CN1012181B - P-added ferritic stainless steel having excellent formability and secondary workability - Google Patents
P-added ferritic stainless steel having excellent formability and secondary workabilityInfo
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- CN1012181B CN1012181B CN 85104196 CN85104196A CN1012181B CN 1012181 B CN1012181 B CN 1012181B CN 85104196 CN85104196 CN 85104196 CN 85104196 A CN85104196 A CN 85104196A CN 1012181 B CN1012181 B CN 1012181B
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Abstract
The present invention relates to phosphorus added ferritic stainless steel having excellent formability and secondary workability, which is basically prepared from elements of the following weight percentage: 0.0050 to 0.050 of carbon, 10.00 to 18.00 of chromium, at most 0.50 of silicon, at most 0.50 of manganese, more than 0.040 and at most 0.200 of phosphorus, at most 0.030 of sulfur, at most 0.60 of nickel, 0.005 to 0.200 of soluble aluminum and a small amount of 0.0050 of boron. Fe and impurities are balanced, and the contents of the carbon, the chromium, the phosphorus, the soluble aluminum and the boron are further balanced, so that points of which the abscissa is (Cr+50*P) percentage and the ordinate is (C+10*B+Sol Al) percentage can fall on the regions of a diagram 1ABCD quadrangle.
Description
The present invention relates to the P-added ferritic stainless steel of excellent formability and secondary workability.
Ferritic stainless steel has moderate formability and erosion resistance.With austenitic stainless steel relatively, they are more cheap, therefore relatively large ferritic stainless steel is used to make durable consumer goods commercial, comprises cooker and as material of construction.On the other hand, low chrome ferritic stainless steel comprises by AISI 409 and SUS410L to be produced, and at high temperature has high strength and oxidation-resistance, and soft steel has erosion resistance relatively, thereby be used to make automatic exhaust system in a large number.Yet compare with soft steel, suitable commercial ferritic stainless steel comprises low chrome ferritic stainless steel, and is much still expensive.So press for the more cheap ferritic stainless steel of development.
The purpose of this invention is to provide a kind of novel ferritic stainless steel, it can cheaply produce and have good formability and secondary workability.
Can provide a kind of P-added ferritic stainless steel according to the present invention, it has good formability and secondary workability, and the weight percent of this each component of stainless steel is as follows substantially:
Carbon: 0.0050 to 0.0500%
Chromium: 10.00 to 18.00%
Silicon: be up to 0.50%
Manganese: be up to 0.50%
Phosphorus: greater than 0.040% but be no more than 0.200%
Nickel: be up to 0.60%
Soluble aluminum: 0.0050 to 0.200%
Boron: trace is to 0.0050%
Iron and unavoidable impurities balance and further with the alloying element balance, so that abscissa is for (percentage ratio of Cr+50 * P) and ordinate are for (point of the percentage ratio of C+10 * B+Sol.Al) can drop in Figure 1A BCD quadrilateral area, wherein A, B, C and the D coordinate of ordering is respectively (12.0,0.30), (12.0,0.005) (22.0,0.020) and (22.0,0.30).
Brief Description Of Drawings
Fig. 1 is the curve that concerns between carbon, chromium, soluble aluminum and the boron content in the expression steel produced according to the invention.
Fig. 2 is the curve that phosphorus content influences the r value in the expression 13%Cr-0.03%C ferritic stainless steel.
Fig. 3 is that soluble aluminum content is to the curve of charpy impact test value influence in the expression 13%Cr-0.03%C-0.10%P ferritic stainless steel.
Fig. 4 is the curve that secondary workability test (enlarge test CuP expansiontest) result is measured in expression, has obtained relation between carbon in the steel of the present invention, chromium, phosphorus, soluble aluminum and the boron content based on The above results.
The ferritic stainless steel essential characteristic of producing according to the present invention is the effect of phosphorus, accurately add an amount of phosphorus relevant with other alloying element, and require to reduce phosphorus in common ferritic stainless steel.
