CN115928084A - Cleaning antirust agent suitable for multi-material automobile parts and preparation method thereof - Google Patents
Cleaning antirust agent suitable for multi-material automobile parts and preparation method thereof Download PDFInfo
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- CN115928084A CN115928084A CN202211673842.4A CN202211673842A CN115928084A CN 115928084 A CN115928084 A CN 115928084A CN 202211673842 A CN202211673842 A CN 202211673842A CN 115928084 A CN115928084 A CN 115928084A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention discloses a cleaning antirust agent suitable for multi-material automobile parts, which consists of the following components in percentage by weight: 7 to 8.5 percent of alkali salt, 2.5 to 3 percent of chelating agent, 8 to 12 percent of nonionic surfactant, 0.2 to 0.5 percent of cationic surfactant, 2 to 2.5 percent of antirust agent, 0.5 to 1 percent of corrosion inhibitor and the balance of water. The cleaning antirust agent disclosed by the invention effectively solves the problem that the collinear cleaning of ferrous metal, die-casting aluminum alloy and magnesium alloy cannot simultaneously consider cleaning, rust prevention and corrosion inhibition of nonferrous metals, and can simultaneously ensure the cleanliness and corrosion inhibition effects of various materials during cleaning on the basis of stable stock solution.
Description
Technical Field
The invention relates to a cleaning antirust agent suitable for multi-material automobile parts and a preparation method thereof.
Background
The main problem of the new energy automobile is cruising ability, and factors affecting the cruising ability are very important influence factors of automobile body weight besides the performance of a battery. Compare traditional fuel oil car, new energy automobile more needs the lightweight to solve the problem of the automobile body weight increase that the electromotion brought, thereby improve continuation of the journey mileage and dynamic behavior. Research shows that the driving range can be increased by 2.5km when the whole weight of the pure electric vehicle is reduced by 10 kg.
At present, die-casting aluminum alloy and magnesium alloy are widely used for automobile lightweight due to excellent mechanical properties, but because aluminum and magnesium are very active metals, the processing difficulty is high, and particularly when multiple materials are processed in a collinear mode, the universality of metal processing media, particularly cleaning antirust agents, needs to be considered. Most of automobile part enterprises can involve processing of multi-material parts such as ferrous metal, die-casting aluminum alloy and die-casting magnesium alloy materials, and the parts are cleaned by adopting special cleaning agents on different cleaning lines respectively after machining, so that the problems of cleanliness, corrosion, product stability and the like are avoided, the equipment and labor investment of enterprises are increased, the management complexity is increased, and the cleaning efficiency is reduced.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a cleaning antirust agent suitable for multi-material automobile parts, which can simultaneously ensure the cleanliness and corrosion inhibition effect of various materials during cleaning on the basis of ensuring the stability of stock solution; the invention also aims to provide a preparation method of the cleaning antirust agent.
The technical scheme is as follows: the invention relates to a cleaning antirust agent suitable for multi-material automobile parts, which consists of the following components in percentage by weight: 7 to 8.5 percent of alkali salt, 2.5 to 3 percent of chelating agent, 8 to 12 percent of nonionic surfactant, 0.2 to 0.5 percent of cationic surfactant, 2 to 2.5 percent of antirust agent, 0.5 to 1 percent of corrosion inhibitor and the balance of water.
Wherein the alkali salt is a composition prepared by mixing potassium hydroxide and sodium metasilicate pentahydrate according to the mass ratio of 5.5-5:2; the potassium hydroxide is used for removing metal powder on the surface of the part to be cleaned, and the potassium hydroxide and the sodium metasilicate pentahydrate can resist corrosion and discoloration of the die-cast aluminum alloy caused by the potassium hydroxide through the synergy of the sodium metasilicate pentahydrate and the corrosion inhibitor only in the proportion; if sodium metasilicate pentahydrate is replaced by potassium pyrophosphate or sodium tripolyphosphate which has a corrosion inhibition effect on the aluminum alloy, the processing surface of the die-casting magnesium alloy after being cleaned becomes yellow and dark.
