WO2023071899A1 - 一种用于金属表面处理的无磷前处理剂 - Google Patents
一种用于金属表面处理的无磷前处理剂 Download PDFInfo
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- WO2023071899A1 WO2023071899A1 PCT/CN2022/126320 CN2022126320W WO2023071899A1 WO 2023071899 A1 WO2023071899 A1 WO 2023071899A1 CN 2022126320 W CN2022126320 W CN 2022126320W WO 2023071899 A1 WO2023071899 A1 WO 2023071899A1
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- phosphorus
- pretreatment agent
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- metal surface
- free pretreatment
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 17
- 239000002184 metal Substances 0.000 title claims abstract description 17
- 238000004381 surface treatment Methods 0.000 title claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920000056 polyoxyethylene ether Polymers 0.000 claims abstract description 21
- 229940051841 polyoxyethylene ether Drugs 0.000 claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 12
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 8
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims abstract description 6
- WXKDNDQLOWPOBY-UHFFFAOYSA-N zirconium(4+);tetranitrate;pentahydrate Chemical compound O.O.O.O.O.[Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WXKDNDQLOWPOBY-UHFFFAOYSA-N 0.000 claims abstract description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003112 inhibitor Substances 0.000 claims abstract description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 5
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 5
- -1 nitric acid hexahydrate Lanthanum Chemical compound 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
- HJVAFZMYQQSPHF-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;boric acid Chemical compound OB(O)O.OCCN(CCO)CCO HJVAFZMYQQSPHF-UHFFFAOYSA-N 0.000 claims description 2
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000001033 ether group Chemical group 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 11
- 238000000576 coating method Methods 0.000 abstract description 11
- 239000003973 paint Substances 0.000 abstract description 10
- 238000000926 separation method Methods 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 9
- 239000012530 fluid Substances 0.000 abstract description 8
- 238000009825 accumulation Methods 0.000 abstract description 6
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000005406 washing Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 16
- 230000008569 process Effects 0.000 description 13
- 238000005238 degreasing Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 6
- 238000002203 pretreatment Methods 0.000 description 5
- 238000005237 degreasing agent Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 239000008399 tap water Substances 0.000 description 4
- 235000020679 tap water Nutrition 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000010960 cold rolled steel Substances 0.000 description 2
- 239000013527 degreasing agent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- HVMFKXBHFRRAAD-UHFFFAOYSA-N lanthanum(3+);trinitrate;hydrate Chemical compound O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HVMFKXBHFRRAAD-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000015227 regulation of liquid surface tension Effects 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 238000004017 vitrification Methods 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G5/00—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents
- C23G5/02—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents
- C23G5/032—Cleaning or de-greasing metallic material by other methods; Apparatus for cleaning or de-greasing metallic material with organic solvents using organic solvents containing oxygen-containing compounds
Definitions
- the invention relates to a phosphorus-free pretreatment agent for metal surface treatment.
- phosphorus-free pretreatment agents As the environmental protection pressure faced by the metal material surface treatment industry increases year by year, phosphorus-free pretreatment agents have emerged as the times require. Among them, ceramic technology and silane technology, as typical representatives of phosphorus-free surface treatment, occupy a pivotal position in phosphorus-free pretreatment agents. Compared with traditional metal surface treatment processes such as phosphating and passivation technologies, phosphorus-free pretreatment agents have incomparable advantages in environmental protection, with little environmental pollution and no eutrophication of water bodies. There are also obvious advantages in maintenance and other aspects. After continuous development in recent years, phosphorus-free technology has been able to meet the needs of most coating industries, with great potential.
- the present invention provides a collection agent with good water washing and oil removal ability, good adhesion and corrosion resistance. Degreasing and film-forming two-in-one phosphorus-free pretreatment agent.
- the phosphorus-free pretreatment agent for metal surface treatment contains 30-40 g of zirconium nitrate pentahydrate, 70-80 g of fluorozirconic acid aqueous solution, 5-8 g of six Lanthanum nitrate hydrate, 3-6g cerium nitrate hexahydrate, 9-12g nitric acid solution, 3-5g rust inhibitor, 200-300g graphene oxide aqueous solution, 80-100g phenylene polyoxyethylene ether surfactant, 100-150g organic Solvent and water balance.
- the zirconium nitrate pentahydrate used has a purity of more than 98%, and its solid content is 1.5% to 4%;
- the fluozirconic acid used is a commercially available mass concentration of 50% fluozirconic acid aqueous solution, and its solid content is 4% to 8%.
