the one hand, the present invention provides an environmentally friendly surface cleaner for cold-rolled titanium and titanium alloy plates. The raw materials for its preparation include at least 5-10 parts of modified organic material, 0.1-1 parts of passivator, 1-3 parts of corrosion inhibitor, 3-8 parts of complexing agent, 10-20 parts of non-ionic surfactant and 50-70 parts of water, calculated by weight.

[0006] As a preferred technical solution, the modified organic material is selected from one or a combination of modified polyvinyl alcohol, modified starch, and modified carboxymethyl cellulose. Preferably, the modified organic material is modified starch; preferably, the raw materials for preparing the modified starch include at least corn starch, ethylene glycol, and dodecanol; preferably, the preparation method of the modified starch is to mix corn starch, ethylene glycol, and dodecanol in a mass ratio of (1-3): (4-6): (1-2), and then control the temperature to 100-110°C and maintain for 60-90 minutes to obtain the modified starch.

[0007] The surface of titanium plates and their alloys after long-term use will change color due to the interference of the surface titanium oxide layer. Therefore, strong inorganic acids need to be used for pickling in the prior art. However, this will cause the dissolution loss of the base titanium on the one hand. On the other hand, inorganic acids are highly polluting, producing waste acid, acid mist, waste residue and acid-containing wastewater, which will cause serious pollution to water bodies, soil and atmosphere, and will also cause long-term damage to the human body, seriously harm the health of operators, and also create safety hazards. During the exploration process, the inventors found that the use of modified starch in combination with non-ionic surfactants, chelating agents and corrosion inhibitors in the system can effectively promote the dissolution of the titanium oxide layer on the surface of titanium plates and their alloys, without causing the dissolution loss of the base titanium, and also help to delay the corrosion of titanium plates and their alloys and protect the metal surface.

[0008] As a preferred technical solution, the nonionic surfactant is selected from one or more of alkyl alcohol amides, fatty alcohol polyoxyethylene ethers, alkylphenol polyoxyethylene ethers, fatty acid methyl ester polyoxyethylene ethers, and sorbitan esters; preferably, the nonionic surfactant is selected from one or more of lauryl alcohol polyoxyethylene ether, octanol polyoxyethylene ether, isomeric tridecanol polyoxyethylene ether, nonylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether, coconut oil fatty acid diethanolamide, Tween, and Span; preferably, the nonionic surfactant is a combination of lauryl alcohol polyoxyethylene ether, octylphenol polyoxyethylene ether, octyl alcohol polyoxyethylene ether, and coconut oil fatty acid diethanolamide; preferably, the lauryl alcohol polyoxyethylene ether, octylphenol polyoxyethylene ether, octyl alcohol polyoxyethylene ether, and coconut oil fatty acid diethanolamide. The mass ratio of lauryl alcohol polyoxyethylene ether, octanol polyoxyethylene ether and coconut oil fatty acid diethanolamide is (4-6): (5-8): (1-2): (2-4); based on the system of the present invention, the introduction of lauryl alcohol polyoxyethylene ether, octylphenol polyoxyethylene ether, octylphenol polyoxyethylene ether and coconut oil fatty acid diethanolamide in the mass ratio of (4-6): (5-8): (1-2): (2-4) can maximize the synergistic compounding effect, interact with the modified starch in the system, reduce the interfacial tension between the oil stain and the titanium substrate, effectively wet the oil stain, promote the separation of the oil stain, and have low foaming property, thereby ensuring normal operation under spraying, effectively capturing the oil stain while avoiding a large amount of foam remaining on the surface of the titanium substrate, and ensuring the beauty of the product.

[0009] As a preferred technical solution, the complexing agent is selected from one or a combination of oxalic acid, citric acid, malic acid, lactic acid, tartaric acid, gluconic acid, p-hydroxybenzenesulfonic acid, disodium ethylenediaminetetraacetic acid, triethanolamine, potassium sodium tartrate, sodium citrate, sodium silicate, sodium gluconate; preferably, the complexing agent is a combination of potassium sodium tartrate, sodium silicate, and sodium gluconate; preferably, the mass ratio of potassium sodium tartrate, sodium silicate, and sodium gluconate is (2-4): (4-6): (3-5). Based on the system of the present invention, a combined complexing agent of potassium sodium tartrate, sodium silicate, and sodium gluconate is introduced, and the mass ratio of potassium sodium tartrate, sodium silicate, and sodium gluconate is controlled to be (2-4): (4-6): (3-5), which can play a synergistic role. Under the action of the surfactant in the system, it has a good dissolving effect on the oil stains and impurities on the surface of the cold-rolled titanium and titanium alloy plates, thereby improving the surface cleaning effect.