Wherein the corrosion inhibitor is prepared by the following method: putting 65% by mass of N-methyl sodium taurate aqueous solution and methanol into a four-neck flask provided with a stirring device, a thermometer and a dropping funnel according to a mass ratio of 1:1, adding epoxy silane with the mass of N-methyl sodium taurate and the like into the dropping funnel, controlling the dropping speed to be 5g/min, controlling the reaction temperature to be 25-50 ℃, adding pure water with the mass 2 times of that of the N-methyl sodium taurate into the mixture after dropping is finished, and distilling out methanol and water by heating to obtain the corrosion inhibitor. The main component of the corrosion inhibitor is a ring-opening reaction product of N-methyl sodium taurate and epoxy silane, and N atoms in the N-methyl sodium taurate and CH after ring opening of epoxy groups 2 The groups are linked.
The corrosion inhibitor is a siloxane modifier, can generate a synergistic corrosion inhibition effect with sodium metasilicate pentahydrate on one hand, can resist corrosion discoloration of die-casting aluminum alloy, can increase the stability of stock solution on the other hand, and overcomes the defects that the sodium metasilicate pentahydrate gradually generates turbidity and flocculent precipitates in the process of being placed at the normal temperature to 50 ℃. The biggest problem of sodium metasilicate pentahydrate in the aqueous solution is the stability problem, white precipitates are easy to separate out, the epoxy siloxane is modified by the hydrophilic groups, the solubility of the sodium metasilicate pentahydrate in water after hydrolysis is improved, and meanwhile, when more Si-OH exists in the aqueous solution, the hydrolysis tendency of the sodium metasilicate pentahydrate can be inhibited.
Wherein the epoxy silane is gamma-glycidoxypropyltrimethoxysilane or gamma-glycidoxypropyltriethoxysilane.
Wherein the chelating agent is citric acid or EDTA; the selected chelating agent can effectively disperse metal ions in the cleaning bath solution (the metal ions are generated by metal powder on the surface of a part to be cleaned) and avoid the metal ions from being deposited on the surface to be cleaned for the second time, thereby realizing the brightening effect of the metal surface after cleaning, and if citric acid and EDTA salt such as sodium citrate and EDTA-4Na salt are adopted, the brightening effect can not be generated. If the amount of citric acid and EDTA exceeds 3%, hydrogen is generated during the cleaning of the magnesium alloy, the processed surface becomes dark and loses luster, and if the amount is less than 2.5%, metal ions cannot be effectively dispersed, and the brightening effect after cleaning cannot be generated.
Wherein the nonionic surfactant is carbonyl alcohol EO-PO block polyether and branched secondary alcohol polyoxyethylene ether in a mass ratio of 5:3 the combination of carbonyl alcohol EO-PO block polyether and branched secondary alcohol polyoxyethylene ether can ensure both foam-suppressing ability and oil-emulsifying ability only at the above-mentioned ratio, the foam-suppressing ability is insufficient when the ratio of the former is less than 5 or the ratio of the latter is more than 3, the oil-emulsifying ability is insufficient when the ratio of the former is more than 5 and the ratio of the latter is less than 3.
Wherein, the carbon chain of the carbonyl alcohol EO-PO block polyether is isomeric C8-C10, and the composition ratio of EO and PO is 5:5; the carbon chain length of the carbonyl alcohol EO-PO block polyether is C8-C10, wetting, rapid permeation and surface activity are considered, the activity is low when the carbon chain is lower than 8, and the permeation capability is weakened when the carbon chain is higher than 10; the composition ratio of EO to PO is 5:5, low foam, foam inhibition and cleaning capability are considered, the cleaning capability is reduced when the EO number is lower, the foam performance is poor when the EO number is higher, the foam inhibition capability is poor when the PO number is lower, the water solubility is poor when the PO number is higher, when the ratio of the EO to the PO is 5:5, the good cleaning capability and the low foam performance can be maintained, and the EO and PO can inhibit the foams of other surfactants at the temperature of more than 50 ℃; wherein the carbon chain of the branched secondary alcohol polyoxyethylene ether is C12, the branched secondary alcohol polyoxyethylene ether comprises three methyl substituents, and the EO number is 5-6; the branched secondary alcohol polyoxyethylene ether is used for forming a synergistic effect with the permeability of carbonyl alcohol EO-PO block polyether by utilizing the super-strong emulsifying capacity of the branched secondary alcohol polyoxyethylene ether, cleaning liquid can quickly permeate to the surface to be cleaned firstly, oil stain is rolled off through the emulsifying effect, the EO number is 5-6, the surface activity and the foam performance can be well coordinated, when the EO number is lower than 5, the surface activity is reduced, more solubilizer is needed for solubilizing the oil stain, when the EO number is higher than 6, the foam is too rich, and the inhibiting effect cannot be generated on the oil stain by the carbonyl alcohol EO-PO block polyether at the temperature of 50 ℃.