- the purity of the lanthanum nitrate hexahydrate used is above 98%, and its solid content is 0.4% to 1%.
- the purity of the cerium nitrate hexahydrate used is above 98%, and its solid content is 0.2% to 0.7%. %, its solid content is 0.5% to 1.5%.
- the benzene-containing polyoxyethylene ether surfactant is one or more of styrene polyoxyethylene ether, benzyl alcohol polyoxyethylene ether, phenol polyoxyethylene ether or alkylphenol polyoxyethylene ether .
- n 3-50, and its solid content is 5%-10%.
- the solid content of the graphene oxide aqueous solution is 0.5%.
- the rust inhibitor is one of triethanolamine, monoethanolamine or triethanolamine borate.
- the organic solvent is one of dipropylene glycol, benzyl alcohol or butyl glycol ether.
- graphene oxide is a two-dimensional nano-carbon material, and the carbon atom planes in its structure are stacked in the form of sp2 hybridization to form a regular hexagonal honeycomb structure; at the same time, the oxidized Graphene can have ⁇ - ⁇ interaction with aromatic hydrocarbon structure substances (there is a ⁇ - ⁇ conjugation effect between the benzene ring structure and graphene oxide), and enhance the benzene-containing polyoxyethylene ether surfactant (surfactant activity) through synergistic effect.
- the agent emulsifies the oil into small particles, thereby removing it from the metal surface), because the surface of graphene oxide is rich in oxygen-containing groups, so it can exist stably in the bath, and graphene oxide can
- the interfacial tension of the emulsified oil in the middle reduces the stability of the emulsified oil, improves the oil-water separation efficiency under normal temperature conditions, slows down the accumulation rate of oil in the bath, and thus prolongs the service life of the working fluid;
- rare earth elements are introduced to form a hybrid film during the film formation process (the local pH of the metal surface increases, zirconium ions and rare earth elements co-precipitate to form a hybrid film), and the coating film is improved on the substrate.
- the remarkable advantage of the present invention is that the phosphorus-free pretreatment agent integrating oil removal and film formation of the present invention uses benzene-containing polyoxyethylene ether surfactants and graphene oxide to synergistically remove The oil, together with the organic solvent, also has a good oil-water separation efficiency while improving the oil removal efficiency. Since the emulsification of the removed oil and the tank liquid will reduce the service life of the working fluid, the present invention improves the stability of the emulsified oil by reducing the stability of the emulsified oil.
- the oil-water separation performance under certain conditions ensures good adhesion and corrosion resistance between the subsequent metal surface and the painted paint film, prolonging the service life of the working fluid; solving the problem of reduced service life of the working fluid caused by the accumulation of oil in the existing bath question.
- the phosphorus-free pretreatment agent for metal surface treatment of the present invention is prepared by adding the following components into each liter of the phosphorus-free pretreatment agent: 30g of zirconium nitrate pentahydrate, 70g of fluorozirconic acid aqueous solution, and 5g of nitric acid hexahydrate Lanthanum, 6g cerium nitrate hexahydrate, 9g nitric acid solution, 5g triethanolamine, 300g graphene oxide aqueous solution, 100g benzyl alcohol polyoxyethylene ether surfactant, 100g dipropylene glycol and the balance of water.
- the phosphorus-free pretreatment agent for metal surface treatment of the present invention is prepared by adding the following components into each liter of the phosphorus-free pretreatment agent: 40g of zirconium nitrate pentahydrate, 80g of fluorozirconic acid aqueous solution, and 8g of nitric acid hexahydrate Lanthanum, 3g cerium nitrate hexahydrate, 12g nitric acid solution, 3g monoethanolamine, 200g graphene oxide aqueous solution, 80g styrene polyoxyethylene ether surfactant, 150g benzyl alcohol and the balance of water.
- the use concentration (mass concentration) of the non-phosphorus pretreatment agent of the present invention is 3%, promptly adds the non-phosphorus pretreatment agent of 30g embodiment 1 or embodiment 2 in every kilogram of water, obtains dilute treatment liquid (working liquid), uses 1%
- the sodium hydroxide solution adjusts the pH to 4.5-5.
- Test plate commercially available standard cold-rolled low-carbon steel plate with a specification of (150mm ⁇ 70mm ⁇ 0.8mm).
