CN103147015B - There is the hot rolling acid-cleaning plate of excellent phosphorus characteristic - Google Patents
There is the hot rolling acid-cleaning plate of excellent phosphorus characteristic Download PDFInfo
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- CN103147015B CN103147015B CN201110405045.3A CN201110405045A CN103147015B CN 103147015 B CN103147015 B CN 103147015B CN 201110405045 A CN201110405045 A CN 201110405045A CN 103147015 B CN103147015 B CN 103147015B
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Abstract
The present invention discloses a kind of hot rolling acid-cleaning plate with excellent phosphorus characteristic, and its chemical composition by mass percentage, contains: C:0.020 ~ 0.070%; Si :≤0.020%; Mn:0.20 ~ 0.50%; Al:0.005 ~ 0.040%; Also containing at least one element in Cr, Ti, Nb, V, Ni, Mo element, below Cr:0.30%; Below Mo:0.5%; Below Ni:0.5%, below Ti:0.1%; Below Nb:0.1%; Below V:0.2%, surplus is iron and inevitable impurity.Advantage of the present invention and effect are, improve the phosphatization effect of hot rolling acid-cleaning plate, " with hot Dai Leng " is achieved technically, can be that enterprise is cost-saving, reduce user's purchase cost; Improve the popularity of manufacturing enterprise, the share of market of expanding production enterprise product and competitive power, for manufacturing enterprise creates maximum benefit.
Description
Technical field
The present invention relates to a kind of hot rolling acid-cleaning plate with excellent phosphorus characteristic, this hot rolling acid-cleaning plate is mainly used in the hot rolling acid-cleaning plate that body of a motor car uses.
Background technology
Along with the continuous progress of steel rolling process technology, the performance of latten can reach the performance of cold-reduced sheet in certain fields, makes " with hot Dai Leng " become possibility technically.Hot rolling acid-cleaning plate is a kind of product that the cost performance between cold-reduced sheet and hot-rolled sheet is higher, the ideal of part hot-rolled sheet and cold-reduced sheet, economic substitute products, development of the national economy every profession and trade especially needs, direct applied strip product, can be that enterprise is cost-saving, have good market development prospect.
Hot rolling acid-cleaning plate for raw material, on pickling unit, mainly removes the iron scale of belt steel surface, trimming, smooth and to obtain after being coated with the process of wet goods operation through pickling with high-quality hot-rolled sheet coil.Hot rolling acid-cleaning plate comprises the series such as cold formability steel, structural steel, vehicle structure steel, deep-draw steel, Glassed Steel, is mainly used in the field that automobile and the industry such as compressor, universal machine and other use hot rolling acid-cleaning plate.
Compared with hot-rolled sheet, the advantage of acid-cleaning plate is mainly:
1, surface quality is good, because hot rolling acid-cleaning plate eliminates scale on surface, improves the surface quality of steel, is convenient to welding, oiling and japanning;
2, dimensional precision is high, after smooth, template can be made to change a lot, thus reduces the deviation of roughness;
3, improve surface smoothness, enhance appearance effect;
4, the environmental pollution that user disperses pickling to cause can be reduced.
Compared with cold-reduced sheet, the advantage of acid-cleaning plate is: under the prerequisite ensureing surface quality and service requirements, make user effectively reduce purchase cost.
At present, many enterprises propose more and more higher requirement to the high-performance of steel, low cost.Some auto vendors also begin one's study successively and use hot rolling acid-cleaning plate to replace cold rolled automobile sheet, reduce the production cost of automobile production producer with this.Hot rolling acid-cleaning plate uses and also develops to vehicle body from automobile traveling parts gradually in automobile industry, as Guangzhou Nissan determines that starting bid in November, 2011 on the free and unfettered objective body of a motor car of the next generation uses hot rolling acid-cleaning plate.