The cationic surfactant is di-C16-C18 alkyl dihydroxyethyl ammonium chloride, and mainly has the effects that quaternary ammonium salt positive ions and hydroxyethyl groups are adsorbed on the cleaned metal surface, the alkyl chain faces outwards to form a protection effect, secondary pollution and water stain residue of impurities on the cleaned surface are reduced, and the processed surface has certain glossiness after being cleaned.
The antirust agent is C21 dibasic acid, is synthesized from tall oil acid, ricinoleic acid or rapeseed oleic acid and acrylic acid through Diels-Alder reaction, has good compatibility with sodium metasilicate pentahydrate, and does not generate white floccule and precipitate.
The preparation method of the cleaning antirust agent specifically comprises the following steps: adding pure water with the formula amount into a reaction kettle, adding alkali salt into the reaction kettle at normal temperature, stirring until the alkali salt is uniform and transparent, adding a chelating agent, stirring until the alkali salt is uniform and transparent, then respectively adding a nonionic surfactant, a cationic surfactant and an antirust agent, and stirring until the alkali salt is uniform and transparent; and finally adding the corrosion inhibitor and stirring until the mixture is uniform and transparent, wherein the feeding speed is controlled within 5kg/min, otherwise, agglomeration is easy to generate, and thus, the stable stock solution for cleaning the antirust agent is obtained.
Has the beneficial effects that: compared with the prior art, the invention has the following remarkable advantages: (1) The cleaning antirust agent effectively solves the problem that the collinear cleaning of ferrous metal, die-casting aluminum alloy and magnesium alloy can not simultaneously take cleaning, rust prevention and corrosion inhibition of nonferrous metal (including die-casting aluminum alloy and magnesium alloy) into consideration, and can simultaneously ensure the cleanliness and corrosion inhibition effects of various materials during cleaning on the basis of stable stock solution; (2) The cleaning antirust agent can achieve the effect of brightening the metal surface after cleaning the die-casting aluminum alloy and the magnesium alloy; (3) The problem that sodium metasilicate is incompatible with organic carboxylic acid is solved, and through compatibility with C21 long carbon chain dibasic acid, silicate does not react to generate white precipitate in the preparation process of the cleaning antirust agent; (4) The problem of long-term storage stability of the silicate in an aqueous solution is solved by compatibility of the silicate and a corrosion inhibitor, and no white precipitate is generated no matter the silicate is placed at normal temperature or 50 ℃; (5) Through the compatibility of the surfactants with specific structures and mixing ratios, the cleaning agent can meet the requirement that no shrinkage occurs within 5 seconds for a 42mN/m dyne pen after parts are cleaned, can also meet the low-foaming performance at 50 ℃, and can be used for spray cleaning.
Detailed Description
Example 1
The invention relates to a cleaning antirust agent suitable for multi-material automobile parts, which consists of the following components in percentage by weight: 5% sodium metasilicate pentahydrate, 2.5% potassium hydroxide, 3.0% EDTA, 5% carbonyl alcohol EO-PO block polyether, 3% branched secondary alcohol polyoxyethylene ether, 0.2% bis C16-C18 alkyl diethoxy ammonium chloride, 2% C21 dibasic acid, 0.5% silicone modifier, and the balance water.
