When evaluating the corrosion resistance of paint films in the laboratory, it is usually necessary to pre-treat the painted samples before the salt spray test
The marking process is the result of artificial destruction of the vehicle being scratched in actual use and accelerated corrosion damage in the salt spray atmosphere, which can reflect the durability of the paint film in the corrosion test
However, different scribing tools used in different regions, the blade, and scribe depth and area of exposed metal are not the same, which have a greater impact on the test results of the coating line coatingol.
At present, there is no unified method for the scribing operation of each host plant, and there is no comparative analysis of the effects of different scribing treatments on the spread of paint film corrosion, and the mechanism has not been discussed in depth
In this study, common tools were selected to perform different scribing treatments on the electrophoretic paint films of iron-based, aluminum-based, and iron-based galvanized sheets.
Corrosion tests were performed in different salt spray environments, and a stereo microscope was used to scribe the lines from a microscopic perspective.
The mechanism of the processing morphology affecting the corrosion propagation of the coating was explored and studied, and the influence of different scribing treatments on the corrosion propagation performance of the paint film was analyzed
The purpose is to reveal the influencing factors of the scribing process and improve the paint film corrosion resistance evaluation system
The samples were scribed according to the following five knife shapes.
The tools used were a: ERICHSEN 0.
5 mm; b: ERICHSEN 1.
0 mm; c: V-shaped pointed scribe; d: V-shaped arc-shaped scribe; e: U-shaped knife
Figure 1 Schematic diagram of 5 kinds of tool marking
The influence of different knife shapes
The galvanized sheet was marked with c and d in Figure 1 and subjected to 840h neutral salt spray (NSS) test
Figure 2 shows the micro-topography of the two scribing methods
It can be seen from the figure that the scratches produced by the two scribing methods are wedge-shaped.
In Figure b, the bottom of the scratch is wider than a, and both scribing have penetrated the galvanized layer to the iron matrix
Figure 3 shows the scribing morphology of the sample surface with corrosion products removed after the neutral salt spray test
It can be seen from the figure that, after the test, obvious corrosion spread occurred at the scribed area, but no obvious red rust appeared
After removing the loose paint film and corrosion products on the surface, visually observe that the corrosion spread obtained by the two scribing methods is similar
Figure 2 Scribing micrographs of two V-shaped tools
Figure 3 The spread of paint film corrosion under two V-shaped tools a: V-shaped tip; b: V-shaped arc tip
At present, the evaluation of corrosion spread in domestic and foreign standards is mainly divided into two types: one is to calculate the average value according to ISO 4628-8, and the other is to directly measure the maximum spread width
3, a unilateral average corrosion spread is 1.
69 cm, the maximum unilateral spread is 2.
50 cm; b unilateral average corrosion spread is 1.
40 cm, and the maximum unilateral spread is 2.
It can be seen that the corrosion spread obtained by the scribing treatment using method a is slightly greater than that of method b.
For the 840h long-period NSS test, the corrosion spread between the two methods is not much different
The influence of different marking methods
At present, the major OEMs have not unified the shape and angle of the scribing, and the influence of different scribing methods on the spread of corrosion has not been studied in depth
Figure 4 shows 5 ways of scribing on the same galvanized sheet using cutters of the same width.
Among them, a, b, and c are the most commonly used scribing methods at present
Figure 4 Corrosion spread in different scribing methods
It can be seen from Figure 4 that the corrosion spread at the horizontal lines in c and e is significantly smaller than in other directions, and at the same time, due to rust in c and d, the scribe line below it is disturbed
Ignore the horizontal lines in c and e, and take the average of the spread at the five scribes.
The results show that the spread of a, b, c, and e is basically the same.
The difference between a and d is analyzed.