Hot rolling acid-cleaning plate is in the use procedure of automobile production producer, when adopting electrophoretic painting etc. to paint to surface of steel plate, usually bonderizing is carried out as base treatment, thus seek the sticking power and the solidity to corrosion that improve the film applied on this chemical conversion film, this has good phosphorus characteristic with regard to needing the hot rolling acid-cleaning plate used.
About the manufacture method of hot rolling acid-cleaning plate, propose following scheme in the prior art.Such as publication number is CN1875123A patent, discloses a kind of hot-rolled steel sheet and manufacture method thereof of chemical conversion film excellent property; Publication number is the patent of CN1732281A, discloses the excellent high-strength steel sheet of a kind of hole expandability, ductility and chemical conversion film forming handling property and manufacture method thereof.These two kinds of patents above-mentioned are all be applicable to the high strength of automobile traveling parts and the hot-rolled steel sheet of high working property, because the performance such as chemical composition, metallographic structure, surface topography of phosphorus characteristic and steel plate all has close contacting, therefore these two patents are unsuitable for the hot rolling acid-cleaning plate that uses on body of a motor car is applied.
Publication number is CN1064320A patent, disclose a kind of Nickel alloy electroplating cold-rolled steel sheet and the manufacture method thereof with excellent punching formation property and bonderizing, this patent is applicable to the cold rolled sheet having electroplated one deck nickelalloy at surface of steel plate, and the content of this patent is unsuitable for realizing on hot rolling acid-cleaning plate.
Publication number is CN101370954B patent, disclose a kind of manufacture method of high strength cold rolled steel plate, even the method is applicable to the addition of Mo to realize high strength, also there is the stable excellent manufacture method changing into the high strength cold rolled steel plate of performance, but the content of this patent is unsuitable for using on hot rolling acid-cleaning plate.
Publication number is CN102011054A patent, disclose a kind of hot rolling acid-cleaning plate and low titanium strengthened production process thereof, this invention is controlled by the low titanium Composition Design of the low manganese of low-carbon (LC) and rolling process temperature and is produced the hot rolling acid-cleaning plate that surface quality is good, processing characteristics is superior, but this patent does not relate to the content of hot rolling acid-cleaning plate phosphorus characteristic.
At present all concentrate on about the patent of hot rolling acid-cleaning plate phosphorus characteristic and document the hot rolling acid-cleaning plate that automobile structure uses, and also do not retrieve about the patent of the hot rolling acid-cleaning plate phosphorus characteristic that body of a motor car uses and document.Because automobile structure hot rolling acid-cleaning plate needs higher intensity, general needs change the metallographic structure of hot rolling acid-cleaning plate as dual phase steel (F+M) etc. by the strengthening element adding some amount as Mo element etc. or by thermal treatment, the composition of this and body of a motor car hot rolling acid-cleaning plate and metallographic structure there is larger difference, Wu Chunsu " chemical conversion film " (Wu Chunsu. chemical conversion film [M]. Beijing: Chemical Industry Press, 1988) introduce in 136th ~ 137 pages, substrate composition and the phosphorus characteristic of metallographic structure on steel plate have larger impact, in steel plate, the element such as Mo can generate with carbon the carbide being an impediment to the complete covering of phosphate layer, phosphatize phosphate coat porosity is increased, and martensite is the sosoloid of carbon in α-iron, phosphate-treated solution is very faint to its corrosive nature, very thin film inferior can only be formed on its surface, if carry out bonderizing with the phosphating process of existing Steel Plate Used for Vehicle Body to it, phosphatize phosphate coat crystallization will be there will be thick, phosphatize phosphate coat film heavy and light, the phosphatization defect such as the low and corrosion resisting property of P ratio is poor, existing automobile production technique cannot be met.