- Degreasing pottery the non-phosphorus pretreatment agent of the present invention, the use concentration is 3%, the pH is controlled at 4.5-5, and the process of spraying or pendulum washing is adopted at room temperature, and the treatment is 3 minutes; wherein, the spray pressure is 0.1Mpa, and the pendulum washing process is 3 minutes; The washing frequency is 1 reciprocation/s.
- Degreasing treatment Use a commercially available degreasing agent for heated cold-rolled sheets, soak the cold-rolled sheets at 50 °C for 5 minutes, supplemented by manual swinging and scrubbing, etc., to ensure that the surface is degreased and clean.
- Water washing after degreasing wash in tap water at room temperature for 1 minute, and in pure water for 1 minute.
- Comparative example 1 Ceramic agent KR-S110 (commercially available product) of Nanjing Kerun Company, the use concentration is 1%, the pH is controlled at 4-5, spraying or pendulum washing at room temperature for 3 minutes;
- Proportion 2 Commercially available coating and phosphating JD-PLA (purchased from Yangzhou Sanming Metal Surface Treatment Co., Ltd.), the use concentration is 10-15%, the acid ratio is controlled at about 8, spray or wash at room temperature 7.5min.
- Electrophoretic coating HT8000C water-based cathodic electrophoretic coating produced by Xiangjiang Kansai Paint Co., Ltd. on the market, the film thickness is controlled at 20-22 ⁇ m.
- the washed electrophoresis test plate was cured at 170° C. for 20 minutes, taken out and dried at room temperature.
- Table 1 is the electrophoretic paint film sample treated with the non-phosphorus pretreatment agent in Example 1, and Comparative Example 1 is the electrophoretic paint film sample treated with zirconium salt surface treatment agent, and Comparative Example 2 is the electrophoretic paint film treated with phosphating agent Paint film properties of the sample.
- Example 1 the electrophoretic paint film sample plate after the treatment of the phosphorus-free pretreatment agent in Example 1 has excellent adhesion between the surface of the plate and the paint film.
- Example 1 has no The corrosion resistance of the coated test panel treated with phosphorus pretreatment agent is equivalent to that of the conventional process without phosphorus pretreatment agent.
- the non-phosphorus pretreatment agent of the present invention has the same neutral salt spray performance and cycle corrosion resistance of the plate after coating, but reduces the number of procedures, thereby reducing energy consumption.
- the phosphorus-free pretreatment agent of the present invention can meet the working conditions of 2 stations or 3 stations, and the phosphorus-free pretreatment agent shows good degreasing effect and film formation on cold-rolled steel sheets, galvanized sheets and aluminum sheets It also has good anti-rust performance between processes, and the bonding force between the painted film and the substrate is also good.
- Example 1 Use relevant equipment to characterize the cleaning performance of the phosphorus-free pretreatment agent in Example 1, and compare it with common commercially available degreasing agents and two-in-one phosphorus-free pretreatment agents.
- the performance of the characterization includes the cleaning ability and foam performance of different oil products (JB/T 4323.2-199), upper limit oil content.
- the oil-water separation efficiency is carried out with reference to the standard GB/T 7305, and the time for 90% separation of oil and water is recorded.
- comparative example 3 is a commercially available two-in-one phosphorus-free pretreatment agent
- comparative example 4 is Nanjing Kerun’s KR-SC620 and KR-SC63L.
- the treatment process is 3 minutes of pendulum washing, and the frequency of pendulum washing is 1 reciprocation/s .
- Table 3 shows the cleaning ability, foam performance and oil-water separation efficiency of the phosphorus-free pretreatment agent of Example 1 and Comparative Examples 3-4.
- the two-in-one phosphorus-free pretreatment agent of the present invention has a considerable degreasing and cleaning ability, which is higher than the cleaning ability of the existing two-in-one phosphorus-free pretreatment agent; meanwhile, The two-in-one phosphorus-free pretreatment agent of the present invention has good oil-water separation efficiency and rate, slows down the accumulation speed of oil in the bath, and the oil-water separation efficiency is much higher than the existing two-in-one phosphorus-free pretreatment agent and degreasing agent .
