EP1563103A1

EP1563103A1 - Method for making an abrasion resistant steel plate and steel plate obtained

Info

Publication number: EP1563103A1
Application number: EP03782550A
Authority: EP
Inventors: Jean Beguinot; Jean-Georges Brisson
Original assignee: Industeel Creusot
Current assignee: Industeel Creusot
Priority date: 2002-11-19
Filing date: 2003-11-13
Publication date: 2005-08-17
Anticipated expiration: 2023-11-13
Also published as: PL375541A1; AU2009201117B2; DE60319567T2; KR20050083912A; FR2847271A1; PL203154B1; US7462251B2; ES2300636T3; DE60319567D1; RU2005119211A; BR0315694A; ATE388247T1; FR2847271B1; PT1563103E; CA2506347C; US20060144483A1; AU2009201117A1; CA2506347A1; US7998285B2; PE20040486A1

Abstract

The invention concerns a method for making an abrasion-resistant steel part consisting of 0.1 % </= C </= 0.23 %; 0 % </= Si </= 2 %; 0 % </= AI </= 2 %; 0.5 % </= Si + AI </= 2 %; 0 % </= Mn </= 2.5 %; 0 % </= Ni </= 5 %; 0 % </= Cr </= 5 %; 0 % </= Mo </= 1 %; 0 % </= W </= 2 %; 0.05 % </= Mo +W/2 </= 1 %; 0 % </= B </= 0.02 %; 0 % </= Ti </= 0.67 %; 0 % </= Zr </= 1.34 %; 0.05 % < Ti + Zr/2 </= 0.67 %; 0 % </= S </= 0.15 %; N < 0.030, optionally 0 % to 1.5 % of Cu; optionally Nb, Ta and V such that Nb/2 + Ta/4 + V </= 0.5 %; optionally Se, Te, Ca, Bi, Pb contents </= 0.1 %; the rest being iron and impurities. Additionally: 0.095 % </= C* = C - Ti/4 - Zr/8 + 7xN/8, Ti + Zr/2 - 7xN/2 </= 0.05 % and 1.05xMn + 0.54xNi +0.5OxCr + 0.3x(Mo + W/2)<1/2> + K > 1.8, with K = 1 if B >/= 0.0005 % and K = 0 if B < 0.0005 %. After austenitization, the method consists in: cooling at a speed > 0.5 DEG C/s between AC3 and T = 800 - 270xC* - 90xMn -37xNi - 70XCr - 83x(Mo + W/2) and about T-50 DEG C; then cooling at a speed 0.1 < VR < 1150XEP<-1.7> between T and 100 DEG C, (ep = thickness of plate in mm); cooling down to room temperature and optionally planishing. The invention also concerns the resulting plate.

Description

METHOD FOR MANUFACTURING AN ABRASION RESISTANT STEEL SHEET AND SHEET OBTAINED

The present invention relates to an abrasion-resistant steel and its method of manufacture.

Abrasive steels of hardness close to 400 Brinell containing about 0.15% of carbon as well as manganese, nickel, chromium and molybdenum are known at levels of less than a few% in order to have sufficient quenchability. These steels are soaked so as to have a completely martensitic structure. They have the advantage of being relatively easy to implement by welding, cutting or folding. But they have the disadvantage of having a limited resistance to abrasion. It is certainly known to increase the resistance to abrasion by increasing the carbon content and therefore the hardness. But this way of proceeding has the disadvantage of deteriorating the ability to implement.

The object of the present invention is to overcome these disadvantages by providing an abrasion-resistant steel sheet which, all things being equal, has a better abrasion resistance than that of known steels having a hardness of 400. Brinell, while having an implementation ability comparable to that of these steels.