Example 2
The invention relates to a cleaning antirust agent suitable for multi-material automobile parts, which consists of the following components in percentage by weight: 5% sodium metasilicate pentahydrate, 3% potassium hydroxide, 3% citric acid, 5% carbonyl alcohol EO-PO block polyether, 3% branched secondary alcohol polyoxyethylene ether, 0.2% di-C16-C18 alkyl diethoxy ammonium chloride, 2% C21 dibasic acid, 0.5% siloxane modifier, and the balance water.
Example 3
The invention relates to a cleaning antirust agent suitable for multi-material automobile parts, which consists of the following components in percentage by weight: 5% sodium metasilicate pentahydrate, 2.5% potassium hydroxide, 3% EDTA, 5% carbonyl alcohol EO-PO block polyether, 3% branched secondary alcohol polyoxyethylene ether, 1% bis C16-C18 alkyldihydroxyethylammonium chloride, 2% C21 dibasic acid, 1% silicone modifier, and the balance water.
Comparative example 1
A cleaning antirust agent comprises the following components in percentage by weight: 5% sodium metasilicate pentahydrate, 2.5% potassium hydroxide, 3% EDTA, 5% carbonyl alcohol EO-PO block polyether, 3% branched secondary alcohol polyoxyethylene ether, 0.2% di C16-C18 alkyldihydroxyethyl ammonium chloride, 2% C21 dibasic acid and the balance water.
Comparative example 2
A cleaning antirust agent comprises the following components in percentage by weight: 5% potassium pyrophosphate, 3% potassium carbonate, 3% EDTA, 5% carbonyl alcohol EO-PO block polyether, 3% branched secondary alcohol polyoxyethylene ether, 1% bis C16-C18 alkyldihydroxyethylammonium chloride, 2% C21 dibasic acid, 1% siloxane modification, and the balance water.
Comparative example 3
A cleaning antirust agent comprises the following components in percentage by weight: 5% sodium metasilicate pentahydrate, 2.5% potassium hydroxide, 3% EDTA, 5% carbonyl alcohol EO-PO block polyether, 3% branched secondary alcohol polyoxyethylene ether, 1% di C16-C18 alkyldihydroxyethyl ammonium chloride, 1% silicone modifier, and the balance water.
Comparative example 4
A cleaning antirust agent comprises the following components in percentage by weight: 5% sodium metasilicate pentahydrate, 2.5% potassium hydroxide, 3% EDTA-4Na, 5% carbonyl alcohol EO-PO block polyether, 3% branched secondary alcohol polyoxyethylene ether, 2% C21 dibasic acid, 1% silicone modifier, and the balance water.
Comparative example 5
A cleaning antirust agent comprises the following components in percentage by weight: 5% sodium metasilicate pentahydrate, 2.5% potassium hydroxide, 3% EDTA, 5% carbonyl alcohol EO-PO block polyether, 3% branched secondary alcohol polyoxyethylene ether, 1% di C16-C18 alkyldihydroxyethyl ammonium chloride, 2% sebacic acid, 1% silicone modifier, and the balance water.
Comparative example 6
A cleaning antirust agent comprises the following components in percentage by weight: 5% sodium metasilicate pentahydrate, 2.5% potassium hydroxide, 3% EDTA, 3% carbonyl alcohol EO-PO block polyether, 5% branched secondary alcohol polyoxyethylene ether, 1% bis C16-C18 alkyldihydroxyethylammonium chloride, 2% C21 dibasic acid, 1% silicone modifier, and the balance water.
Comparative example 7
A cleaning antirust agent comprises the following components in percentage by weight: 5% sodium metasilicate pentahydrate, 2.5% potassium hydroxide, 3% EDTA, 5% carbonyl alcohol EO-PO block polyether (EO to PO composition ratio of 10, 4, e.g., antarox BL-240), 3% branched secondary alcohol polyoxyethylene ether, 1% bis C16-C18 alkyldihydroxyethyl ammonium chloride, 2% C21 dibasic acid, 1% silicone modifier, and the balance water.