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
本发明公开了一种用于金属表面处理的无磷前处理剂，每升无磷前处理剂中，含有30～40g五水合硝酸锆、70～80g氟锆酸水溶液、5～8g六水合硝酸镧、3～6g六水合硝酸铈、9～12g硝酸溶液、3～5g防锈剂、200～300g氧化石墨烯水溶液、80～100g含苯聚氧乙烯醚表面活性剂、100～150g有机溶剂以及水余量。本发明利用含苯表面活性剂和氧化石墨烯的协同作用以及连同有机溶剂，在提高除油效率的同时通过降低乳化油的稳定性从而提升常温条件下油水分离效率，保证了后续金属表面与涂装漆膜的良好附着力和耐蚀性，延长了工作液的使用寿命；解决了现有槽液中油品累积导致的工作液使用寿命下降的问题。
Description
本发明涉及一种用于金属表面处理的无磷前处理剂。
随着金属材料表面处理行业面临的环保压力逐年增加，无磷前处理剂应运而生。其中，陶化技术和硅烷技术作为无磷表面处理的典型代表，在无磷前处理剂中占有举足轻重的地位。与传统的磷化、钝化技术等金属表面处理工艺相比，无磷前处理剂在环保方面具有不可比拟的优势，对环境污染小，不会导致水体富营养化，在消耗量、成本、维护等方面同样优势明显。经过近年来的不断发展，无磷技术已经可以满足大部分涂装行业的需求，潜力巨大。
为保证无磷前处理剂的良好性能，无磷前处理往往会有多道水洗工艺，而水洗时间过长引起的生锈问题会导致涂装漆膜性能的明显下降。此外，部分使用前处理剂的企业受成本、场地等限制，前处理生产线只有2-3个工位，无法满足常规前处理的工艺要求。因此二合一系列的无磷前处理剂产品开始逐步出现。由于水洗工序的减少、槽液中油品的累积，会导致工作液使用寿命下降的问题，同时二合一无磷前处理剂相比于单一的无磷前处理工艺，其附着力、耐蚀性也会发生明显的下降。
发明内容
发明目的：针对目前二合一无磷前处理剂除油效率、油品累积和使用寿命的问题，本发明提供一种既具有良好的水洗除油能力又具有良好附着力和耐蚀性的集脱脂、成膜二合一的无磷前处理剂。
技术方案：本发明所述的用于金属表面处理的无磷前处理剂，每升无磷前处理剂中，含有30～40g五水合硝酸锆、70～80g氟锆酸水溶液、5～8g六水合硝酸镧、3～6g六水合硝酸铈、9～12g硝酸溶液、3～5g防锈剂、200～300g氧化石墨烯水溶液、80～100g含苯聚氧乙烯醚表面活性剂、100～150g有机溶剂以及水余量。
本发明配方中，使用的五水合硝酸锆纯度在98％以上，其固含量为1.5％～4％；使用的氟锆酸为市售的质量浓度为50％氟锆酸水溶液，其固含量为4％～8％。使用的六水合硝酸镧纯度在98％以上，其固含量为0.4％～1％；使用的六水合硝酸 铈纯度在98％以上，其固含量为0.2％～0.7％；使用的硝酸纯度为68％，其固含量为0.5％～1.5％。
其中，所述含苯聚氧乙烯醚表面活性剂为苯乙烯聚氧乙烯醚、苯甲醇聚氧乙烯醚，苯酚聚氧乙烯醚或烷基苯酚聚氧乙烯醚中的一种或几种的混合。
其中，苯甲醇聚氧乙烯醚的结构式为：
聚氧乙烯醚链段中n＝3～50，其固含量为5％～10％。
其中，氧化石墨烯水溶液的固含量为0.5％。
使用如下方法制备400mL氧化石墨烯(GO)水溶液：
首先，将46mL浓硫酸倾倒入500mL四口烧瓶中，并在400rpm和冰水浴条件下进行机械搅拌，再往其中倒入2g石墨粉和1g硝酸钠，均匀搅拌；接着称取15g高锰酸钾粉末在30min内慢慢倒入反应烧瓶中，可观察到烧瓶中混合液体逐渐变为墨绿色；然后移除冰水浴设备，在常温下搅拌直至反应物呈现棕色泥巴状；接着快速倒入92mL去离子水，烧瓶温度逐渐上升，并有大量气体释放，待温度低于35℃后，加入大量的过氧化氢溶液至烧瓶内的反应物溶液变为金黄色，反应结束后将反应物溶液加入透析袋中，透析七天至反应物溶液的pH值为中性7；通过固含量数据补加纯水，最终获得固含量为0.5％的氧化石墨烯水溶液。