For this purpose, the subject of the invention is a process for manufacturing a part, and in particular a sheet, made of steel for abrasion, the chemical composition of which comprises, by weight: 0.1% <C <0.23%

0% <If <2%

0% <Al <2%

0.5% <Si + Al <2%

0% <Mn <2.5% 0% <Ni <5%

0% <Cr <5%

0% <Mo <1%

0% <W <2%

0.05% <Mo + W / 2 <1% 0% <Cu <1, 5% 0% <B <0.02% 0% <Ti <0.67% 0% <Zr <1, 34% 0.05% <Ti + Zr / 2 <0.67 %

0% <S <0.15% N <0.03% - optionally at least one element selected from Nb, Ta and V in contents such that Nb / 2 + Ta / 4 + V <0.5%, - optionally at least one element selected from Se, Te, Ca, Bi, Pb in contents of less than or equal to 0.1%, the balance being iron and impurities resulting from the preparation, the chemical composition further satisfying the following relationships :

C * = C - Ti / 4 - Zr / 8 + 7xN / 8> 0.095% and:

Ti + Zr / 2 - 7xN / 2> 0.05% and:

1, 05xMn + 0.54xNi + 0.50xCr + 0.3x (Mo + W / 2) ^1/2 + K> 1, 8 or better 2 with: K = 1 if B> 0.0005% and K = 0 if B <0.0005%, the steel having a structure consisting of martensite or a mixture of martensite and self-tempering bainite, said structure further containing carbides and 5% to 20% o austenite.

According to this method, the part or the sheet is subjected to a quenching heat treatment, carried out in hot hot shaping such as rolling or after austenitization by reheating in an oven, which consists in:

- cool the sheet at an average cooling rate greater than 0.5 ° C / s between a temperature above AC ₃ and a temperature T = 800 - 270xC * - 90xMn -37xNi - 70XCr - 83x (Mo + W / 2) , and T-50 ° C approximately, the temperature being expressed in ° C and the contents of C *, Mn, Ni, Cr, Mo and W being expressed in% by weight,

- Then cool the sheet at an average core cooling rate Vr <1150xep ^"1.7 (in ° C / s) and greater than 0.1 ° C / s between the temperature T and 100 ° C, ep being the thickness of the sheet expressed in mm, - And to cool the sheet to room temperature, optionally, it performs a planing.

Optionally, quenching may be followed by tempering at a temperature below 350 ° C, and preferably below 250 ° C. The invention also relates to a sheet obtained in particular by this method, whose flatness is characterized by an arrow less than or equal to 12 mm / m and preferably less than 5 mm / m, the steel having a structure consisting of 5% to 20% of retained austenite, the rest of the structure being martensitic or martensito- bainitic, and contains carbides. The thickness of the sheet may be between 2 mm and 150 mm.

Preferably, the hardness is between 280 HB and 450 HB. The invention will now be described in a more precise but nonlimiting manner and be illustrated by examples.

To manufacture a sheet according to the invention, a steel is produced whose chemical composition comprises, in% by weight:

more than 0.1% of carbon so as to have a sufficient hardness and to allow the formation of carbides, but less than 0.23%, and preferably less than 0.22%, so that the welding and cutting is good.

from 0% to 0.67% of titanium and from 0% to 1.34% of zirconium, these contents being such that the sum Ti + Zr / 2 is greater than 0.05%, preferably greater than 0, 1%, and more preferably greater than 0.2%, for the steel to contain large titanium or zirconium carbides which increase the abrasion resistance. But the sum Ti + Zr / 2 must remain below 0.67% because, beyond, the steel would not contain enough free carbon for its hardness is sufficient. In addition, the Ti + Zr / 2 content will be preferentially lower than

0.50%) or better 0.40% or 0.30% if one needs to favor the tenacity of the material.

From 0% (or traces) to 2% silicon and 0% (or traces) at 2% aluminum, the sum Si + Al being between 0.5%) and 2% and preferably greater at 0.7% or better, greater than 0.8%. These elements, which are deoxidizing agents, also have the effect of favoring the obtaining of a metastable retained austenite highly loaded with carbon, the transformation of which in martensite is accompanied by a large swelling favoring the anchoring of the titanium carbides. - From 0% (or traces) to 2% or even 2.5% of manganese, from 0% (or traces) to 4% or even 5% of nickel and 0% (or traces) at 4% or even 5% of chromium, to obtain a sufficient quenchability and to adjust the different mechanical characteristics or use. Nickel has a particularly favorable effect on toughness, but this element is expensive. Chromium also forms fine carbides in martensite or bainite favorable to abrasion resistance.

