Metal ready to use wire and method of manufacturing the wire

 

(57) Abstract:

The invention relates to metal finish the wire and to a method of production of this wire. The wire used, for example, to reinforce plastics and rubber, in particular pipes, belts, films, tyres pneumatic tyres. The technical result of the invention is the provision of sufficient strength before drawing, stability, mechanical properties and annealing the steel to martensite. Ready to use metal wire contains micro steel, which has a structure consisting almost entirely of tempered cold-deformed martensite. Minimum wire diameter is 0.1 mm and the maximum diameter of 0.50 mm Minimum tensile strength of the wire is equal to 2800 MPa. The production method of this wire includes a rod deformation, strain hardening wire and heated to the tempering temperature to provide education structure, consisting almost entirely of tempered martensite. Then the wire is cooled and deform. Modular products that contain at least one wire, this wire or prefabricated wire products used in the refers to metal ready to use wire and to a method of production of this wire. This ready to use wire used, for example, amplification products from plastics and rubber, in particular pipes, belts, films, tyres pneumatic tyres.

The term "ready to use wire", which is used in this application means known in the industry notion, according to which this wire can be used for the intended purpose, without subjecting it to heat treatment, which may cause the change of its metal structure without deformation of the metallic substance, such as drawing, which can change its diameter.

In the patent application WO-A-92/14811 described method for the production of ready to use wire that has a substrate of steel, the structure of which contains more than 90% tempered and cold-deformed martensite, while the carbon content in the steel is equal to 0.05 to 0.6%, and this substrate is covered with a metal alloy that is different from steel, such as brass. The production method of this wire includes heat treatment, which is subjected subjected to cold deformation of the wire by heating the wire above the temperature of transformation of GCC, in order to ensure the establishment is equal to 150oC/C below the temperature of the end of martensite transformation. After this heat treatment, the wire is applied at least two metals is heated wire in order to ensure the formation of an alloy of these metals, usually brass, by diffusion, then cooled wire and subjected to cold deformation.

Described in this document method has in particular the following advantages:

- use as a starting billet rod, the carbon content of which is less than the carbon content of the pearlitic steel

- large choice of rod diameters and ready for use made of wire,

- drawing rod, taken as initial workpiece at high speeds and with fewer breaks,

- diffusion processing is carried out simultaneously with the leave of the wire, which limits the cost of production.

However, as described in this document, the method has the following disadvantages:

a) the temperature of the vacation, which is necessary to ensure good diffusion of the coating, does not always accurately correspond to the temperature which is necessary to obtain sufficient strength before drawing.

c) the Hardenability of steel is insufficient, i.e., it must be cooled with a higher rate in order to obtain a fully or almost fully martensitic structure. If the cooling rate is too slow, can occur instead of the martensite phase, other phases such as bainite phase. This high speed quenching creates a great complication in production.

Generally, it is known that in the production of parts made of martensitic steels the addition of the alloying element, such as vanadium or chromium improves the hardenability and strength due to the release of carbonitrides and/or carbides of vanadium or chromium with vacations. Typically, however, the value of the processing time amounts to a few tens of minutes or several hours, to ensure the selection.

The applicant has unexpectedly found that the selection of carbonitrides and/or carbides of any alloying element, such as vanadium, molybdenum or chromium, may be quicker in the wires, the diameter of which is less than 3 mm, and this selection during holidays allows you to eliminate the aforementioned disadvantages of a) and b), while the presence of these alloying is estline milder quenching.

Consequently, the invention relates to metal ready to use the wire that has the following characteristics:

a) it contains micro steel, the carbon content is 0.2 to 0.6 wt.%, moreover, this steel contains, in addition, at least one alloying element taken from the group consisting of vanadium, molybdenum and chromium, and the minimum content of the alloying element in steel or set of alloying elements in the steel is equal to 0.08 wt. % and the maximum content is 0.5 wt.%;

b) this steel has a structure consisting almost entirely of tempered cold-deformed martensite;

(C) minimum wire diameter of 0.10 mm and a maximum diameter equal to 0.50 mm;

d) minimum tensile strength of the wire is equal to 2800 MPa.

According to a preferred variant implementation, ready for use, the wire has a coating of a metal alloy which is an alloy other than steel, which is located on the substrate of the micro-steel having the aforementioned characteristics.