其中，所述防锈剂为三乙醇胺、单乙醇胺或三乙醇胺硼酸酯中的一种。
其中，所述有机溶剂为二丙二醇、苯甲醇或乙二醇丁醚中的一种。
本发明无磷前处理剂的作用机理：氧化石墨烯为一种二维纳米碳材料，其结构中的碳原子平面通过sp2杂化的形式堆叠，形成正六边形的蜂巢式结构；同时，氧化石墨烯可与芳烃结构的物质发生π-π相互作用(苯环结构与氧化石墨烯之间存在π-π共轭效应)，通过协同作用提升含苯类聚氧乙烯醚表面活性剂(表面活性剂将油乳化成小微粒，从而将其从金属表面除去)的除油效率，因为氧化石墨烯表面具有丰富的含氧基团，因此可以在槽液中稳定存在，氧化石墨烯通过改变槽液中乳化油的界面张力，降低乳化油的稳定性，提升常温条件下的油水分离效率，减缓槽液中的油品累积速度，从而延长工作液的使用寿命；同时，为了缓解 表处理膜层耐蚀性能的下降，引入稀土元素，使其在成膜过程中形成杂化薄膜(金属表面局部pH升高，锆离子和稀土元素共沉淀成膜形成杂化膜)，提升涂装漆膜在基材表面的耐蚀性；最后，通过引入高沸点有机溶剂，通过油品与有机溶剂的相似相容原理，使得无磷前处理剂的除油性能进一步提升，降低后续防锈压力。
有益效果：与现有技术相比，本发明的显著优点在于：本发明集除油、成膜于一体的无磷前处理剂使用含苯聚氧乙烯醚类表面活性剂和氧化石墨烯协同除油，连同有机溶剂，在提高除油效率的同时还具有良好的油水分离效率，由于除下来的油与槽液乳化会降低工作液的使用寿命，本发明通过降低乳化油的稳定性从而提升常温条件下油水分离性能，保证了后续金属表面与涂装漆膜的良好附着力和耐蚀性，延长了工作液的使用寿命；解决了现有槽液中油品累积导致的工作液使用寿命下降的问题。
下面结合具体实施例对本发明技术方案作进一步阐述。
实施例1
本发明用于金属表面处理的无磷前处理剂，每升无磷前处理剂中，加入如下质量的组分混合配制而成：30g五水合硝酸锆、70g氟锆酸水溶液、5g六水合硝酸镧、6g六水合硝酸铈、9g硝酸溶液、5g三乙醇胺、300g氧化石墨烯水溶液、100g苯甲醇聚氧乙烯醚表面活性剂、100g二丙二醇以及水余量。
实施例2
本发明用于金属表面处理的无磷前处理剂，每升无磷前处理剂中，加入如下质量的组分混合配制而成：40g五水合硝酸锆、80g氟锆酸水溶液、8g六水合硝酸镧、3g六水合硝酸铈、12g硝酸溶液、3g单乙醇胺、200g氧化石墨烯水溶液、80g苯乙烯聚氧乙烯醚表面活性剂、150g苯甲醇以及水余量。
本发明无磷前处理剂的使用浓度(质量浓度)为3％，即每公斤水中加入30g实施例1或实施例2的无磷前处理剂，得到稀释处理液(工作液)，使用1％氢氧化钠溶液调整pH为4.5～5。
用实施例1制得的无磷前处理剂进行电泳涂装漆膜性能测试：
试验板材：采用市售标准冷轧低碳钢板，规格为(150mm×70mm×0.8mm)。
用实施例1制得的无磷前处理剂的工艺流程：脱脂陶化→自来水洗→纯水洗→电泳涂装→高温固化
对比例1和对比例2的工艺流程：脱脂除油→自来水洗→纯水洗→表面前处理→自来水洗→纯水洗→电泳涂装→高温固化
各工艺流程简介：
脱脂陶化：本发明无磷前处理剂，使用浓度为3％，pH控制在4.5～5，室温条件下采用喷淋或者摆洗的工艺，处理3min；其中，喷淋压力为0.1Mpa，摆洗频率为1个往复/s。
脱脂处理：采用市售某加热冷轧板脱脂剂，在50
℃条件下浸泡冷轧板材5分钟，辅以人工摆动搓洗等，以保证表面脱脂洁净。
脱脂后的水洗：在室温下自来水中摆洗1分钟，纯水中摆洗1分钟。