[0010] As a preferred technical solution, the corrosion inhibitor is selected from at least one of benzotriazole, methylbenzotriazole, and mercaptobenzothiazole; preferably, the corrosion inhibitor is a combination of benzotriazole and mercaptobenzothiazole; preferably, the mass ratio of benzotriazole to mercaptobenzothiazole is (2-4):(1-3).

[0011] As a preferred technical solution, the passivator is a mixture of one or more of a molybdate passivator, a silicate passivator, a tungstate passivator, a polyphosphate passivator, and an organic amine passivator; preferably, the passivator is a combination of sodium molybdate and sodium tungstate; the mass ratio of the sodium molybdate to the sodium tungstate is 1:(3-5); based on the system of the present invention, sodium molybdate and sodium tungstate in a mass ratio of 1:(3-5) are used as passivators, and benzotriazole and mercaptobenzothiazole in the synergistic system are used to put the metal in a passivated state in which the oxidation effect is lost.

[0012] The second aspect of the present invention provides a method for preparing an environmentally friendly surface cleaner for cold-rolled titanium and titanium alloy plates. The modified organic material, passivator, corrosion inhibitor, complexing agent, non-ionic surfactant and water are mixed by weight at 30-40°C, the speed of the stirring device is controlled to 300-500rpm, and the mixture is stirred for 20-30 minutes to obtain the cleaning agent.

[0013] Beneficial effects:

[0014] 1. The present invention provides an environmentally friendly surface cleaner for cold-rolled titanium and titanium alloy plates, which uses environmentally friendly special structure organic materials as the main components, and after modification, is supplemented with appropriately matched passivators, corrosion inhibitors, chelating agents, and surfactants. A new generation of green, environmentally friendly, high-performance, and easy-to-use metal surface cleaning new materials are developed through optimized combination. The new materials are particularly suitable for surface cleaning of titanium plates and their alloys, which has important market application and promotion value.

[0015] 2. Based on the system of the present invention, lauryl alcohol polyoxyethylene ether, octylphenol polyoxyethylene ether, octanol polyoxyethylene ether, and coconut oil fatty acid diethanolamide are introduced in a mass ratio of (4-6): (5-8): (1-2): (2-4), which can maximize the synergistic compounding effect, interact with the modified starch in the system, reduce the interfacial tension between the oil stain and the titanium substrate, effectively wet the oil stain, promote the separation of the oil stain, and have low foaming properties, thereby ensuring normal operation under spraying, effectively capturing the oil stain while avoiding a large amount of foam remaining on the surface of the titanium substrate, thereby ensuring the beauty of the product.

[0016] 3. Based on the system of the present invention, a combined complexing agent of potassium sodium tartrate, sodium silicate and sodium gluconate is introduced, and the mass ratio of potassium sodium tartrate, sodium silicate and sodium gluconate is controlled to be (2-4): (4-6): (3-5), which can play a synergistic role. Under the action of the surfactant in the system, it has a good dissolving effect on the oil stains and impurities on the surface of the cold-rolled titanium and titanium alloy plates, thereby improving the surface cleaning effect.

[0017] 4. The surface cleaning agent product provided by the present invention is non-toxic and harmless, does not contain heavy metals, toluene, and strong acids such as hydrochloric acid, sulfuric acid, and hydrofluoric acid, meets the RoHS testing requirements, and is a green and environmentally friendly product. The entire cleaning process is green and environmentally friendly, no strong acid, no waste acid is generated, no dust, and no pollution is generated, which is in line with the national industrial development direction. The cleaned plate and coil surface is bright and suitable for processing high-end titanium and titanium alloy products. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] Figure 1 Titanium coils before (left) and after (right) cleaning with the environmentally friendly cold-rolled titanium and titanium alloy plate surface cleaner prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0019] Example 1

[0020] On the one hand, the present invention provides an environmentally friendly surface cleaner for cold-rolled titanium and titanium alloy plates. The raw materials for its preparation include, by weight: 8 parts of modified organic material, 0.5 parts of passivator, 2 parts of corrosion inhibitor, 5 parts of complexing agent, 15 parts of non-ionic surfactant and 60 parts of water.

[0021] The modified organic material is modified starch; the raw materials for preparing the modified starch include corn starch, ethylene glycol, and dodecanol; the preparation method of the modified starch is to uniformly mix corn starch, ethylene glycol, and dodecanol in a mass ratio of 2:5:1.5, and then control the temperature to be 105°C and maintain for 90 minutes to obtain the modified starch.

[0022] The nonionic surfactant is a combination of lauryl alcohol polyoxyethylene ether, octylphenol polyoxyethylene ether, octanol polyoxyethylene ether, and coconut oil fatty acid diethanolamide; the mass ratio of lauryl alcohol polyoxyethylene ether, octylphenol polyoxyethylene ether, octanol polyoxyethylene ether, and coconut oil fatty acid diethanolamide is 5:7:1.5:3.