The method according to the invention, for the production of this ready to use wire different slania carbon in the steel is between 0.2 - 0.6 wt.%, in addition, this steel contains at least one alloying element, which is taken from the group consisting of vanadium, molybdenum and chromium, and the minimum content of the alloying element or alloying elements in the steel is equal to 0.08 wt.%, and the maximum content of 0.5 wt.%;

b) this wire rod is subjected to deformation so that after this deformation, the diameter would be less than 3 mm;

c) deformation interrupt and perform heat treatment of the deformed wire, and this processing is that the wire is heated above the temperature of transformation of GCC in order to provide for the establishment in it of a homogeneous austenitic structure, then its cool, at least until the end of martensite transformation MFwhile the rate of cooling at least equal to 60oC/s thus, to provide a structure consisting almost entirely of martensite;

d) then heat the wire to a temperature called the temperature tempering, the minimum value of which is equal to 250oC, and the maximum value 700oC, thus to cause the formation in steel deposition, at least, carbonitride and/or micro-grain tungsten is almost entirely of tempered martensite;

e) then cooled wire at a temperature of less than 150oC,

f) then deform the wire, the minimum degree of deformation is equal to at least 1.

According to a preferred variant, after the implementation of the above-mentioned step (C), the wire is applied at least two metals that can form in the diffusion alloy, while the above-mentioned micro steel is thus a substrate, and performed in the above step (d) heating at a temperature of vacation also serves to cause the formation of an alloy of these metals, such as brass, by means of diffusion.

The invention relates also to the collecting articles containing at least one ready to use wire made according to the invention. Such modular products, as strands, cables wires, in particular, the cables for the layers of wires or cables consisting of strands of wires.

The invention relates also to the products, which are reinforced at least partially ready for use wires or precast products that meet the previously mentioned features, these products can be, n the Ki entirely of tempered martensite" means, this structure contains less than 1% nematocytes phase (nematandani phases), and this is another phase or other phases are formed as a result of the inevitable heterogeneity of steel.

The invention is illustrated by the following examples.

Definition and testing.

1. Torque measurement.

Measurement of tensile strength is the tensile according to the method described in the French standards AFNOR NF And 03-151, introduced in July 1978.

2. The deformation.

To determine the deformation formula:

( = ln (So/Sf)

where ln denotes the natural logarithm; So- the initial section of wire in front of this strain and Sf- the section of wire after deformation.

3. Structure steel

The structure of the steel is determined visually using an optical microscope at a magnification of 400 times. Sample preparation by means of chemical etching, as well as the study of structures was carried out in accordance with the following document: "De Ferri Metallographica vol. N II, A. Schrader, A. Rose, Edition Verlay Stahleisen GmbH. Dusseldoft.

4. The definition of a point Mf.

Point Mfthe end of martensitic excellent>/P>For this purpose use the following:

Mf= Ms- 215oC

with the relation: Ms= 539 - 423.With - 30,4. Mn - 17,7. Ni - 12.1. Cr - 7,5. Mo - 7,5.Si+10.Co.

Where C, Mn, Ni, Cr, Mo, Si and represent mass%, i.e., the mass percent of chemical substances, legend, which they are.

We accept the fact that vanadium can be used in this formula and can provide the same result as molybdenum, while in the above examples, the vanadium was not specified.

5. Hardness Vickers.

This hardness, as well as the method used for its determination, described in the French AFNOR norms And 03-154.

6. The degree of diffusion of brass. This degree is determined by using x-ray diffraction and through the anode of cobalt (30 kV, 30 mA), determine the area of maximum values of phase (pure copper is determined in mixtures with phase ) after disconnecting the two maximum values.

The degree of diffusion Tdrepresented by the formula:

Td= [area of maximum phase values ] / [the area of the maximum phase + square maximum value phase ]

The maximum value of the phase to meet the main 51o.

Examples

Use four wire rod with a diameter of 5.5 mm, indicated by letters a, b, C, and D. the Composition of the steel of these katenok are listed in the following table 1.

Steel these katanec has a pearlitic structure.

Other elements of these katenok are in a state of inevitable impurities and in such quantities, which are not taken into account, the values of MFand GCC for these katenok are listed in table 2.

Values in GCCoWith given by the formula Andrews (JISI, July, 1967, S. 721 - 727).