Described on end, the existing patent about hot rolling acid-cleaning plate phosphorus characteristic and document cannot be applicable to body of a motor car hot rolling acid-cleaning plate.And the hot rolling acid-cleaning plate used on body of a motor car, that the one that hot rolling acid-cleaning plate uses on existing automobile extends, also be the continuous progress of steel rolling process technology, make the symbol that " with hot Dai Leng " becomes possible technically, the realization of this technology can be that enterprise is cost-saving, there is good market development prospect, therefore to need a kind ofly to use on body of a motor car, there is the hot rolling acid-cleaning plate of excellent phosphorus characteristic to meet existing automobile phosphating production process, thick to solve the phosphatize phosphate coat crystallization that existing automobile structure hot rolling acid-cleaning plate occurs in existing automobile phosphating production process, phosphatize phosphate coat film heavy and light, the phosphatization defect such as the low and corrosion resisting property of P ratio is poor.
Summary of the invention
The object of the invention is to provide a kind of being used in that body of a motor car has excellent phosphorus characteristic hot rolling acid-cleaning plate, solves that the phosphatize phosphate coat crystallization that existing automobile structure hot rolling acid-cleaning plate occurs in existing automobile phosphating production process is thick, phosphatize phosphate coat film heavy and light, P ratio are low and the phosphatization defect such as corrosion resisting property is poor.
Steel plate of the present invention is on the basis not affecting hot rolling acid-cleaning plate and other performance, and its basal component mass percent, contains: C:0.020 ~ 0.070%; Si :≤0.020%; Mn:0.20 ~ 0.50%; Al:0.005 ~ 0.040%.In addition, also containing at least one element in Cr, Ti, Nb, V, Ni, Mo element, surplus is that iron and inevitable impurity element are formed.
The reason of the chemical composition composition specifying the hot rolling acid-cleaning plate that the present invention uses is described:
C:0.020 ~ 0.070%, C content too low cementite quantity is few, and hot rolling acid-cleaning plate surface not easily forms uniform corrosion, not easily forms excellent phosphatize phosphate coat; C content is too high, easily forms a large amount of perlite in tissue, and cementite is easily separated out at ferrite grain boundaries simultaneously, forms cementite network time serious, makes phosphorization film quality deterioration.
, easily there is selective oxidation on hot rolling acid-cleaning plate surface in Si :≤0.020%, Si too high levels, forms Si oxide compound (Si on hot rolling acid-cleaning plate surface
xo
y), this Si
xo
yin parkerizing process, hinder the formation reaction of phosphate crystal, phosphating reaction cannot be carried out, cannot phosphatize phosphate coat be produced.
Mn:0.20 ~ 0.50%, Mn element effectively and Si element generation association reaction, can generate Mn
2siO
4suppress the generation of Si oxide compound, improve the good quality of phosphatize phosphate coat, Mn content is too low, the generation that Mn element suppresses Si oxide compound cannot be played, only have when Mn/Si ratio reaches more than 7, competence exertion effect, but because Mn element is easy in hot rolling acid-cleaning plate surface " enrichment ", too high levels, easily generates Mn oxide compound, affects the formation of excellent phosphatize phosphate coat.
Al:0.005 ~ 0.040%, Al element has desoxydatoin, and content is too low, and deoxidation becomes not enough, can generate a large amount of MnO, SiO
2deng oxide compound, have a strong impact on phosphatization quality; Content is high, and phosphatize phosphate coat crystal grain can be made thick, makes phosphorization film quality deterioration.
As other element, can Cr, Ti, Ni etc. be listed, but when the content of these elements is too much, phosphatization effect deteriorate may be made, bad impact is caused on bonderizing, therefore, they should be controlled as: below Cr:0.30%; Below Mo:0.5%; Below Ni:0.5%.Carbide, can play the effect of crystal grain thinning, be effective, but too high levels easily causes Hardening Of Steel, they should be controlled: below Ti:0.1% for raising hot-rolled sheet uniform corrosion; Below Nb:0.1%; Below V:0.2%.Inevitable impurity.