From 0% (or traces) to 1% molybdenum and 0% (or traces) at 2% tungsten, the sum Mo + W / 2 being between 0.05% and 1%, and preferably remains less than 0.8%, or better, less than 0.5% _o . These elements increase the quenchability and form in martensite or bainite thin carbides hardening, including self-precipitation precipitation during cooling. It is not necessary to exceed a molybdenum content of 1% in order to obtain the desired effect, particularly as regards the precipitation of hardening carbides. Molybdenum can be replaced in whole or in part by a double weight of tungsten. However, this substitution is not sought in practice because it offers no advantage over molybdenum and is more expensive.

- Possibly from 0% o to 1.5% copper. This element can provide additional hardening without damaging the weldability. Above 1, 5%, it has no significant effect, it generates hot rolling difficulties and unnecessarily expensive.

0% to 0.02% boron. This element can be added optionally to increase quenchability. For this effect to be obtained, the boron content should preferably be greater than 0.0005% o or better 0.001%, and need not exceed substantially 0.01%.

- up to 0.15%) sulfur. This element is a residual usually limited to 0.005% or less, but its content can be voluntarily increased to improve machinability. It should be noted that in the presence of sulfur, in order to avoid difficulties of hot transformation, the manganese content must be greater than 7 times the sulfur content.

- Possibly at least one of niobium, tantalum and vanadium, in such contents that Nb / 2 + Ta / 4 + V remains less than 0.5%) to form relatively large carbides that improve the holding abrasion. But the carbides formed by these elements are less effective than the carbides formed by titanium or zirconium, that is why they are optional and added in limited quantities.

- Possibly one or more elements selected from selenium, tellurium, calcium, bismuth and lead in contents of less than 0.1% each. These elements are intended to improve machinability. It should be noted that when the steel contains Se and / or Te, the manganese content must be sufficient in view of the sulfur content so that selenides or tellurides of manganese can be formed. - The rest being iron and impurities resulting from the elaboration. Among the impurities, there is in particular nitrogen, the content of which depends on the production process but does not exceed 0.03%, and remains generally less than

0.025%. Nitrogen can react with titanium or zirconium to form nitrides that should not be too big to deteriorate toughness. In order to avoid the formation of large nitrides, titanium and zirconium can be added to the liquid steel in a very gradual manner, for example by contacting the oxidized liquid steel with an oxidized phase such as a slag loaded with oxides of titanium or zirconium, then deoxidizing the liquid steel, so as to slowly diffuse titanium or zirconium from the oxidized phase to the liquid steel. In addition, in order to obtain satisfactory properties, the carbon, titanium, zirconium and nitrogen contents are chosen such that:

C * = C - Ti / 4 - Zr / 8 + 7xN / 8> 0.095% And preferably, C *> 0.12% to have a higher hardness and therefore a better abrasion resistance. The quantity C * represents the free carbon content after precipitation of the titanium and zirconium carbides, taking into account the formation of titanium and zirconium nitrides. This free carbon content C * must be greater than 0.095%) to have a martensitic or martensitobasicite structure having a sufficient hardness.