9 kinds of ferritic stainless steel hot-rolling sheet materials are unified among the Japanese JISG4304, and 10 kinds of ferritic stainless steel cold rolled sheets are unified among the Japanese JISG4305.Phosphorus content about above-mentioned stdn ferrite stainless steel, standard code SUS447JI(Cr:28.50 to 32.00%) and SUSXM27(Cr:25.00 to 27.50%) the stainless phosphorus content of two classes is not more than 0.030%, and the stainless phosphorus content of other classification is not more than 0.040%.On the one hand, ferritic stainless steel is the body-centered cubic lattice crystalline structure, and this crystalline structure constitutionally causes reducing the toughness of material.On the other hand, in the material up to 11% or more chromium also further reduce the toughness of material.Can distinguish that relative substance especially phosphorus is unfavorable to the influence of toughness of material.Standard code phosphorus content strict guarantee is no more than 0.03%(or 0.040%).
Have been found that an amount of phosphorus of interpolation can improve the pickling of hot-finished material in ferritic stainless steel, and can improve the secondary workability of cold rolling material.
Fig. 2 illustrates the influence of phosphorus to cold-rolled products r value with curve, estimates that this influence has some variation in the measurement that the shadow zone is represented.According to being 0.7mm, different phosphate content and (13%Cr-0.03%C) measurement of the cold-rolled steel sheet of basal component to thickness, obtain the result that Fig. 2 represents.Prepare the Total Test steel plate with identical common process process, this technological process comprises the annealing steps of the annealing of hot rolling, hot-rolled steel sheet, cold rolling and cold-rolled steel sheet.In the well-known above-mentioned technological process, the r value is the typical observed value of expression material deep-draw performance.The r value is bigger, especially surpasses 1.0 bigger r value, and then the deep-draw performance of material better.As can be seen from Figure 2, when 0.025% phosphorus content is arranged approximately, find that usually the r value is lower than 1.0 in common ferritic stainless steel, when phosphorus content increased and surpass 0.075%, the r value was finally up to 1.4 or bigger.
Said, improved the stainless pickling performance of hot rolled ferrite owing to add phosphorus.Thereby needn't use the nitric acid-hydrochloric acid of the costliness of using usually in the pickling ferritic stainless steel, the hydrochloric acid that only is used in common usefulness in the pickling soft steel just can be finished pickling well.
Can improve the processibility and the pickling of ferritic stainless steel by the phosphorus that concentrates, from the viewpoint of cheap ferritic stainless steel is provided, it is very useful.At first, phosphorus itself is exactly very cheap element.All be to use the alloying element of costlinesses such as titanium, niobium and aluminium to improve the secondary workability of ferritic stainless steel in the past, this certainly will cause the increase of product price.By adding phosphorus source such as suitable iron-phosphorus alloy or using the phosphorated molten iron, can realize the phosphorus that concentrates.Use iron-phosphorus to close the phosphorus that concentrates, the product price increase is seldom more.Use contains the phosphorus molten pig iron phosphorus that concentrates, and product price can reduce on the contrary, because the phosphorus of having removed before having effectively utilized, and therefore can cancel or reduce the dephosphorization furnace charge.In addition, using molten iron to concentrate under the situation of phosphorus, adopting cheap contain ferrophosphorus and chrome ore raw material to produce stainless steel as starting material be possible, because their phosphorus content height.Secondly can also use hydrochloric acid pickler to finish the acid pickling step of hot-finished material, its advantage is that not only economy but also technology are simple.
Yet can not deny: the phosphorus in the ferritic stainless steel usually produces harmful effect to some performance of steel, and the existence of phosphorus usually weakens the toughness and the secondary workability of ferritic stainless steel.
We find, by control carbon, chromium content and interpolation trace soluble aluminum, can overcome phosphorus to ferritic stainless steel flexible harmful effect.
Fig. 3 shows soluble aluminum content to flexible influence (being reflected by the charpy impact test value) with curve.By measure different soluble aluminum content basal components be 13%Cr-0.03%C-0.10%P test sample, obtained the result that Fig. 3 represents.Each sample all is like this preparation, and 30 kilograms of ingots with above-mentioned basal component and certain soluble aluminum content forge down at 1100 ℃, subsequently with forging 760 times equal thermal treatment 4 hours, the material from all thermal treatment downcuts test sample at last.Under 20 ℃ and 0 ℃, carry out charpy impact test respectively.Qualified shock test value is at least 5kgf.m/cm
2Fig. 3 shows, and under test temperature, the whole shock test values of steel that contain 0.002% soluble aluminum nearly all are zero, and surpasses 0.0050% and near 0.010% the time when soluble aluminum content, and the shock test value of steel sharply increase substantially exceeds to little acceptance value 5kgf.m/cm
2, and at soluble aluminum content greater than 0.020% o'clock, soluble aluminum is improved flexible influence and is tending towards saturated.
