CN110591663A - High-performance modified concentrated automobile antifreeze fluid and preparation method thereof - Google Patents
High-performance modified concentrated automobile antifreeze fluid and preparation method thereof Download PDFInfo
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- C09K5/20—Antifreeze additives therefor, e.g. for radiator liquids
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Abstract
The invention provides a high-performance modified concentrated automobile antifreeze fluid and a preparation method thereof, belonging to the technical field of antifreeze fluids. The antifreezing solution consists of the following components in parts by weight: 50.7 parts of ethylene glycol, 26.3 parts of silicate composite additive, 18.0 parts of glycerol and 5.0 parts of water-soluble conductive polyaniline. According to the invention, the water-soluble conductive polyaniline is added into the antifreezing agent, and is used in combination with the silicate composite additive, so that a better anti-corrosion effect is achieved, the anti-corrosion performance of the antifreezing solution is greatly improved, the anti-corrosion difficulty of a multi-metal cooling system is overcome, the water-soluble conductive polyaniline has the advantages of good stability, energy conservation, environmental protection and high efficiency, the influence of the product on the environment can be reduced when the antifreezing solution is put into use, and due to the high efficiency performance of the water-soluble conductive polyaniline, a very good effect can be achieved with a small dosage.
Description
Technical Field
The invention belongs to the technical field of antifreeze, and particularly relates to a high-performance modified concentrated automobile antifreeze and a preparation method thereof.
Background
In order to improve the performance of automobiles, the automobile bodies of the automobiles are continuously improved, the air resistance is reduced by adopting a streamline design, the engine material is changed into an all-aluminum structure, the structural quality of the automobile bodies is reduced, the speed is improved, and the like. The automobile cooling system is an important component of an automobile, and because of the multi-metallization of an automobile structure, the difficulty is increased on the corrosion resistance of the automobile cooling system, namely the requirement on the anti-freezing solution in the cooling system is increased, and the corrosion resistance of the existing anti-freezing solution is not ideal.
Disclosure of Invention
The invention aims to solve the problem of poor corrosion resistance of the existing antifreeze solution, and provides a high-performance modified concentrated automobile antifreeze solution and a preparation method thereof.
The invention firstly provides a high-performance modified concentrated automobile antifreeze fluid which comprises the following components in parts by weight:
preferably, the water-soluble conductive polyaniline has a conductivity of 10-1S/cm。
Preferably, the silicate-based composite additive is selected from the group consisting of basf, model G140 KSC.
The invention also provides a preparation method of the high-performance modified concentrated automobile antifreeze fluid, which comprises the following steps:
mixing ethylene glycol, silicate composite additive and glycerol until the mixture is uniform liquid, then adding water-soluble conductive polyaniline, and continuously stirring until the mixture is uniform liquid to obtain the high-performance modified concentrated automobile antifreeze fluid.
Preferably, the mixing temperature is normal temperature, and the mixing time is 30-40 min.
Preferably, the stirring temperature is normal temperature, and the stirring time is 30-40 min.
The invention has the advantages of
Compared with the prior art, the high-performance modified concentrated automobile antifreeze fluid adopts ethylene glycol as an antifreeze agent and silicate compound additives to play roles in resisting corrosion, adjusting pH value, defoaming and coloring; glycerol was used as a bulking agent; on the other hand, water-soluble conductive polyaniline is added into the antifreeze, and is compounded with silicate composite additives, so that a better anti-corrosion effect is achieved, the anti-corrosion performance of the antifreeze is greatly improved, the difficulty of corrosion prevention of a multi-metal cooling system is overcome, the water-soluble conductive polyaniline has the advantages of good stability, energy conservation, environmental protection and high efficiency, the influence of the product on the environment can be relieved when the water-soluble conductive polyaniline is put into use, and due to the high efficiency performance of the water-soluble conductive polyaniline, a very good effect can be achieved with a small using amount.