Comparative example 8
A cleaning antirust agent comprises the following components in percentage by weight: 5% sodium metasilicate pentahydrate, 2.5% potassium hydroxide, 3% EDTA, 5% carbonyl alcohol EO-PO block polyether, 2% branched secondary alcohol polyoxyethylene ether, 1% bis C16-C18 alkyldihydroxyethylammonium chloride, 2% C21 dibasic acid, 1% silicone modifier, and the balance water.
Comparative example 9
A cleaning antirust agent comprises the following components in percentage by weight: 5% sodium metasilicate pentahydrate, 2.5% potassium hydroxide, 3% EDTA, 5% carbonyl alcohol EO-PO block polyether, 3% secondary alcohol polyoxyethylene ether (e.g., DOW 15-S-7), 1% bis C16-C18 alkyldihydroxyethyl ammonium chloride, 2% C21 dibasic acid, 1% siloxane modifier, and the balance water.
The performance indexes of the cleaning rust inhibitors of examples 1 to 3 and comparative examples 1 to 8 are shown in Table 1.
TABLE 1
Remarking: a represents a test method of corrosion inhibition performance of die-casting aluminum alloy and magnesium alloy, parts made of AlSi12Cu and AZ91D are washed in working solution of 5 percent and 50 ℃ for 5min, the parts are washed by tap water and then dried by blowing hot air, whether the surfaces of the parts are corroded and discolored is observed, and the parts are judged to be discolored when the brightness of a processed surface is reduced.
And b represents a test method of the brightness of the cleaned parts, the parts made of AlSi12Cu and AZ91D are washed in working solution of 5 percent and 50 ℃ for 5min, then the parts are dried by blowing hot air, and the non-processed surfaces of the parts are recorded as natural colors if no obvious change exists, and are recorded as brightness if the non-processed surfaces are brighter than the surfaces before cleaning.
c represents a test method of cleanliness of the cleaned parts, the parts made of 45# steel, alSi12Cu and AZ91D are subjected to swing cleaning in working solution at 50 ℃ for 5min at 5%, then are dried by hot air blowing, after the parts are cooled to normal temperature, a 42mN/m dyne pen is used for scribing, whether the parts shrink or not is observed after 5 seconds, and whether the parts shrink or not is qualified or not is judged if the parts do not shrink or not is unqualified.
As can be seen from Table 1, the stock solutions of the cleaning rust inhibitors prepared in examples 1 to 3 are stable at normal temperature and 50 ℃, have a rust-preventing effect on ferrous metals, and have no corrosion discoloration phenomenon of nonferrous metals after cleaning die-casting aluminum alloys and magnesium alloys at 50 ℃, so that the appearance is brighter, the foam is low, and the cleanliness can pass the 42mN/m dyne pen test. Comparative example 1 no corrosion inhibitor is added, stock solution is unstable, corrosion inhibition of aluminum alloy is insufficient, and appearance is corroded and discolored; comparative example 2 in which potassium pyrophosphate and potassium carbonate were used instead of the alkali salt of the present invention, corrosion and discoloration of the magnesium alloy occurred with the generation of bubbles after the washing at 50 ℃; comparative example 3 no rust inhibitor was added, the rust inhibiting effect was significantly reduced; in comparative example 4, EDTA-4Na was used in place of EDTA, and the cationic surfactant was removed, and the aluminum alloy and magnesium alloy did not become bright after cleaning at 50 ℃; in the comparative example 5, sebacic acid is used for replacing the C21 dibasic acid antirust agent, the stock solution has insufficient stability, and the corrosion inhibition performance of the aluminum alloy is reduced and the aluminum alloy is discolored after being cleaned at 50 ℃; in comparative example 6, the foam performance is obviously deteriorated after the proportion of the carbonyl alcohol EO-PO block polyether and the branched secondary alcohol polyoxyethylene ether is changed; in comparative example 7, the foam properties were seriously deteriorated by changing the addition ratio of EO and PO in the carbonyl alcohol EO-PO block polyether molecule; in the comparative example 8, the dosage of branched chain secondary alcohol polyoxyethylene ether is reduced, and the cleanliness does not reach the standard after cleaning at 50 ℃; in comparative example 9, secondary alcohol polyoxyethylene ether is used to replace branched secondary alcohol polyoxyethylene ether, and the cleanliness of the product after cleaning at 50 ℃ does not reach the standard.