表面前处理：对比例1：南京科润公司的陶化剂KR-S110(市售产品)，使用浓度为1％，pH控制在4～5，室温条件下喷淋或摆洗处理3min；对比例2：市售的涂装磷化JD-PLA(购自扬州三铭金属表面处理有限公司)，使用浓度为10～15％，控制酸比在8左右，室温条件下喷淋或摆洗处理7.5min。
电泳涂装：市面湘江关西涂料公司生产的HT8000C水性阴极电泳涂料，控制膜厚在20-22μm。将水洗后的电泳后试板在170℃条件下固化20分钟，取出后在室温下晾干。
漆膜性能：
表1为经过实施例1无磷前处理剂处理后的电泳漆膜样板以及对比例1为锆盐表面处理剂处理后的电泳漆膜样板以及对比例2为磷化剂处理后的电泳漆膜样板的漆膜性能。
表1
通过表1可知，经实施例1无磷前处理剂处理后的电泳漆膜样板，板材表面与漆膜附着力优良，通过30周期CCT试验和1000h的中性盐雾试验对比，实施例1无磷前处理剂处理的涂装试板耐蚀性与常规工艺的无磷前处理剂相当。本发明无磷前处理剂与传统无磷前处理工艺相比，其涂装后板材的中性盐雾性能和耐循环腐蚀性能相当，但是减少了工序，从而降低能源消耗。本发明无磷前处理剂能够满足2工位或者3工位的使用工况，该无磷前处理剂在冷轧钢板、镀锌板材和铝板材上均表现出良好的除油效果和成膜性能，还具有良好的工序间防锈性能，涂装漆膜与基材结合力也良好。
裸膜性能见表2
表2
通过表2可知，低碳钢冷轧钢板在实施例1无磷前处理剂处理后的裸膜膜层耐蚀性良好，与常规工艺的无磷前处理剂相当，受膜层厚度限制，略弱于磷化试板。
本发明实施例1无磷前处理剂的清洗性能与油水分离效率测试：
利用相关设备对实施例1无磷前处理剂的清洗性能进行表征，与常见的市售 脱脂剂和二合一无磷前处理剂进行比较，表征的性能包括不同油品的清洗能力、泡沫性能(JB/T 4323.2-199)、上限油含量。油水分离效率参照标准GB/T 7305进行，记录油水90％分离时的时间。
其中对比例3为市售的二合一无磷前处理剂，对比例4是南京科润的KR-SC620和KR-SC63L，处理工艺为摆洗处理3min，摆洗频率为1个往复/s。
实施例1无磷前处理剂以及对比例3～4的清洗能力、泡沫性能和油水分离效率如表3所示。
表3
通过表3可知，与专门的脱脂剂相比，本发明二合一无磷前处理剂具有相当的除油清洗能力，高于现有的二合一无磷前处理剂的清洗能力；同时，本发明二合一无磷前处理剂具有良好的油水分离效率和速率，减缓了槽液中的油品累积速度，油水分离效率远高于现有的二合一无磷前处理剂和脱脂剂。
Claims (6)
- 一种用于金属表面处理的无磷前处理剂，其特征在于：每升无磷前处理剂中，含有30～40g五水合硝酸锆、70～80g氟锆酸水溶液、5～8g六水合硝酸镧、3～6g六水合硝酸铈、9～12g硝酸溶液、3～5g防锈剂、200～300g氧化石墨烯水溶液、80～100g含苯聚氧乙烯醚表面活性剂、100～150g有机溶剂以及水余量。
- 根据权利要求1所述的用于金属表面处理的无磷前处理剂，其特征在于：所述含苯聚氧乙烯醚表面活性剂为苯乙烯聚氧乙烯醚、苯甲醇聚氧乙烯醚，苯酚聚氧乙烯醚或烷基苯酚聚氧乙烯醚中的一种或几种的混合。
- 根据权利要求2所述的用于金属表面处理的无磷前处理剂，其特征在于：所述苯甲醇聚氧乙烯醚的结构式为：
其中，聚氧乙烯醚链段中n＝3～50，其固含量为5％～10％。 - 根据权利要求1所述的用于金属表面处理的无磷前处理剂，其特征在于：氧化石墨烯水溶液的固含量为不高于0.5％。
- 根据权利要求1所述的用于金属表面处理的无磷前处理剂，其特征在于：所述防锈剂为三乙醇胺、单乙醇胺或三乙醇胺硼酸酯中的一种。
- 根据权利要求1所述的用于金属表面处理的无磷前处理剂，其特征在于：所述有机溶剂为二丙二醇、苯甲醇或乙二醇丁醚中的一种。
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