[0023] The complexing agent is a combination of potassium sodium tartrate, sodium silicate and sodium gluconate; the mass ratio of potassium sodium tartrate, sodium silicate and sodium gluconate is 3:5:4.

[0024] The corrosion inhibitor is a combination of benzotriazole and mercaptobenzothiazole; the mass ratio of the benzotriazole to mercaptobenzothiazole is 3:2.

[0025] The passivating agent is a combination of sodium molybdate and sodium tungstate; the mass ratio of the sodium molybdate to the sodium tungstate is 1:4.

[0026] The second aspect of the present invention provides a method for preparing an environmentally friendly surface cleaner for cold-rolled titanium and titanium alloy plates. The modified organic material, passivator, corrosion inhibitor, complexing agent, non-ionic surfactant and water are added by weight at 35°C, the speed of the stirring device is controlled to 500 rpm, and the mixture is stirred for 20 minutes to obtain the cleaning agent.

[0027] Example 2

[0028] On the one hand, the present invention provides an environmentally friendly surface cleaner for cold-rolled titanium and titanium alloy plates. The raw materials for its preparation include, by weight: 10 parts of modified organic material, 1 part of passivator, 3 parts of corrosion inhibitor, 8 parts of complexing agent, 20 parts of non-ionic surfactant, and 70 parts of water.

[0029] The modified organic material is modified starch; the raw materials for preparing the modified starch include corn starch, ethylene glycol, and dodecanol; the preparation method of the modified starch is to uniformly mix corn starch, ethylene glycol, and dodecanol in a mass ratio of 3:6:2, and then control the temperature to be 105°C and maintain for 90 minutes to obtain the modified starch.

[0030] The nonionic surfactant is a combination of lauryl alcohol polyoxyethylene ether, octylphenol polyoxyethylene ether, octanol polyoxyethylene ether, and coconut oil fatty acid diethanolamide; the mass ratio of lauryl alcohol polyoxyethylene ether, octylphenol polyoxyethylene ether, octanol polyoxyethylene ether, and coconut oil fatty acid diethanolamide is 6:8:1:2.

[0031] The complexing agent is a combination of potassium sodium tartrate, sodium silicate and sodium gluconate; the mass ratio of potassium sodium tartrate, sodium silicate and sodium gluconate is 4:6:5.

[0032] The corrosion inhibitor is a combination of benzotriazole and mercaptobenzothiazole; the mass ratio of the benzotriazole to mercaptobenzothiazole is 4:3.

[0033] The passivating agent is sodium molybdate.

[0034] The second aspect of the present invention provides a method for preparing an environmentally friendly surface cleaner for cold-rolled titanium and titanium alloy plates. The modified organic material, passivator, corrosion inhibitor, complexing agent, non-ionic surfactant and water are added by weight at 35°C, the speed of the stirring device is controlled to 500 rpm, and the mixture is stirred for 20 minutes to obtain the cleaning agent.

[0035] Example 3

[0036] On the one hand, the present invention provides an environmentally friendly surface cleaner for cold-rolled titanium and titanium alloy plates. The raw materials for its preparation include, by weight: 5 parts of modified organic material, 0.1 parts of passivator, 1 part of corrosion inhibitor, 3 parts of complexing agent, 10 parts of non-ionic surfactant, and 50 parts of water.

[0037] The modified organic material is modified starch; the raw materials for preparing the modified starch include corn starch, ethylene glycol, and dodecanol; the preparation method of the modified starch is to uniformly mix corn starch, ethylene glycol, and dodecanol in a mass ratio of 1:4:1, and then control the temperature to be 105°C and maintain for 90 minutes to obtain the modified starch.

[0038] The nonionic surfactant is a combination of lauryl alcohol polyoxyethylene ether, octylphenol polyoxyethylene ether, octanol polyoxyethylene ether, and coconut oil fatty acid diethanolamide; the mass ratio of lauryl alcohol polyoxyethylene ether, octylphenol polyoxyethylene ether, octanol polyoxyethylene ether, and coconut oil fatty acid diethanolamide is 4:5:1:2.

[0039] The complexing agent is a combination of potassium sodium tartrate, sodium silicate and sodium gluconate; the mass ratio of potassium sodium tartrate, sodium silicate and sodium gluconate is 2:4:3.

[0040] The corrosion inhibitor is a combination of benzotriazole and mercaptobenzothiazole; the mass ratio of the benzotriazole to mercaptobenzothiazole is 2:1.

[0041] The passivating agent is a combination of sodium molybdate and sodium tungstate; the mass ratio of the sodium molybdate to the sodium tungstate is 1:5.

[0042] The second aspect of the present invention provides a method for preparing an environmentally friendly surface cleaner for cold-rolled titanium and titanium alloy plates. The modified organic material, passivator, corrosion inhibitor, complexing agent, non-ionic surfactant and water are added by weight at 35°C, the speed of the stirring device is controlled to 500 rpm, and the mixture is stirred for 20 minutes to obtain the cleaning agent.