Drawings
FIG. 1 shows copper T2Photographs of macroscopic corrosion morphology of the test piece after being soaked in F0 (figure a) and F5 (figure A) for 20 days;
FIG. 2 is a photograph of the macroscopic corrosion morphology of the copper cast iron HT300 test piece after being soaked in F0 (FIG. B) and F5 (FIG. B) for 20 d;
FIG. 3 is a photograph of the macroscopic corrosion morphology of the aluminum LY12 coupon after being soaked in F0 (FIG. C) and F5 (FIG. C) for 20 d;
FIG. 4 is a photograph of the macroscopic corrosion morphology of the steel 45# coupon after being soaked in F0 (FIG. D) and F5 (FIG. D) for 20D;
FIG. 5 shows copper T2Microscopic corrosion morphology photographs of the test pieces after being soaked for 21d in F0 (figure a) and F5 (figure A);
FIG. 6 is a photograph of the macroscopic corrosion morphology of the copper cast iron HT300 test piece after being soaked in F0 (FIG. B) and F5 (FIG. B) for 21 d;
FIG. 7 is a photograph of the macroscopic corrosion morphology of the aluminum LY12 coupon after being soaked in F0 (FIG. C) and F5 (FIG. C) for 21 d;
FIG. 8 is a photograph of the macroscopic corrosion morphology of the steel 45# coupon after 21D immersion in F0 (FIG. D) and F5 (FIG. D);
FIG. 9 is a macroscopic corrosion morphology of cast aluminum alloy metal coupons after immersion for 7d in F0 (panel A) and F5 (panel a).
Detailed Description
The invention firstly provides a high-performance modified concentrated automobile antifreeze fluid which comprises the following components in parts by weight:
according to the invention, the water-soluble conductive polyaniline is a dark green uniform liquid, purchased from Jilin Zhengji science and technology Limited and has conductivityPreferably 10-1S/cm。
According to the invention, the silicate-based composite additive is selected from the group consisting of the BASF corporation, model number G140 KSC.
The content of the water-soluble conductive polyaniline added in the invention is 5%, and when the dosage of the water-soluble conductive polyaniline is lower than or higher than 5%, the corrosion resistance of the invention is affected. The corrosion prevention mechanism of the conductive polyaniline is mainly that the conductive polyaniline forms a passivation film on the surface of metal through the electrochemical principle so that the metal is not corroded. If the concentration is lower than 5%, the concentration in the solution is not high enough to form an effective passive film, so that the optimal corrosion prevention effect cannot be achieved; if the concentration is higher than 5%, after polyaniline forms a layer of protective film on the metal surface, excessive accumulation is continued, but the metal quality is increased, and the corrosion inhibition effect tends to be stable and cannot be improved.
The invention also provides a preparation method of the high-performance modified concentrated automobile antifreeze fluid, which comprises the following steps:
mixing the glycol, the silicate composite additive and the glycerol at normal temperature, preferably mixing for 30-40min, stirring until the mixture is uniform liquid, then adding the water-soluble conductive polyaniline, preferably continuously stirring at normal temperature, and stirring for 30-40min until the mixture is uniform liquid to obtain the high-performance modified concentrated automobile antifreeze fluid.
The present invention is described in further detail below with reference to specific examples, in which the starting materials are all commercially available.
Example 1
Mixing 50.7G ethylene glycol, 26.3G silicate composite additive (selected from Pasteur, model G140KSC) and 18G glycerol at room temperature, stirring for 30min to obtain uniform liquid, and adding 5G water-soluble conductive polyaniline (with conductivity of 10)-1S/cm) and continuously stirring at normal temperature for 30min until the mixture becomes uniform liquid, thus obtaining the high-performance modified concentrated automobile antifreeze fluid, which is recorded as F5.
Comparative example 1
Mixing 50.7g of ethylene glycol, 26.3g of silicate composite additive and 18g of glycerol at normal temperature, stirring for 30min until the mixture is uniform liquid, then respectively adding 0g, 3g and 8g of water-soluble conductive polyaniline, and continuously stirring at normal temperature for 30min until the mixture is uniform liquid to obtain antifreeze solutions, wherein the antifreeze solutions are marked as F0, F3 and F8.
Example 2 full immersion corrosion weight loss method test
First, sample preparation
1. Preparation of test piece for full-immersion corrosion weight loss method
The metal test pieces used in the test are four materials (50.8 multiplied by 25.4 multiplied by 1.58mm) of steel No. 45 (50.8 multiplied by 25.4 multiplied by 1.58mm), copper T2(50.8 multiplied by 25.4 multiplied by 1.58mm), cast iron HT300(50.8 multiplied by 25.4 multiplied by 3.18mm) and cast aluminum LY12, and the materials and specifications of the four test pieces are all specified in the international standard ASTM D1384. The surface of the metal coupon was sanded with a grit (1#) sandpaper and deburred to make the surface bright and shiny without any visible oxide film or stain. Thoroughly washing the sample by tap water; washed with absolute ethanol, dried and weighed. Before recording the weight, the cast aluminum sample should be dried in a drying oven at 100 ℃ for 1 hour to reach the constant weight. After weighing, the four metal test pieces are arranged on a brass bracket according to a certain sequence to form a test piece bundle.