GCC = 910 - 203 15,2. Ni + 104.V + 31,5.Mo - 30. Mn + 13,1.W - 20. Cu + 700. P + 400. Al + 120. As + 400. Ti ,

in which, Ni, Si, V, Mo, Mn, W, Cu, P, Al, As and Ti represent mass%, the legend that they are. Therefore, the wire samples a and b are identical and not micro, and the wire samples C and D micro-and differ from each other.

These samples wire is subjected to drawing to a diameter of 1.3 mm, the degree of deformation is equal 2,88.

Then these four wires are subjected to hardening, including the following:

- heating up to 1000oC, the shutter speed for 5s;

- rapid cooling to ambient temperature (about 20oC).

as a gas for quenching the mixture of hydrogen and nitrogen (about 75. % hydrogen, about 25. % nitrogen).

Wire In the cool speed 180oC/s, using, as a gas for quenching the mixture of hydrogen and nitrogen (about 75. % hydrogen, 25% vol. nitrogen).

Wire B is cooled with a speed of 180oC/s using pure hydrogen.

The Vickers hardness was measured for each of the obtained wires A1, B1, C1 and D1, with each letter a, b, C, and D stands referred to the original rod.

The obtained values are identical in table 3.

Wire A1 cannot be used because of its low hardness, which is due to the fact that its structure consists only of martensite. It contains both martensite and banit. Each sample wire B1 and D1 is composed almost exclusively of martensite and its Vickers hardness is satisfactory.

Wire C1 and D1, are made of micro steel, made with easy-to-do quenching (relatively low speed, inexpensive and safe gas mixture), while the method of manufacturing a wire B1 is difficult and expensive (high speed quenching carried out using pure hydrogen), although this method allows you to get access to the S="ptx2">

So it is established that vanadium can improve the hardenability of steel, i.e., it allows for the formation of martensitic phase during hardening.

Then, using a known method on three samples of wire B1, C1 and D1 is applied by electrolysis of the copper layer, and then a layer of zinc. The total number of two deposited metal is 390 mg per 100 g of each of the wires, with 64 wt. % of copper and 36 wt.% zinc. Thus made three wire B2, C2 and D2.

After this heated control sample wire B2, using the Joule-Lenz, 5 seconds each time at three temperatures vacation T, (525oC, 590oC, 670oC), then cooled to ambient temperature (about 20oC) in order to determine the effect of this heat treatment on tensile strength Rmthe degree of diffusion Tdbrass, formed by the fusion of copper and zinc, in this case, the thus obtained wire B3.

The results are shown in table 4.

It is noted that at a temperature of 525oC the degree of diffusion Tdis insufficient (less than 0.85) but that the tensile strength is higher than the tensile strength while the other is the more 0,85), but the tensile strength is much lower than the strength obtained at a temperature of 525oC, and it is insufficient to provide for subsequent drawing high tensile strength. When processing at a temperature of 590oC tensile strength is slightly higher than the tensile strength achieved at a temperature of 670oC, and diffusion brass is somewhat lower, although acceptable, but this strength is also insufficient to ensure strength after drawing.

On the other hand, it is noted that the degree of diffusion increases with decreasing strength, which is a disadvantage, because in practice the degree of diffusion should be as high as is more high tensile strength in order to ensure the possibility of subsequent deformation (for example, deformation in the drawing) without breakage of the wire. So, the point here is that, on the contrary, the deformability decreases with increasing tensile strength, which is contrary to the task.

Two samples of wire C2 and D2 containing vanadium, heated to 590oC for only 5 to ensure a vacation, then cooled at ambient temperature (about 20

Found that in two cases, the degree of diffusion brass more of 0.9. This means that the diffusion is very good and that the tensile strength is also very good. It far exceeds the strength obtained for the control sample B3, when the diffusion brass more of 0.9. So the presence of vanadium allows to provide unexpectedly good tensile strength due to the formation of fine precipitates of carbonitrides and/or carbide of vanadium, which were in the solution after a period of hardening and this despite the very short duration of the leave.

It is known that vanadium is excreted in steels during the holidays for a very large length from ten minutes to several hours, but it is surprising that such separation is carried out at such short intervals that are less than one minute, such as less than 10C.