About " secondary workability " term, we refer to the processibility of deep-draw material.We learn, when the rich phosphorus ferrite stainless-steel cold-rolling sheet material of deep-draw (draw for the first time) then repeated impact it the time, perhaps when vibrations that the rich phosphorus ferrite of deep-draw stainless steel materials causes through being impacted, brittle rupture often takes place, and is being parallel on the direction of drawing for the first time.Owing to draw for the first time, toughness of material reduces and has caused this class fracture, and temperature is lower, it is stronger to draw for the first time, and this class fracture then more may take place.Secondary workability is a kind of performance of material, it is different from toughness and plasticity, therefore should note, this situation is usually arranged, even a kind of material has the good deep-draw performance by high r value representation, but because this material secondary poor processability also can't successfully be processed into desirable the finished product to it.
Relevant phosphorus is not also got a thorough understanding of its mechanism of action accurately fully to the influence of rich phosphorus ferritic stainless steel suitability for secondary processing.Yet we can suppose, in view of phosphorus is a kind of element that the segregation trend is arranged at crystal boundary in essence, the phosphorus at grain boundary segregation plays a part to weaken the intergranular bonding force, owing to draw for the first time this effect is strengthened, thereby just may be taken place by the fracture that intercrystalline failure causes.
Have been found that adding some strict equilibrated alloying elements can overcome the harmful effect of phosphorus to secondary workability, as what this book proposed, they not only also concur separately.
Fig. 4 is the curve that secondary workability test (enlarge test) result is measured in expression, on the The above results basis, has obtained the relation between carbon in the steel of the present invention, chromium, phosphorus, soluble aluminum and the boron content.The result that Fig. 4 represents is to be that the cold-rolled steel sheet test of 0.7mm, different components obtains by thickness.Prepare this cold-rolled steel sheet with identical common process, this technology comprises hot rolling, hot-rolled steel sheet annealing, cold rolling and cold-rolled steel sheet annealing steps.It is the cup of 27.0mm that each block plate that is used to test is all become external diameter with 2.0 the rate of drawing by deep-draw, cup is expand into the circular cone stamping machine at 0 ℃ and breaks.Check that cup is ductile failure or brittle rupture,, prepare 5 to 10 cups and carry out the expansion damage test, measure the percentage ratio that the brittle rupture cup takes place, i.e. the brittle rupture rate the steel that each certain component is used to test.This test will be defined as enlarge test (cup expansion test).If brittle rupture does not all take place in enlarge test whole cups of the certain component that is used to test, promptly the brittle rupture rate is zero, we can say that so the secondary workability of this kind component steel is gratifying.
The component of test steel is illustrated in the set of coordinates among Fig. 4, and abscissa is that (percentage ratio of the expression of Cr+50 * P), ordinate are the formula (percentage ratio of expression of C+10 * B+SoI.Al) to formula.Cr, P, C, B and SoI in formula.Al represents the per-cent of respective element in the steel.Fig. 4 has showed between the component of steel and the cold rolling material secondary workability and has existed clearly dependency.More precisely, as can be seen from Figure 4 to belonging to B(12.0,0.005) C(22.0,0.020) the above and C(22.0 of line, 0.020) D(22.0,0.30) steel of component shown in the point in the line left area, except P
1And P
2Beyond the steel, in enlarge test, do not observe brittle rupture fully.Fig. 4 has showed that further chromium and phosphorus weaken the effect of secondary workability, and carbon, boron and soluble aluminum help to strengthen secondary workability.