In order to ensure the phosphorus characteristic of hot rolling acid-cleaning plate of the present invention, the hot rolling acid-cleaning plate of mentioned component, surface roughness requirements reaches between profile arithmetic average error (Ra) 0.85 μm ~ 1.30 μm, the peak of surfaceness counting (RPc) is between 90 peak numbers/peak, cm ~ 120 number/cm, and meets Ra × RPc >=95.
Its metallographic structure of the hot rolling acid-cleaning plate of mentioned component is ferrite+a small amount of perlite+a small amount of cementite, and its ferrite accounts for 95 ~ 98 area %, and cementite accounts for 1.5 ~ 3.0 area %, and grain fineness number is between 8.0 ~ 9.0 grades.
To specifying that the reason that the metallographic structure of the hot rolling acid-cleaning plate that the present invention uses is formed is described:
When cementite is evenly separated out at intra-die, cementite particle plays a part activated cathode, the area of its quantity shared by the scope of afore mentioned rules is larger, and in Phosphating Treatment Process, hot rolling acid-cleaning plate surface is just more easily by uniform corrosion, and formed phosphorization film quality is more excellent; When cementite surround continuously ferrite crystal grain periphery reach more than 1/2 or form continuously along ferrite grain boundaries or be bordering on continuous net-shaped time, phosphatization quality deterioration.
Hot rolling acid-cleaning plate of the present invention has excellent phosphorus characteristic, and phosphatize phosphate coat is fine and close, evenly, phosphatize phosphate coat film is heavily not less than 2.10g/m
2, P ratio is greater than 85%, soaks and start the time of getting rusty>=60min in 5% salt solution.
Advantage of the present invention and effect are, improve the phosphatization effect of hot rolling acid-cleaning plate, " with hot Dai Leng " is achieved technically, can be that enterprise is cost-saving, reduce user's purchase cost; Improve the popularity of manufacturing enterprise, the share of market of expanding production enterprise product and competitive power, for manufacturing enterprise creates maximum benefit.
Accompanying drawing explanation
Fig. 1 represents hot rolling acid-cleaning plate chain of mountains shape typical surface pattern schematic diagram;
Fig. 2 represents hot rolling acid-cleaning plate polygon typical surface pattern schematic diagram;
Fig. 3 represents model a phosphatization Quality Map in embodiment;
Fig. 4 represents model b phosphatization Quality Map in embodiment;
Fig. 5 represents model c phosphatization Quality Map in embodiment;
Fig. 6 represents model d phosphatization Quality Map in embodiment;
Fig. 7 represents model e phosphatization Quality Map in embodiment;
Fig. 8 represents model f phosphatization Quality Map in embodiment.
Embodiment
Below by specific embodiment, technical scheme of the present invention and product performance test are described in detail:
Step 1, get the slab of the present component of a ~ d shown in table 1 and comparative example e, f, respectively steel plate is heated to Ac
3after the temperature that point is above, under the conditions shown in Table 2, by its hot rolling to 2.8mm thickness.After cool to room temperature, carry out pickling under the conditions shown in Table 3, then carry out smooth by the leveling roll different use age to model, flattening process, in table 4, oiling, packaging, makes a, b, c, d, e, f six kinds of hot rolling acid-cleaning plate models.
Table 1
Table 2
Table 3
| Concentration of hydrochloric acid (quality %) | Pickling temperature | Pickling time | Other |
| 10％～18％ | 75℃ | 40s | The residual acid of thorough removing |
Table 4
| Leveling roll initial stage surfaceness | Unit elongation, % |
| Ra:2.2 μm; RPc:120 peak number/cm | 1.8 |
Step 2, the six kinds of hot rolling acid-cleaning plate models of a, b, c, d, e, the f in step 1 are cleaned after, utilize scanning electron microscope under the multiplying power of 1000 times, carry out the observation of surface topography, surface topography observations schematic diagram is in table 5; By (adopting the HNO of 4% mass percent to the capable etch of a, b, c, d, e, f six kinds of hot rolling acid-cleaning plate model longitudinal feeds
3-CH
3cH
2oH, solution at room temperature) after 16s, utilize metaloscope to observe with the multiplying power of 100 times and 1000 times, the organizational composition in grain fineness number and cross section is differentiated and obtained area occupation ratio, the results are shown in Table 6; The From Talysurf Intra percent ripple instrument utilizing TaylorHobson company of Britain to produce is measured the profile arithmetic average error (Ra) of a, b, c, d, e, f six kinds of hot rolling acid-cleaning plate models and peak count value (RPc), and measuring result is in table 7.