Then the wire samples B3, C3 and D3 is subjected to deformation by drawing in order to obtain a final diameter of approximately 0.18 mm, which corresponds to the degree of deformation is equal to 4, and receive, thus, ready to use samples of wire B4, C4 and D4, for which the values are, which were given previously for a vacation, the values of Tdare the values that were specified previously and which were determined after the operation of applying a brass coating before drawing, with values of Tdvirtually unchanged when being drawn.

It is noted that the wire samples C4 and D4, made according to the invention and, therefore, obtained using the method according to the invention, are characterized by both good degree of diffusion brass (greater than 0.9) and excellent tensile strength (in excess of 2900 MPa). Control samples of wire B4 are the values of tensile strength, which is significantly lower values of tensile strength wire samples C4 and B4, made according to the invention, except wire B4, which was first treated at a temperature of vacation equal to 525oC, but then the degree of diffusion brass is insufficient (less than 0,85), i.e. it indicates that the drawing difficult to implement and leads to frequent breakages of the wire during its deformation, which greatly complicates the manufacture of the wire than in the case of wire samples C4 and D4, according to the invention.

In the described examples of the invention use NR of metals, such as molybdenum and chromium, and in embodiments that use at least two of the metals selected from the group consisting of vanadium, molybdenum and chromium.

Wire rod, which is used for carrying out the invention, is produced in the same way, which is usually used for the production of wire rod, intended for processing into ready to use a wire used to reinforce tires pneumatic tires. Starting therefore from the bath of molten steel having the composition specified for wire rod according to the invention. This steel is produced first in the electric furnace or basic oxygen envelope, then raskalyaetsya in the bucket with the help of an oxidant, such as silicon, which may not cause the formation of inclusions of alumina. Then enter the vanadium in the bucket in bulk in the form of pieces of ferrovanadium, adding it to the metal bath.

In the case of use as an alloying element chromium or molybdenum, the process is the same.

After preparation of the bath became continuously casting steel ingots or blooms. These semi-finished products then subjected to rolling, according to a known method or directly produce wire rod, if you use blanks.

Run the wire according to a preferred variant of the invention achieves at least one of the following characteristics:

the carbon content in steel is 0.3-0.5 wt.%, moreover, this contents, such as, preferably, equal to 0.4%;

- steel meets the following relationship: 0.3% of Mn 0,6%; 0,1 Si 0,3%; P 0,02%; S 10,02% (wt.%);

- the maximum content of the alloying element or set of alloying elements is 0.3 wt.% steel;

- minimum tensile strength equal to 2900 MPa;

the minimum diameter of 0.15 mm and a maximum diameter equal to 0.40 mm

The implementation of the method according to the preferred variant of the invention achieves at least one of the following characteristics:

the carbon content in the steel used rod, is 0.3-0.5. %, and the content is, for example, preferably, 0.4 per cent;

- steel rod used corresponds to the following relationship: 0.3% of Mn and 0.6%; 0.1% of Si 0,3%; P 0,02%; S 0,02% (wt.%);

- the maximum content of the alloying element or set of alloying elements in the steel wire rod is 0.3 wt.%;

the cooling rate during quenching is less than 150oC/s,

- mgreaney wire up to the tempering temperature it is cooled to ambient temperature;

the minimum degree of deformation after the holidays is 3.

According to a further preferred variant of the invention the production of ready to use wire and method corresponding to the invention, as an alloying element used only one vanadium, the advantage of which is that it provides education melkodisperstnoy allocations, while chromium contributes to the formation of large precipitates, and molybdenum tends to cause delamination. When using only one chrome, its minimum preferred content in the steel is equal to 0.2%.

In the above embodiments, the wire deformation was carried out using drawing, but you can use other ways, such as rolling, if necessary, in combination with the drawing, at least for one of the operations of the deformation.

Of course, the invention is not limited to the above examples, for example, the coating is ready for use in the wire according to the invention, may be made not of brass and the other of any alloy, this alloy can be obtained from two or more metals, for example from Trajano the Xia is to used metals could form an alloy by diffusion at a temperature not exceeding the temperature of the vacation.