Given the possible formation of titanium nitrides or zirconium, so that the amount of titanium or zirconium carbides is sufficient, the contents of Ti, Zr and N must be such that:

Ti + Zr / 2 - 7xN / 2> 0.05% In addition, the chemical composition is chosen so that the quenchability of the steel is sufficient, given the thickness of the sheet that is to be manufactured. For this, the chemical composition must satisfy the relation:

Tremp = 1, 05xMn + 0.54xNi + 0.50xCr + 0.3x (Mo + W / 2) ^1/2 + K> 1, 8 or better 2 with: K = 1 if B> 0.0005% o and K = 0 if B <0.0005%,

In addition, and to obtain a good resistance to abrasion, the micrographic structure of the steel consists of martensite or bainite or a mixture of these two structures, and from 5% to 20% _> austenite retained . In addition, this structure comprises large titanium or zirconium carbides formed at high temperature, and optionally carbides of niobium, tantalum or vanadium. Due to the manufacturing process that will be described later, this structure is returned, so that it also includes molybdenum carbides or tungsten and possibly chromium carbides.

The inventors have found that the effectiveness of large carbides for the improvement of the abrasion resistance could be obelated by premature loosening thereof and that this loosening could be avoided by the presence of metastable austenite which is transformed under the effect of abrasion phenomena. The transformation of the metastable austenite is by swelling, this transformation in the abraded undercoat increases the resistance to carburetion and thus improves abrasion resistance.

On the other hand, the high hardness of the steel and the presence of embrittling titanium carbides make it necessary to limit the leveling operations as much as possible. From this point of view, the inventors have found that by slowing down cooling sufficiently in the bainitomensitic transformation domain, the residual deformations of the products are reduced, which makes it possible to limit the leveling operations. The inventors have found that cooling the workpiece or the sheet at a mean core cooling rate Vr <1150xep ^{"1, 7} , (in this formula, ep is the thickness of the sheet expressed in mm, and the speed of cooling is expressed in ° C / s) below a temperature T = 800 - 270xC * - 90xMn -37xNi - 70XCr - 83x (Mo + W / 2), (expressed in ° C), the residual stresses generated were reduced This slower cooling in the bainitomensitic range has, in addition, the advantage of causing self-tempering which gives rise to the formation of molybdenum, tungsten or chromium carbides and improves the resistance to wear of the matrix surrounding the large carbides. In order to manufacture a flat sheet having good abrasion resistance and good processability, the steel is made, cast in the form of a slab or ingot. The slab or slug is hot-rolled to obtain a sheet which is subjected to a heat treatment which makes it possible at the same time to obtain the desired structure and a good flatness without subsequent planing or with limited planing. The heat treatment can be carried out in the hot rolling or later, possibly after a cold or mid-heat planing.

In all cases, to achieve the heat treatment:

the steel is heated above the point AC ₃ so as to give it a completely austenitic structure, in which, however, titanium or zirconium carbides remain,

- Then it is cooled to an average cooling rate with a core higher than the critical bainitic transformation speed up to a temperature between T = 800 - 270xC * - 90xMn -37xNi - 70XCr - 83x (Mo + W / 2), and T-50 ° C, approximately, so as to avoid the formation of ferrito-pearlitic constituents, for this, it is generally sufficient to cool at a speed greater than 0.5 ° C / s,

- Then, between the temperature thus defined (that is to say between T and T-50 ° C approximately) and 100 ° C .environment, the sheet is cooled to an average cooling rate at heart Vr less than 1150xep ^{"1 , 7} , and greater than 0.1 ° C / s, to obtain the desired structure,

and the sheet is cooled to room temperature, preferably, but not necessarily, at a slow speed.

In addition, an expansion treatment, such as a tempering at a temperature of less than or equal to 350 ° C, and preferably less than 250 ° C, can be carried out. By average cooling rate is meant the cooling rate equal to the difference between the start and end temperatures of cooling divided by the cooling time between these two temperatures.

This gives a sheet, whose thickness can be between 2 mm and 150 mm, having excellent flatness characterized by an arrow less than 3 mm per meter without planing or with moderate planing. The sheet has a hardness between 280HB and 450HB. This hardness depends mainly on the free carbon content C * = C - Ti / 4 - Zr / 8 + 7xN / 8. The higher the free carbon content, the greater the hardness. The lower the free carbon content, the more work is easy. At equal free carbon content, the higher the titanium content, the better the abrasion resistance.