Table 5
| Model | a | b | c | d | e | f |
| Surface topography schematic diagram | Fig. 1 | Fig. 1 | Fig. 1 | Fig. 1 | Fig. 2 | Fig. 1 |
Table 6
| Model | Grain fineness number | Ferrite area occupation ratio | Perlite area occupation ratio | Cementite area occupation ratio |
| a | 8.5 level | 98％ | - | 2％ |
| b | 8.5 level | 98％ | - | 2％ |
| c | 9.0 level | 97.5％ | 0.7％ | 1.8％ |
| d | 8.5 level | 97.5％ | 0.5％ | 2.0％ |
| e | 7.5 level | 98％ | 0.5％ | 1.5％ |
| f | 8.0 level | 95.3％ | 1.4％ | 3.3％ |
Table 7
| Model | Profile arithmetic average error (Ra), μm | Peak count value (RPc), peak number/cm | Ra×RPc |
| a | 1.21 | 114 | 137.94 |
| b | 1.15 | 104.9 | 120.64 |
| c | 1.06 | 105.1 | 111.41 |
| d | 1.04 | 99 | 102.96 |
| e | 0.84 | 103.6 | 87.02 |
| f | 0.88 | 88 | 77.44 |
Step 3, to the six kinds of hot rolling acid-cleaning plate models of a, b, c, d, e, the f in step 1 in automobile factory production scene, bonderizing commerical test is carried out by situ production processing step, the steps include: that degreasing → washing (tap water) → table tune → phosphatization → washing (tap water) → pure water washes (specific conductivity≤5 μ s/cm) → drying (80 DEG C, 10min), a, b, c, d, e, f six kinds of hot rolling acid-cleaning plate phosphatization models are obtained after processing, wherein degreasing condition is in table 8, and phosphatization condition is in table 9.
Table 8
| PH value | Temperature | Time | Mode | Other |
| 10.0 | 40℃ | 2min | Soak | Stir, 80 ~ 150rpm/min |
Table 9
| FA | TA | Temperature | Time | Other |
| 0.6 | 2.5 | 33 | 120s | Stir, 80 ~ 150rpm |
Step 4, scanning electron microscope is utilized to observe a, b, c, d, e, f six kinds of hot rolling acid-cleaning plate phosphatization specimen surface patterns that step 3 obtains with the multiplying power of 1000 times, observations is shown in Fig. 3, Fig. 4, Fig. 5, Fig. 6, Fig. 7, Fig. 8, and phosphatize phosphate coat surface topography evaluation result is in table 10.
Table 10
| Model | Evaluation result |
| a | Phosphatize phosphate coat is silver gray, and phosphatize phosphate coat crystal grain is tiny, even, fine and close |
| b | Phosphatize phosphate coat is silver gray, and phosphatize phosphate coat crystal grain is tiny, even, fine and close |
| c | Phosphatize phosphate coat is silver gray, and phosphatize phosphate coat crystal grain is fine and close, but phosphatize phosphate coat crystal grain elongated, uneven, show slightly thick |
| d | Phosphatize phosphate coat is silver gray, and phosphatize phosphate coat crystal grain is fine and close, but phosphatize phosphate coat crystal grain is elongated, uneven, thick |
| e | Phosphatize phosphate coat is silver gray, and phosphatize phosphate coat crystal grain is elongated, even, but phosphatize phosphate coat is imperfect, defectiveness |
| f | Phosphatize phosphate coat is silver gray, phosphatize phosphate coat coarse grains, uneven, regional area " phosphatization does not go up " |
Step 5, measure the diffracted ray intensity in Hopeite (020) face and Phosphophyllite (100) face according to X-ray diffraction method, deduction background, peak-seeking definite value, by formula P ratio=I
p/ (I
p+ I
h) calculate phosphatize phosphate coat P ratio, wherein I
pthe diffracted ray intensity (CPS) in-Phosphophyllite (100) face, I
hthe diffracted ray intensity (CPS) in-Hospeite (020) face, P ratio calculation the results are shown in Table 11.