Can think P
1And P
2The exception of steel is caused by specific alloy elements.By the way, P
1And P
2Steel has the component of following table 1 expression.Because P
1The carbon content that steel 0.0035% is very low, we think, although exist a considerable amount of soluble aluminum, P in the steel
1Steel can not show gratifying secondary workability yet.Because P
2Steel contains the chromium (18.60%) of undue excess, and lower phosphorus content has weakened its secondary workability.Therefore for the object of the invention, except the upper limit of regulation chromium, also be necessary the lower limit of regulation carbon.
Table 1 chemical composition (weight percent)
Based on above-mentioned enlarge test result and importance thereof, we stipulate that according to curve among Fig. 4 some adds the mutual ratio of alloying element, and promptly regulation carbon per-cent minimum value is 0.005%, and chromium per-cent maximum value is 18.00%.
Also do not get a thorough understanding of the accurate mechanism of action that carbon, boron and soluble aluminum strengthen secondary workability fully.But it is as follows that we can suppose, about the effect of carbon and boron, estimates that they are own to grain boundary segregation, thereby strengthen crystal boundary or stop the deleterious phosphorus of secondary workability at grain boundary segregation.About the effect of soluble aluminum, it helps to suppress the precipitating of chromium carbide, reduces as carbon that chromium carbide consumed, and the carbon amount is also dissolved or increase in the segregation of crystal boundary.According to above-mentioned mechanism, the effect of this carbon can strengthen secondary workability.
Each adds the numerical limits of alloying element with explanation now.
Carbon should be 0.0050% at least, as above to P
1Steel is illustrated, will can not get desirable secondary workability if carbon content is too low.But too high carbon content not only makes material become really up to the mark, causes plasticity unsatisfactory, also is harmful to material welding performance.For fear of these the trouble, require regulation carbon on be limited to 0.0500%.
In order to obtain desirable corrosion resistance nature, require the following of chromium to be limited to 10.00%.From this lower limit of chromium and minimum possible carbon content recorded figure/the AB line.As above to P
2Steel is illustrated, and too high chromium content can weaken the secondary workability that toughness is material.For this reason, the upper limit of chromium is defined as 18.00%.
Silicon helps to improve the antioxidant silicon of material under the high temperature, but the upper limit of silicon is defined as 0.50% because too high silicone content makes material become really up to the mark.
Manganese is a kind of material hot workability and welding zone flexible element of improving.Manganese content was greater than 0.50% o'clock, and this effect is tending towards saturated, and product becomes expensive.The upper limit of manganese is defined as 0.50% for this reason.
Sulphur is a kind of harmful element, erosion resistance of its unfavorable material and hot workability.Thereby sulphur content is lower, and we more like.The admissible upper limit of sulphur is defined as 0.030% at present.
Nickel is of value to the toughness of improving ferrite material, but high-load nickel makes product become expensive, and this violates purpose of the present invention.Therefore adopt the upper limit of the conventional criteria ferritic stainless steel 0.60% nickel upper limit at present as nickel in the alloy of the present invention.
Phosphorus content is vital for the object of the invention.Phosphorus content is not more than at 0.040% o'clock, and requirement removes dephosphorization in advance from the pig iron or special disposal is to remove dephosphorization in converter, and this causes increasing production cost.And be without access to the effect of the enriched phosphorus that can improve pickling and plasticity.Thereby the content that requires phosphorus is greater than 0.040%.But too high phosphorus content is harmful to toughness, hot workability and the secondary workability of material, though can reduce this harmful effect by other alloying element of accurate balance according to the present invention.At present our regulation phosphorus on be limited to 0.20%.
Aluminium can reduce oxygen content in steel and cleaning steel as the reductor in the steel production process.Solubility in acid aluminium (soluble aluminum) helps to suppress the deleterious effect of phosphorus to toughness of products and secondary workability.In order to obtain this beneficial effect of soluble aluminum, need 0.005% soluble aluminum at least.But soluble aluminum content was greater than 0.200% o'clock, and this effect is tending towards saturated, the technical problem that also may cause geat to stop up in casting step.
Even the boron of minute quantity also can significantly improve the secondary workability of material.The boron of trace is enough to obtain desirable secondary workability, as long as the use level of carbon and soluble aluminum is suitable for specific chromium and phosphorus content.In order to obtain best secondary workability, we recommend boron content to be at least 0.0005% but the upper limit of boron is defined as 0.0050%, because boron often causes weakening the plasticity of product.