As an example, consider sheets of 30mm thick steel, labeled A, B, C and D according to the invention, E and F according to the prior art and G and H given for comparison. The chemical compositions of the steel, expressed as 10 ^"3 wt%, and the hardness and an index of wear resistance Rus, are reported in Table 1.

Table 1

The wear resistance of the steels is measured by the weight loss of a prismatic specimen rotated in a tank containing calibrated granules of quartzite for a period of 5 hours.

The wear resistance index Rus of a steel is the ratio of the wear resistance of the steel F, taken as a reference, to the wear resistance of the steel under consideration.

The sheets A to H are austenitized at 900 ° C. After austenitization:

the steel sheet A is cooled at an average speed of 0.7 ° C./s above the temperature defined above (approximately 460 ° C.), and at an average speed of 0.13 ° C./s. below, according to the invention;

the steel sheets B, C, D are cooled at an average speed of 6 ° C./s above the temperature T defined above (approximately 470 ° C.), and at an average speed of 1.4 ° C. s below, according to the invention;

the steel sheets E, F, G and H, given by way of comparison, were cooled at an average speed of 20 ° C./s above the temperature T defined above, and at an average speed of 12 ° C. C / s below. The sheets A to D have a martensite-bainitic self-regenerating structure containing about 10% retained austenite, as well as titanium carbides, while the plates E to G have a completely martensitic structure, the sheets G and H also containing large titanium carbides. It can be seen that, although having hardnesses less than those of the E and F sheets, the sheets A, B, C and D have substantially better abrasion resistance. The lower hardnesses, which correspond, for the most part, to lower free carbon contents, lead to better processability.

Comparison of Examples C, D, F, G and H shows that the increase in abrasion resistance does not result simply from the addition of titanium, but from the combination of titanium addition and structure. containing residual austenite. In fact, it can be seen that the steels F, G and H, the structure of which does not contain residual austenite, have fairly comparable abrasion resistance, whereas the steels C and D which contain residual austenite have significantly better abrasion.

In addition, the comparison of the pairs G and H on the one hand and C and D on the other hand, show that the presence of residual austenite significantly increases the efficiency of the titanium. For Examples C and D, the change from 0.110% to 0.350% titanium results in an increase in abrasion resistance of 56%, whereas for G and H steels, the increase is only 37%.

This observation is attributable to the increased crimping effect of titanium carbides by the surrounding matrix, when it contains residual austenite that can turn into hard, swelling martensite in service.

In addition, the deformation after cooling, without planing, for steel sheets A or B are 6 mm / m and 17 mm / m for steel sheets E and F. These results show the reduction of deformation of the products obtained. thanks to the invention.

As a result, in practice, depending on the degree of requirement flatness of the users, - either, one can deliver the products without planing (gain on the cost and on the residual stresses), - either, one can carry out a leveling to comply with stricter flatness requirement ^(for example 5 mm / m) but easier and introducing less constraints due to the original deformation less on the products according to the invention.

Claims

1 - Process for manufacturing a part, and in particular a sheet, of abrasion resistant steel whose chemical composition comprises, by weight: 0.1% <C <0.23%

0% <If <2%

0% <Al <2%

0.5% <Si + Al <2%

0% <Mn <2.5% 0% <Ni <5%

0% <Cr <5%

0% <Mo <1%

0% <W <2%

0.05% <Mo + W / 2 <1% o 0% <B <0.02%

0% <Ti <0.67%

0% <Zr <1, 34%

0.05% <Ti + Zr / 2 <0.67% o

0% <S <0.15% N <0.03%

optionally from 0% to 1.5% copper,

optionally at least one element selected from Nb, Ta and V in contents such that Nb / 2 + Ta / 4 + V <0.5% o,

- optionally at least one element selected from Se, Te, Ca, Bi and Pb in contents of less than or equal to 0.1% o, the rest being iron and impurities resulting from the preparation, the chemical composition also satisfying the following relationships:

C * = C - Ti / 4 - Zr / 8 + 7xN / 8> 0.095% and: Ti + Zr / 2 - 7xN / 2> 0.05%, and:

1.05xMn + 0.54xNi + 0.50xCr + 0.3x (Mo + W / 2) ^1/2 + K> 1, 8 with K = 1 if B> 0.0005% and K = 0 if B <0 , 0005% according to which the sheet is subjected to a heat treatment of quenching, carried out in hot hot shaping and for example rolling or after austenitization by reheating in an oven, to carry out quenching:

the part or sheet is cooled to an average cooling rate greater than 0.5 ° C./s between a temperature greater than AC ₃ and a temperature between T = 800 - 270 × C * - 90 × Mn-37 × Ni-70 × C-83 × ( Mo + W / 2), and T-50 ° C approximately,

and then the part or the sheet is cooled to an average core cooling rate Vr <1150xep ^"1.7 and greater than or equal to 0.1 ° C / s between the temperature T and 100 ° C., ep being the thickness sheet metal, expressed in mm,

the part or the sheet is cooled to room temperature and, if necessary, planing is carried out.

2 - Process according to claim 1, further characterized in that: 1. 05xMn + 0.54xNi + 0.50xCr + 0.3x (Mo + W / 2) ^{1 2} + K> 2

3 - Process according to claim 1 or claim 2, further characterized in that:

C <0.22% and:

C *> 0.12%

4 - Process according to any one of claims 1 to 3, further characterized in that: Ti + Zr / 2> 0.10%

5 - Process according to any one of claims 1 to 5, further characterized in that:

If + Al> 0.7%

6 - Process according to any one of claims 1 to 5, characterized in that, in addition, is carried out at a temperature less than or equal to 350 ° C. 7 - Process according to any one of claims 1 to 6, characterized in that to add the titanium in the steel, the liquid steel is placed in contact with a slag containing titanium and the titanium is slowly diffused from slag in liquid steel.

8 - Part, and in particular sheet metal, abrasion-resistant steel whose chemical composition comprises, by weight:

0.1% <C <0.23% 0% <If <2% 0% <Al <2% 0.5% <Si + Al <2%

0% <Mn <2.5%

0% <Ni <5%

0% <Cr <5%

0% <Mo <1% 0% <W <2%>

0.05% <Mo + W / 2 <1%>

0% <B <0.02%

0% <Ti <0.67%

0% <Zr <1.34% 0.05% <Ti + Zr / 2 <0.67%

0% <S <0.15%, N <0.03%

optionally from 0% to 1.5% copper,

optionally at least one element selected from Nb, Ta and V in contents such that Nb / 2 + Ta / 4 + V <0.5%,

- optionally at least one element selected from Se, Te, Ca, Bi and Pb in contents less than or equal to 0.1%, the balance being iron and impurities resulting from the elaboration, the chemical composition further satisfying the following relationships: C - Ti / 4 - Zr / 8 + 7xN / 8> 0.095% and:

Ti + Zr / 2 - 7xN / 2> 0.05% o and

1.05xMn + 0.54xNi + 0.50xCr + 0.3x (Mo + W / 2) ^1/2 + K> 1.8 with: K = 1 if B> 0.0005% and K = 0 if B <0.0005%, the steel having a martensitic or martensite-bainitic structure, said structure containing carbides and 5% to 20% of retained austenite.

9 - part according to claim 8, characterized in that:

1, 05xMn + 0.54xNi + 0.50xCr + 0.3x (Mo + W / 2) ^1/2 + K> 2

10 - part according to claim 8 or claim 9, characterized in that C <0.22% and:

C - Ti / 4 -Zr / 8 + 7xN / 8> 0.12%

11 - Part according to any one of claims 8 to 10, characterized in that:

Ti + Zr / 2> 0.10%

12 - part according to any one of claims 8 to 11, characterized in that: Si + Al> 0.7%)

13 - part according to any one of claims 8 to 12, characterized in that the thickness of the sheet is between 2 mm and 150 mm.