[0043] Comparative Example 1

[0044] Comparative Example 1 of the present invention provides an environmentally friendly surface cleaner for cold-rolled titanium and titanium alloy plates, and its specific implementation method is the same as that of Example 1, except that the raw materials for preparing the environmentally friendly surface cleaner for cold-rolled titanium and titanium alloy plates do not include modified organic materials.

[0045] Comparative Example 2

[0046] Comparative Example 2 of the present invention provides an environmentally friendly surface cleaner for cold-rolled titanium and titanium alloy plates, and its specific implementation method is the same as that of Example 1, except that the nonionic surfactant is Tween 20.

[0047] Comparative Example 3

[0048] Comparative Example 3 of the present invention provides an environmentally friendly surface cleaner for cold-rolled titanium and titanium alloy plates, and its specific implementation method is the same as that of Example 1, except that the complexing agent is sodium citrate.

[0049] Performance Testing Methods

[0050] 1. Mineral oil removal rate: Referring to JBT 4323.2-1999, the environmentally friendly cold-rolled titanium and titanium alloy plate surface cleaners prepared in the examples and comparative examples were quenched at 30±2°C on a 1*2m 2 The oil removal rate of the titanium coil sample for artificial oil pollution was measured, including a cleaning time of 10 minutes. The performance test results are shown in Table 1.

[0051] Oil removal rate = (weight of oil stains before cleaning - weight of oil stains after cleaning) × 100% / weight of oil stains before cleaning.

[0052] 2. Finish: The finish of the surface of the cleaned titanium coil sample is evaluated. The specific evaluation criteria are: the surface of the titanium coil sample is bright and has no spots, and the finish is recorded as "excellent". The surface of the titanium coil sample has spots, and the finish is recorded as "good". The surface of the titanium coil sample is black, and the finish is recorded as "poor". The performance test results are shown in Table 1.

[0053] 3. Corrosion: The cleaned titanium coil samples were placed at room temperature for 7 days, and the appearance of the titanium coil samples was observed and the corrosion was evaluated. The specific evaluation criteria were: if there were no corrosion spots and no obvious discoloration on the surface of the titanium coil samples, the corrosion was recorded as "excellent", if there were corrosion spots or obvious discoloration on the surface of the titanium coil samples, the corrosion was recorded as "good", and if there were corrosion spots and obvious discoloration on the surface of the titanium coil samples, the corrosion was recorded as "poor". The performance test results are shown in Table 1.

[0054] Test items Oil removal rate (%) Finish Corrosive Example 1 99.9 excellent excellent Example 2 99.8 excellent excellent Example 3 99.5 excellent excellent Comparative Example 1 92.8 Difference Difference Comparative Example 2 95.1 good good Comparative Example 3 93.4 Difference good

Claims

1. An environmentally friendly surface cleaner for cold-rolled titanium and titanium alloy plates. It is characterized in that The raw materials for its preparation include at least 5-10 parts of modified organic material, 0.1-1 parts of passivator, 1-3 parts of corrosion inhibitor, 3-8 parts of complexing agent, 10-20 parts of non-ionic surfactant and 50-70 parts of water by weight; the modified organic material is modified starch, the raw materials for the preparation of the modified starch include at least corn starch, ethylene glycol and dodecanol, and the preparation method of the modified starch is to mix corn starch, ethylene glycol and dodecanol in a mass ratio of (1-3): (4-6): (1-2), and then control the temperature to 100-110°C and keep for 60-90 minutes to obtain the modified starch; the non-ionic surfactant is a mass The invention relates to a combination of lauryl alcohol polyoxyethylene ether, octylphenol polyoxyethylene ether, octanol polyoxyethylene ether and coconut oil fatty acid diethanolamide in a ratio of (4-6):(5-8):(1-2):(2-4); the complexing agent is a combination of potassium sodium tartrate, sodium silicate and sodium gluconate, and the mass ratio of potassium sodium tartrate, sodium silicate and sodium gluconate is (2-4):(4-6):(3-5); the passivating agent is a combination of sodium molybdate and sodium tungstate, and the mass ratio of sodium molybdate and sodium tungstate is 1:(3-5); the corrosion inhibitor is a combination of benzotriazole and mercaptobenzothiazole, and the mass ratio of benzotriazole and mercaptobenzothiazole is (2-4):(1-3).

2. A method for preparing the surface cleaning agent according to claim 1, It is characterized in that The modified organic material, passivator, corrosion inhibitor, complexing agent, nonionic surfactant and water are mixed by weight at 30-40° C., the speed of the stirring device is controlled to be 300-500 rpm, and the stirring is performed for 20-30 minutes to obtain the product.

Images