Nitrogen is not very important for the object of the invention, nitrogen can enter product inevitably in the steel production process, in the ferritic stainless steel of producing according to the present invention, the scope of nitrogen content is 0.0050% to 0.05%, and this is the same with situation about occurring in the conventional stainless steel.
To achieve the object of the present invention, alloying element must be controlled at respectively in the above-mentioned scope separately, the content that depends on certain chromium and phosphorus in addition, carbon, boron and soluble aluminum must balances, so that abscissa is for (percentage ratio of Cr+50 * P) and ordinate are for (C+10 * B+SoI.Al) point of percentage ratio can drop in the ABCD quadrilateral area of Fig. 1.
To further introduce characteristic of the present invention and useful result by following work and case of comparative examples.The molten steel that preparation has the chemical composition shown in the table 2.With hot rolled strip that thickness is 3.2mm of each molten steel preparation.To each piece hot rolled strip acid pickling and rust removing, and it is cold-rolled to the thickness of 0.7mm without any intermediate heat treatment, then must through 820 ℃ of following soaking 1 minute and in air the refrigerative step finish annealing, Zhi Bei steel sample is used to test r value and secondary workability like this.The r value is calculated as follows:
r＝（ro+2r
45+r
90）/4
Ro, r in the formula
45And r
90Be respectively along the Lankford value that becomes 0 °, 45 ° and 90 ° directional survey with rolling direction.In order to measure secondary workability, under 0 ℃, carry out enlarge test and estimate the result by Fig. 4 with reference to above-mentioned Fig. 4.
Can show following situation.
No. 1 to No. 7 steel has quite high r value, demonstrates their good deep-draw performances.Brittle rupture does not take place in enlarge test, and this has reflected their gratifying secondary workabilities.
No. 8 the contrast steel contains above the phosphorus amount of stipulating in this book, (Cr+50 * P) per-cent also surpasses the scope that Fig. 1 represents, so although this steel r value is quite high, and its secondary workability and unsatisfactory.
No. 9 contrast steel phosphorus content is low, thereby its r value is also low, and this represents its deep-draw poor performance.
No. 10 the contrast steel contains 0.0028% carbon amount, and this is lower than this book regulation, thereby the secondary workability of this steel is not enough.
The quantity that No. 11 contrast steel contain alloying element is respectively in the scope separately of this book regulation, but (Cr+50P) per-cent surpasses the scope that Fig. 1 represents, makes its secondary workability and unsatisfactory.
No. 12 the contrast steel contains 0.003% soluble aluminum, and this is lower than this book regulation, and (the solvable Al of C+10B+) per-cent is low too with respect to 20.59% (Cr+50P), and secondary workability is also unsatisfactory as a result.
No. 13 contrast steel soluble aluminum content also are lower than this book regulation, and chromium per-cent and (Cr+50P) per-cent is too high, therefore, the secondary workability of this steel is poor.
Table 1 chemical composition (weight percent)
Carbon silicomanganese phosphorus sulphur chromium nickel soluble aluminum nitrogen boron
P
10.0035 0.29 0.18 0.082 0.006 12.09 0.07 0.035 0.0070 trace
P
20.0370 0.08 0.23 0.048 0.005 18.60 0.13 0.023 0.0250 trace
Table 2
Steel grade
C Si Mn P S Cr Ni Sol.Al
Number class
1 A 0.0468 0.35 0.20 0.104 0.005 10.45 0.06 0.045
2 A 0.0121 0.09 0.17 0.089 0.006 11.29 0.10 0.012
3 A 0.0220 0.27 0.23 0.181 0.001 12.43 0.07 0.058
4 A 0.0318 0.42 0.22 0.067 0.010 14.58 0.06 0.033
5 A 0.0450 0.30 0.36 0.092 0.004 16.72 0.30 0.120