Table 11
| Model | a | b | c | d | e | f |
| P ratio, % | 91.2 | 89.5 | 87.6 | 86.1 | 84.3 | 79.2 |
Step 6, a, b, c, d, e, f six kinds of hot rolling acid-cleaning plate phosphatization models step 3 obtained are processed into the model of 7.0cm × 15.0cm, and then utilize weight-loss method to carry out the heavy measurement of phosphatize phosphate coat film, measuring method is in table 12, and measuring result is in table 13.
Table 12
| Solution composition | Temperature | Time |
| Chromium trioxide: 5wt%+ water: 95wt% | 75℃ | 15min |
Table 13
| Model | a | b | c | d | e | f |
| Film weight, g/m 2 | 2.25 | 2.11 | 2.15 | 2.41 | 2.03 | 1.91 |
Step 7, a, b, c, d, e, f six kinds of hot rolling acid-cleaning plate phosphatization models step 3 obtained are processed into the model of 10.0cm × 50.0cm, and be then immersed in 5% salt solution, observe its surface and start the time of getting rusty, measuring result is in table 14.
Table 14
| Model | a | b | c | d | e | f |
| Start the time of getting rusty, min | 88.2 | 74.4 | 65.5 | 62.0 | 58.7 | 49.3 |
Drawn by above-mentioned experiment test, product of the present invention is compared with comparative example, and phosphorus characteristic is excellent, and phosphatize phosphate coat is fine and close, evenly, phosphatize phosphate coat film is great in 2.10g/m
2, P ratio is greater than 85%, soaks and start the time of getting rusty>=60min in 5% salt solution.
Claims (1)
1. have a hot rolling acid-cleaning plate for excellent phosphorus characteristic, it is characterized in that, chemical composition by mass percentage, contains: C:0.020 ~ 0.070%; Si :≤0.020%; Mn:0.20 ~ 0.50%; Al:0.005 ~ 0.040%; Also containing at least one element in Cr, Ti, Nb, V, Ni, Mo element, below Cr:0.30%; Below Mo:0.5%; Below Ni:0.5%, below Ti:0.1%; Below Nb:0.1%; Below V:0.2%, surplus is iron and inevitable impurity, its hot rolling acid-cleaning plate surface roughness requirements reaches between profile arithmetic average error (Ra) 0.85 μm ~ 1.30 μm, the peak of surfaceness counting (RPc) is between 90 peak numbers/peak, cm ~ 120 number/cm, and meet Ra × RPc >=95, its metallographic structure of the hot rolling acid-cleaning plate of mentioned component is ferrite+a small amount of perlite+a small amount of cementite, its ferrite accounts for 95 ~ 98 area %, cementite accounts for 1.5 ~ 3.0 area %, and grain fineness number is between 8.0 ~ 9.0 grades.
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| CN115404475B (en) * | 2021-05-28 | 2023-09-12 | 宝山钢铁股份有限公司 | Steel plate pickling process with excellent phosphating performance |
| CN114032467A (en) * | 2021-11-17 | 2022-02-11 | 攀钢集团攀枝花钢铁研究院有限公司 | Cold-rolled high-strength steel plate and preparation method thereof |
| CN115537653B (en) * | 2022-09-09 | 2023-11-10 | 首钢集团有限公司 | Hot rolled enamelled steel sheet and preparation method thereof |
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