2. Preparation of corrosive water
Respectively weighing 148mg of sodium sulfate, 165mg of sodium chloride and 138mg of sodium bicarbonate by using an electronic balance, dissolving the sodium sulfate, the 165mg of sodium chloride and the 138mg of sodium bicarbonate in distilled water, diluting the solution to 1L by using the distilled water after the solution is dissolved, and reserving the solution for later use. The process of synthesizing the solution should be completed at room temperature of 20 ℃.
3. Test solutions
Polyaniline antifreeze solutions F0, F3, F5 and F8 were mixed with corrosive water to prepare test solutions having a coolant content of 33% by volume.
Second, test method
1. Full immersion corrosion weight loss method
In the experiment, a typical metal test piece is immersed in the antifreeze at a certain temperature to measure the corrosiveness of the test piece in a certain time.
Under the condition of constant temperature and stable solution, the test strip beam is vertically placed into a prepared test solution beaker containing F0, F3, F5 and F8, and the test strip in the test strip beam is not contacted with the cup wall and the cup bottom, is not contacted with air and is completely immersed into the measured solution. The glass ware with the test piece is placed into a constant temperature water bath kettle, the temperature of the water bath is controlled at a fixed value, and the change of the quality of the glass ware is measured at a set time. Before measurement, the test piece bundle is decomposed, corrosion products on the surface of each test piece are removed by using a soft brush and water, and then the test piece bundle is cleaned by using ethanol, dried and measured to be accurate to 0.0001 g. Calculating the value of the corrosion rate according to the change of the sample mass before and after soaking:
in the formula (1-1):
w-corrosion rate of metal;
m 1-mass of sample before etching, mg;
m-mass after soaking for a certain time, mg;
s-surface area of Metal coupon, cm2；
T-soak time, day.
And (3) further calculating the corrosion inhibition efficiency of the anti-freezing solution according to the calculation result of the corrosion rate:
in the formula (1-2):
IE-corrosion inhibition rate of antifreeze solution,%;
W-Corrosion Rate without Corrosion inhibitor addition, mg cm-2·day-1；
W1Corrosion rate in mg cm with addition of corrosion inhibitor-2·day-1。
And calculating the corrosion inhibition rate according to the measured corrosion rate, carrying out an experiment by using the same method, and measuring a blank test, namely the corrosion inhibition rate of the anti-freezing solution without polyaniline as a standard to judge the anti-corrosion performance of the anti-freezing solution with polyaniline.
Before measurement, observing the macroscopic appearance of the test piece to judge the corrosion condition, then observing the microscopic appearance of the corrosion sample piece by using a Scanning Electron Microscope (SEM), and further proving the corrosion resistance of the polyaniline in the common antifreezing fluid
3. Results
1) Influence of polyaniline content on metal corrosion inhibition
The corrosion inhibition effect of the metal test piece is further judged by calculating the corrosion inhibition rate in the soaking time of the metal test piece, and the results are shown in tables 1-4:
TABLE 1 influence of the amount of polyaniline used on the corrosion inhibition rate of cast iron HT300
TABLE 2 Effect of the amount of polyaniline used on the Corrosion inhibition efficiency of copper T2
TABLE 3 influence of the amount of polyaniline used on the corrosion inhibition rate of carbon steel No. 45
TABLE 4 Effect of the amount of polyaniline used on the Corrosion inhibition efficiency of aluminum LY12
As can be seen from the above table, the corrosion prevention effect is best when the polyaniline content is 5 g.
2) Macroscopic and microscopic corrosion morphology of metal test piece
The macroscopic corrosion morphology of the four metal samples after being soaked in F0 and F5 for 20 days is shown in FIGS. 1-4, wherein FIG. 1 is copper T2The photographs of the macroscopic corrosion morphology of the test piece after being soaked in F0 (figure a) and F5 (figure A) for 20d, the photographs of the macroscopic corrosion morphology of the copper cast iron HT300 test piece after being soaked in F0 (figure B) and F5 (figure B) for 20d, and the photographs of the macroscopic corrosion morphology of the aluminum cast iron HT300 test piece after being soaked in F0 (figure B) and F5 (figure B), and the photographs of the aluminum cast iron HT3The macroscopic corrosion morphology photos of the LY12 test piece after being soaked in F0 (figure C) and F5 (figure C) for 20D, and the macroscopic corrosion morphology photos of the steel 45# test piece after being soaked in F0 (figure D) and F5 (figure D) for 20D are shown in figure 4;
as can be seen from FIGS. 1-4, the test piece of F0 antifreeze solution has more serious corrosion than the test piece of F5 antifreeze solution. The copper T2 test pieces in the two antifreeze solutions both have a phenomenon of light loss, and the round holes have obvious corrosion traces. However, the discoloration of the F0 test piece was more obvious. In the two antifreeze liquids, the steel No. 45 and F0 test pieces have obvious light loss and obvious corrosion traces at the round holes. The corrosion of cast iron HT300 and aluminum LY12 is more severe than that of copper and steel test pieces, and the surface corrosion of aluminum LY12 test pieces in F0 is obviously severe compared with that of aluminum LY12 test pieces in F5. The cast iron HT300 has obvious corrosion marks at round holes of two test pieces, but the corrosion of the F5 test piece is lighter than that of the F0 test piece.