6 A 0.0375 0.18 0.12 0.053 0.007 16.85 0.07 0.010
7 A 0.0089 0.25 0.23 0.085 0.005 17.50 0.06 0.052
8 B 0.0308 0.29 0.24 0.250 0.005 11.34 0.07 0.023
9 B 0.0283 0.10 0.28 0.027 0.010 11.03 0.06 0.037
10 B 0.0028 0.48 0.19 0.084 0.008 12.59 0.10 0.063
11 B 0.0359 0.23 0.23 0.151 0.006 16.32 0.08 0.029
12 B 0.0085 0.28 0.20 0.078 0.005 16.69 0.06 0.003
13 B 0.0342 0.36 0.27 0.062 0.006 19.70 0.10 0.004
A: according to the steel of the present invention's production
B: contrast steel
Table 3
Grade of steel kind r value secondary workability
*
1 A 1.50 ○
2 A 1.42 ○
3 A 1.49 ○
4 A 1.37 ○
5 A 1.65 ○
6 A 1.21 ○
7 A 1.34 ○
8 B 1.32 ●
9 B 0.87 ●
10 B 1.45 ○
11 B 1.51 ●
12 B 1.43 ●
13 B 1.33 ●
A: according to the steel of the present invention's production
B: contrast steel
*: the expander experience
Zero: the broken ring rate of fragility is 0
Zero: the brittle rupture rate is less than 50%
●: the brittle rupture rate is not less than 50%
Table 2(is continuous)
C+10B+
N B Cr+50P balance
Sol.Al
0.0982 trace 15.65 0.0918 iron and impurity
0.0120 trace 15.74 0.0241 iron and impurity
0.0250 0.0010 21.48 0.0900 iron and impurity
0.0060 trace 17.93 0.0648 iron and impurity
0.0087 trace 21.32 0.1650 iron and impurity
0.0210 0.0042 19.50 0.0895 iron and impurity
0.0069 0.0035 21.75 0.0959 iron and impurity
0.0103 trace 23.84 0.0538 iron and impurity
0.0081 trace 12.38 0.0653 iron and impurity
0.0143 trace 16.79 0.0658 iron and impurity
0.0121 trace 23.87 0.0649 iron and impurity
0.0230 trace 20.59 0.0115 iron and impurity
0.0080 trace 22.80 0.0382 iron and impurity
Claims (1)
1, ferritic stainless steel is characterized in that this stainless steel chemical component (by weight) is:
C：0.0050-0.0500，
Cr：10.00-18.00，
Si: be up to 0.50,
Mn: be up to 0.50,
S: be up to 0.030,
Ni: be up to 0.60,
P: greater than 0.040, but be not higher than 0.200,
Solvable Al:0.005-0.200
B：0.0005-0.0050，
All the other are iron and unavoidable impurities,
And these alloying elements carry out balance, so that the point of the percentage ratio that is expressed from the next on the abscissa:
(Cr+50×P)
Point with the percentage ratio that is expressed from the next on the ordinate:
(the solvable Al of C+10 * B+)
Can drop in the quadrilateral area of ABCD shown in Fig. 1, wherein the coordinate of 4 of A, B, C and D is respectively: (12.0,0.30), (12.0,0.005), (22.0,0.020) and (22.0,0.30).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85104196 CN1012181B (en) | 1984-06-28 | 1985-06-01 | P-added ferritic stainless steel having excellent formability and secondary workability |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13194784A JPS6112825A (en) | 1984-06-28 | 1984-06-28 | Manufacture of corrosion-resistant alloy steel sheet easy to pickle and having excellent workability |
| CN 85104196 CN1012181B (en) | 1984-06-28 | 1985-06-01 | P-added ferritic stainless steel having excellent formability and secondary workability |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85104196A CN85104196A (en) | 1986-12-31 |
| CN1012181B true CN1012181B (en) | 1991-03-27 |
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ID=25741714
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| CN 85104196 Expired CN1012181B (en) | 1984-06-28 | 1985-06-01 | P-added ferritic stainless steel having excellent formability and secondary workability |
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| CN103436797B (en) * | 2013-09-10 | 2014-10-01 | 郑州永通特钢有限公司 | Method for producing phosphorus-containing ferrite stainless steel by using iron oxide type laterite and product thereof |
| CN111655890B (en) * | 2018-03-30 | 2021-10-29 | 日铁不锈钢株式会社 | Ferritic stainless steel sheet and method for producing same |
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1985
- 1985-06-01 CN CN 85104196 patent/CN1012181B/en not_active Expired
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