The larger spread difference in oblique direction is mainly due to the existence of cross position in a, which leads to heavier corrosion and easier coating peeling
Test two boards at the same time, and the rules obtained are consistent
Therefore, in the actual scribing process, a line in the vertical direction can be used to characterize the anti-scribing spread of the paint film
The reason for the large difference between the spread of horizontal and vertical lines may be that corrosion products and salt are more likely to accumulate in the horizontal direction.
High-concentration corrosion products and salt have a competitive relationship with adsorbed oxygen, which can inhibit the continued expansion of the corrosion reaction.
The influence of different substrates and test conditions
The base metal materials commonly used in the automotive industry include iron-based, aluminum-based, and iron-based galvanizing
The resistance to salt spray corrosion spread at the scribe line of the electrophoretic paint film of the three materials is very different
In order to study the influencing factors of the corrosion propagation performance of the marking, the representative test conditions are selected and the tests are carried out at the same time
Figure 5 shows the corrosion spread data of different substrates under different salt spray test conditions
Figure 5 Corrosion propagation values under different substrates and test conditions
It can be seen from the figure that the corrosion spread of the galvanized electrophoretic plate under NSS conditions is obvious, and there is no obvious corrosion spread of the aluminum-based electrophoretic plate under the three conditions
In the SAE J2334 condition, the corrosion spread of the galvanized electrophoresis plate<the iron-based electrophoresis sheet, which is also the iron-based electrophoresis sheet in the ISO 11997-1 cycle B of the circulating salt spray<the galvanized electrophoretic sheet
First, analyze the obvious reason why the corrosion spread of the galvanized layer under the NSS condition is that the neutral salt spray test continues to spray.
The Cl- concentration and relative humidity in the box are always high.
The corrosion products of the galvanized sheet are loose and cannot prevent the entry of moisture and Cl-.
The corrosion products in the iron-based electrophoresis plate are relatively dense, resulting in slower corrosion progress
Analyze the opposite performance of zinc electrophoresis and iron-based electrophoresis under the two cyclic salt spray conditions, which may be caused by different test solutions and test conditions
The solution used in SAE J2334 contains CaCl2 and NaHCO3, and involves a high temperature stage; while ISO 11997-1 cycle B uses a common NaCl solution and does not have a high temperature stage above 50°C
The solution used in GMW 14872 is similar to SAE J2334 and the temperature in the high temperature stage is maintained at 60°C.
Galvanized and iron-based electrophoresis sheets were used for the same cycle of GMW 14872 test.
The results are shown in Figure 6
It can be seen from the figure that the corrosion spread of the galvanized electrophoretic plate after the GMW 14872 test is significantly smaller than that of the iron-based electrophoretic plate
In summary, the corrosion spread of the galvanized substrate is greater than that of the iron matrix in the non-high temperature stage and the use of NaCl solution in the cyclic corrosion process, and the corrosion spread of the iron-based electrophoretic paint film in the high temperature stage and the corrosion process of the composite salt The value is greater than the galvanized substrate
It can be seen that the extent of corrosion spread has a greater relationship with the electrophoretic matrix and corrosion conditions
Figure 6 Corrosion morphology of different substrates obtained under GMW14872 cyclic salt spray conditions
The effect of scribing depth
Use the same scoring knife to make two sets of scribing on the same galvanized board.
One set of scribing depth touches but does not penetrate the galvanized layer; the other set of scribing lines penetrates the galvanized layer, as shown in Figure 7
Figure 7 Microscopic images of different scribing depths
Perform 5 cycles of ISO 11997-1 cycle B corrosion test on the scribed test board.
The 3 bars on the left of Figure 8 are the test results of penetrating the zinc layer, and the 3 bars on the right are the test results of not penetrating the zinc layer.
It can be clearly seen from the figure that when the depth of the scribe line is deeper, the corrosion spread width is larger than that of the shallower line
Figure 8 Corrosion spread of different scribe depths
This is because the iron matrix leaks out when the line is deep.
The iron matrix and the zinc coating form a galvanic pair, which accelerates the corrosion of zinc.