Claims (10)
1. The cleaning antirust agent suitable for the multi-material automobile parts is characterized by comprising the following components in percentage by weight: 7 to 8.5 percent of alkali salt, 2.5 to 3 percent of chelating agent, 8 to 12 percent of nonionic surfactant, 0.2 to 0.5 percent of cationic surfactant, 2 to 2.5 percent of antirust agent, 0.5 to 1 percent of corrosion inhibitor and the balance of water.
2. The cleaning antirust agent suitable for the multi-material automobile parts as claimed in claim 1, wherein: the alkali salt is a composition formed by mixing potassium hydroxide and sodium metasilicate pentahydrate according to the mass ratio of 5.5-5:2.
3. The cleaning antirust agent suitable for the multi-material automobile parts as claimed in claim 1, wherein: the corrosion inhibitor is prepared by the following method: putting 65% by mass of N-methyl sodium taurate aqueous solution and methanol into a four-neck flask provided with a stirring device, a thermometer and a dropping funnel according to a mass ratio of 1:1, adding epoxy silane with the mass of N-methyl sodium taurate and the like into the dropping funnel, controlling the dropping speed to be 5g/min, controlling the reaction temperature to be 25-50 ℃, adding pure water with the mass 2 times of that of the N-methyl sodium taurate into the mixture after dropping is finished, and distilling out methanol and water by heating to obtain the corrosion inhibitor.
4. The cleaning antirust agent suitable for the multi-material automobile parts as claimed in claim 3, wherein: the epoxy silane is gamma-glycidoxypropyltrimethoxysilane or gamma-glycidoxypropyltriethoxysilane.
5. The cleaning antirust agent suitable for the multi-material automobile parts as claimed in claim 1, wherein: the chelating agent is citric acid or EDTA.
6. The cleaning rust inhibitor for multi-material automobile parts according to claim 1, characterized in that: the nonionic surfactant is carbonyl alcohol EO-PO block polyether and branched secondary alcohol polyoxyethylene ether in a mass ratio of 5:3, and (b) mixing the components.
7. The cleaning antirust agent suitable for the multi-material automobile parts as claimed in claim 6, wherein: the carbon chain of the carbonyl alcohol EO-PO block polyether is isomeric C8-C10, and the composition ratio of EO to PO is 5:5; the branched secondary alcohol polyoxyethylene ether has a carbon chain of C12 and comprises three methyl substituents, and the EO number is 5-6.
8. The cleaning rust inhibitor for multi-material automobile parts according to claim 1, characterized in that: the cationic surfactant is di-C16-C18 alkyl dihydroxyethyl ammonium chloride.
9. The cleaning rust inhibitor for multi-material automobile parts according to claim 1, characterized in that: the antirust agent is C21 dibasic acid.
10. The method for preparing a cleaning rust inhibitor according to claim 1, which comprises the following steps: adding pure water with the formula amount into a reaction kettle, adding alkali salt into the reaction kettle at normal temperature, stirring until the alkali salt is uniform and transparent, adding a chelating agent, stirring until the alkali salt is uniform and transparent, then respectively adding a nonionic surfactant, a cationic surfactant and an antirust agent, and stirring until the alkali salt is uniform and transparent; and finally adding the corrosion inhibitor and stirring until the mixture is uniform and transparent, wherein the feeding speed is controlled within 5kg/min, otherwise, agglomeration is easy to generate, so that the stable stock solution for cleaning the antirust agent is obtained.
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| CN202211673842.4A CN115928084A (en) | 2022-12-26 | 2022-12-26 | Cleaning antirust agent suitable for multi-material automobile parts and preparation method thereof |
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| CN202211673842.4A CN115928084A (en) | 2022-12-26 | 2022-12-26 | Cleaning antirust agent suitable for multi-material automobile parts and preparation method thereof |
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