1. Metal ready to use wire made of micro steel containing carbon and alloying elements, having a structure composed almost completely released from cold-deformed martensite, tensile strength not less than 2800 MPa, characterized in that the steel contains carbon from 0.2 to 0.6 wt.%, at least one alloying element from the group consisting of vanadium, molybdenum and chromium content of the alloy or set of alloying elements 0,08-0,5 wt.%, the wire has a diameter of 0.1-0.5 mm

2. Metal wire under item 1, characterized in that the wire has a coating of a metal alloy whose composition differs from the composition of the micro-steel, serving as a substrate.

3. Metal wire under item 2, characterized in that the coating is made of brass.

4. Metal wire according to any one of paragraphs.1-3, characterized in that the steel contains carbon in an amount of 0.3-0.5 wt.%.

5. Metal wire according to any one of paragraphs.1-4, characterized in that the steel contains carbon steel conforms to the following ratios: 0,3Mn0,6; 0,1Si0,3; P0,02; S0,02 wt%.

7. Metal wire according to any one of paragraphs.1-6, characterized in that the maximum content of the alloying element or alloying elements in steel is 0.3 wt.% steel.

8. Metal wire according to any one of paragraphs.1-7, characterized in that as an alloying element used only vanadium.

9. Metal wire according to any one of paragraphs.1-7, characterized in that as an alloying element used only chromium content in the steel of 0.2 wt.%.

10. Metal wire according to any one of paragraphs.1-9, characterized in that the wire has a minimum tensile strength equal to 2900 MPa.

11. Metal wire according to any one of paragraphs.1-10, characterized in that the wire has a diameter of 0.15 to 0.4 mm

12. Method for the production of metal ready to use wire, including the production of wire rod from micro steel containing carbon and alloying elements, the deformation of the rod, heat treatment of the wire by heating it above the temperature of transformation AU3ensuring a homogeneous austenitic structure, cooling at least until the end of martensite transformation MFwith the speed of the of Tuska with software selection, steel, at least, carbonitride and/or carbide alloying elements to form a structure consisting almost entirely of martensite tempering, the subsequent cooling and deformation of the wire, characterized in that the steel contains carbon of 0.2-0.6 wt.%, at least one alloying element from the group consisting of vanadium, molybdenum and chromium content of the alloying element or set of alloying elements 0,08-0,5 wt.%, after deformation of the rod to receive a wire diameter less than 3 mm, the cooling of the wire heating temperature above AU3until the end of martensite transformation lead with a speed of at least 60oWith a/C, heating under leave to carry 250-700oWith cooling from the tempering temperature of the lead up to a temperature of less than 250oWith and deformation of the wire is carried out with a minimum degree of deformation of at least 1%.

13. The method according to p. 12, wherein after cooling the wire heating temperature above AU3until the end of martensite transformation MFperform drawing on a wire, at least two metals, which form in the diffusion alloy that is different from steel wire, serving as a substrate, and then are heated to a temperature>/P>14. The method according to p. 13, characterized in that the wire is applied layers of copper and zinc to obtain the alloy of brass with the vacation.

15. The method according to any of paragraphs.12-14, characterized in that the steel wire rod containing carbon in a quantity of 0.3-0.5%.

16. The method according to any of paragraphs.12-15, characterized in that the steel wire rod contains carbon in an amount of about 0.4 wt.%.

17. The method according to any of paragraphs.12-16, characterized in that the steel wire rod according to the following ratios: 0,3Mn0,6; 0,1Si0,3; P0,02; S0,02 wt%.

18. The method according to any of paragraphs.12-17, characterized in that the maximum content of the alloying element or alloying elements in the steel wire rod of 0.3 wt.% steel.

19. The method according to any of paragraphs.12-18, characterized in that as an alloying element used only vanadium.

20. The method according to any of paragraphs.12-18, characterized in that as an alloying element only use chrome with minimal content in the steel of 0.2 wt.%.

21. The method according to any of paragraphs.12-20, characterized in that the cooling rate during quenching is less than 150oWith/s

22. The method according to any of paragraphs.12-21, characterized in that the temperature of the leave amounts to 400-650oC.

23. The method according to any is mperature environment.

24. The method according to any of paragraphs.12-23, characterized in that the minimum degree of deformation after the holidays is 3%.

25. Mixed product containing at least one wire, characterized in that use wire according to any one of paragraphs.1-11.

26. The increased product containing partially wire, characterized in that use wire according to any one of paragraphs.1-11, or bulk product on p. 25.

27. The product under item 26, characterized in that the product is made in the form of a pneumatic tyre.

 

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