The corrosion of zinc will form hairy 2ZnCO3•3Zn(OH)2, ZnO, ZnCl2•Zn(OH) ) 2 and so on
These corrosion products are hygroscopic.
In the process of salt spray and high humidity in the cyclic alternating salt spray test, corrosion products gradually accumulate at the scribe line, and the corrosion product fills the groove of the scribe line, and the corrosion gradually develops into the horizontal corrosion under the film.
Since galvanic acceleration is more likely to form corrosion product accumulation, the corrosion spread is more serious when the scribe is deeper than when the scribe is shallow
The influence of different line widths
Scribe lines with a width of 0.
5 mm and 1 mm were performed on the same galvanized sheet, respectively, and the microscopic morphology of the line was shown in Figure 9
It can be seen that the difference between the two knife-shaped scribe lines is only in the width of the scribe line
Figure 9 Microscopic images of different scribing widths
Figure 10 shows the topography after the corrosion test.
The left 3 bars are 0.
5 mm wide, and the right 3 bars are 1 mm wide
Table 1 shows the spread results of the two scribing methods through corrosion tests
It can be seen that the 0.
5mm scribing method has a larger average value in terms of average value, and the 1mm scribing method has greater corrosion in terms of maximum spread
Figure 10 Corrosion spread of different scribe widths
Table 1 Corrosion spread of paint film under different line widths
5 mm scribe line has a strong continuity of paint film peeling off visually.
Because the counting method of average corrosion spread is calculated according to the left and right maximum values measured at a fixed distance in ISO 4628-8, this calculation method better reflects the overall Corrosion spread, but there is a problem of insufficient reflection of the severity of corrosion spread
When the maximum spread is used for evaluation, the ability of the paint film to resist the spread of scratches and corrosion can be clarified, but there is also the problem of data contingency.
Therefore, a better evaluation method should be to record and evaluate both evaluation methods at the same time
In the galvanic corrosion pair formed by the galvanized layer and the iron substrate, zinc is used as the anode and iron is used as the cathode.
The two scribing methods with different widths have the same exposed area of the galvanized layer.
The exposed area of the iron substrate is 0.
5 mm which is half of that under 1 mm.
In this corrosion system, the electrode reaction in the early stage of corrosion is mainly controlled by the cathode.
At this time, the electrode reaction speed increases with the increase of the exposed area; when there are more corrosion products, the corrosion system becomes resistance controlled, and the corrosion products formed by the galvanized layer at this time The number and distribution of the corrosion will completely determine the corrosion reaction speed
The corrosion products that accumulate when the scribe line is wider are more than those when the scribe line is narrower.
The flocculent corrosion product has stronger water absorption and induces strong under-film corrosion.
Therefore, the maximum corrosion spread value is larger when the scribe line is wider.
However, in the scribing method with a narrower scribe line, it seems that the corrosion spread is more uniform
(1) The use of different knife-shaped markings has different effects on the spread of corrosion, and there is little difference between the V-shaped tip and the V-shaped arc tip;
(2) With different scribing angles, the horizontal scribing spread is small, and the vertical and tilt angles are not much different;
(3) The degree of corrosion spread is largely related to the substrate and corrosion conditions, and the aluminum alloy substrate electrophoretic film has the best corrosion resistance performance;
(4) The depth of the scribing affects the corrosion resistance of the paint film, and the corrosion spreads when the scribing is deep;
(5) The impact of different scribe line widths on the paint film is more complicated.
When the scribe line is wider, the maximum corrosion spread value is larger, and the scribe line width is more uniform than h corrosion spread.
The actual test evaluation should be based on the average spread value and the maximum spread value.
The evaluation of each dimension is more reasonable
Authors | Song Hailin, Lu Chenghuan, Chen Yongbin, etc.
(CSTC Standard Technical Service Co.
, Automotive Corrosion Protection Testing Technology Center)