The microscopic corrosion morphology of the four metal samples after being soaked in F0 and F5 for 21d is shown in FIGS. 5-8, wherein FIG. 5 is copper T2The microscopic corrosion morphology photos of the test piece after being soaked in F0 (figure a) and F5 (figure A) for 21D, the macroscopic corrosion morphology photos of the copper cast iron HT300 test piece after being soaked in F0 (figure B) and F5 (figure B) for 21D, the macroscopic corrosion morphology photos of the aluminum LY12 test piece after being soaked in F0 (figure C) and F5 (figure C) for 21D, and the macroscopic corrosion morphology photos of the steel 45# test piece after being soaked in F0 (figure D) and F5 (figure D) for 21D are shown in figure 7;
as can be seen from FIGS. 5-8, the carbon steel, cast iron and copper of FIGS. (a, b, d) were severely corroded, the surface of the coupon was loose, and the surface of the carbon steel and cast iron was cavitated. The surface topography corrosion of F5 was significantly inhibited compared to F0. In the graph (A, B, C, D), the cast iron showed shallow pits due to desorption caused by long-term immersion, and the aluminum, copper and carbon steel surfaces also clearly showed traces of sample polishing, and most of the corrosion of the metal test piece occurred from the texture generated by the polishing of the test piece. The corrosion of the metal surface can be weakened by adding the polyaniline, and a certain corrosion inhibition effect is achieved.
Example 4 cast aluminum alloy corrosion measurement in Heat transfer State
1. Preparation of test piece for corrosion determination test of cast aluminum alloy in heat transfer state
The size of the cast aluminum test piece used in the test is 6.5cm in diameter and 1.3cm in thickness, and a thermocouple hole is reserved. The specific specification of the material conforms to the specification in ASTM D4340. The cast aluminum specimens were polished with a grit (1# abrasive paper) and deburred to make the surfaces bright and shiny without any visible oxide film or stain. Thoroughly washing the sample by tap water; then washed with absolute ethyl alcohol, dried and weighed. Before recording the weight, the mixture should be dried in a drying oven at 100 ℃ for 1 hour to reach the constant weight. If not immediately used after weighing, the sample is placed in a desiccator for later use and removed when needed.
2. Test solutions
In 375 ml distilled or deionized water, 82.5 mg reagent grade sodium chloride was dissolved and 125 ml test coolant was added. These solutions were sufficient for one test.
3. Method for measuring corrosion of cast aluminum alloy in heat transfer state
It is important that the engine antifreeze be effective in inhibiting heat transfer corrosion of the aluminium cylinder head during operation of the engine, since any corrosion products formed may deposit on the inner surfaces of the radiator, leading to overheating of the cooling system and boiling of the coolant over-flow. The test tests whether the unused antifreeze solution for the engine has the performance of inhibiting the heat transfer corrosion of the aluminum cylinder cover.
And soaking the weighed cast aluminum test piece in a prepared test solution containing polyaniline antifreezing solution F0, F3, F5 and F8, applying pressure to the test piece by using air, wherein the pressure value is 190-200 kPa, the temperature is 135 +/-1 ℃, soaking for 168 hours under a constant temperature and constant pressure state, and after the test is finished, cleaning and weighing the test piece. Taking three same test pieces, polishing, cleaning, drying and weighing the test pieces according to the method of the test pieces, cleaning the test pieces according to the treatment method of the test pieces after the test, weighing the test pieces, and taking the average cleaning mass loss value of the three test pieces as a blank cleaning mass loss value. And calculating the heat transfer corrosion rate of the test piece by calculating the mass change value obtained by the experimental test piece to judge the corrosion condition, and referring to SHT 0620-2004 in a detailed method.
Heat transfer corrosion Rate R (mg/cm) of the test specimens2) Calculated as follows:
in the formula (1-3): m 1-mass of test piece before test, g;
m2-test piece mass after test, g;
b, blank cleaning mass loss value of the test piece, g;
a-test piece heat transfer surface area in cm in O-shaped rubber sealing ring2。
3. Results
1. Influence of polyaniline on test results of corrosion measurement method of cast aluminum alloy in heat transfer state
500mL of polyaniline antifreeze fluid F0, F3, F5 and F8 are prepared. The mixture is added into a heat transfer corrosion chamber, the constant pressure is 190 kPa-200 kPa, the constant temperature is 135 +/-1 ℃, and the experiment is carried out for 1 week, namely 168 hours. After the test, the test piece was washed and weighed. And (4) cleaning, weighing and calculating the test piece which is not tested after the test is finished. The calculation results are shown in the following table 5:
TABLE 5 Effect of the amount of polyaniline used on the Corrosion inhibition efficiency of aluminum LY12
From the above table 4, it can be seen that the heat transfer corrosion rate of the F5 antifreeze specimen is lower than that of the specimen in the F0 antifreeze, which indicates that the antifreeze with polyaniline can effectively inhibit the heat transfer corrosion of the aluminum cylinder cover compared with the antifreeze without polyaniline, and the heat transfer corrosion rate in F5 is 62% of that in F0. Therefore, the antifreezing solution added with 5% of polyaniline has the best corrosion inhibition effect.
2. Macroscopic corrosion morphology of cast aluminum test piece
FIG. 9 is a macroscopic corrosion morphology of cast aluminum alloy metal coupons after immersion for 7d in F0 (panel A) and F5 (panel a). It can be seen from fig. 9 that F0 cast aluminum specimen (a) had a marked corrosion mark due to surface delustering and had a number of corrosion points on the surface. The F5 cast aluminum test piece (a) has smooth surface, no corrosion trace and no corrosion point. Therefore, the anti-corrosion performance of the F5 antifreeze is better than that of the F0 antifreeze, namely, polyaniline has the function of inhibiting corrosion in the antifreeze and has good effect.
Claims (6)
1. The high-performance modified concentrated automobile antifreeze fluid is characterized by comprising the following components in parts by weight:
2. the modified concentrated antifreeze fluid for automobiles of claim 1, wherein said water-soluble conductive polyaniline has a conductivity of 10-1S/cm。
3. The modified concentrated antifreeze fluid for automobiles of claim 1, wherein said silicate-based complex additive is selected from the group consisting of Pasteur corporation, model G140 KSC.
4. The method for preparing the high-performance modified concentrated automobile antifreeze fluid according to claim 1, which comprises the following steps:
mixing ethylene glycol, silicate composite additive and glycerol until the mixture is uniform liquid, then adding water-soluble conductive polyaniline, and continuously stirring until the mixture is uniform liquid to obtain the high-performance modified concentrated automobile antifreeze fluid.
5. The method for preparing the high-performance modified concentrated automobile antifreeze fluid according to claim 4, wherein the mixing temperature is normal temperature, and the mixing time is 30-40 min.
6. The method for preparing the high-performance modified concentrated automobile antifreeze fluid according to claim 4, wherein the stirring temperature is normal temperature, and the stirring time is 30-40 min.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114231252A (en) * | 2021-12-29 | 2022-03-25 | 盖姿霖 | Anti-freezing solution for railway wagon and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4210549A (en) * | 1979-01-02 | 1980-07-01 | Basf Wyandotte Corporation | Hydroxybenzoic acid as pH buffer and corrosion inhibitor for alkali metal silicate-containing antifreeze compositions |
| CN101698793A (en) * | 2008-10-15 | 2010-04-28 | 上海港申化工有限公司 | automobile antifreeze |
| CN107011874A (en) * | 2017-06-03 | 2017-08-04 | 湖北文理学院 | A kind of new work engine coolant |
-
2019
- 2019-10-15 CN CN201910977865.6A patent/CN110591663A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4210549A (en) * | 1979-01-02 | 1980-07-01 | Basf Wyandotte Corporation | Hydroxybenzoic acid as pH buffer and corrosion inhibitor for alkali metal silicate-containing antifreeze compositions |
| CN101698793A (en) * | 2008-10-15 | 2010-04-28 | 上海港申化工有限公司 | automobile antifreeze |
| CN107011874A (en) * | 2017-06-03 | 2017-08-04 | 湖北文理学院 | A kind of new work engine coolant |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114231252A (en) * | 2021-12-29 | 2022-03-25 | 盖姿霖 | Anti-freezing solution for railway wagon and preparation method thereof |
| CN114231252B (en) * | 2021-12-29 | 2023-10-10 | 盖姿霖 | Anti-freezing solution for railway wagon and preparation method thereof |
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