The present invention refers to a process for the production of grain oriented electrical steel strip starting from thin slabs, and more precisely refers to a process allowing to simplify the production of grain oriented electrical steel, and moreover to obtain a constant and superior quality product. STATE OF THE ART Grain oriented electrical silicon steel is generically classified into two main categories, essentially differing in relevant induction value measured under the effect of an 800 As/m magnetic field, called B800 value; the conventional grain oriented product has a Bδ00 lower than about 1890 mT, while the high-permeability product has a BδOO higher than 1900 mT. Further subdivisions are made considering the core losses value, expressed in W/kg at given induction and frequency. Said products have essentially the same application field, mainly for the production of transformers cores. The high-permeability oriented grain steel find its applications in those fields in which its advantages of high permeability and low core losses can compensate for the higher costs with reference to the conventional product. In the production of electrical steel strips, the grain orientation is obtained utilizing finely precipitated second phases which, in one of the last production steps called secondary recrystallization. inhibit the growth of the grains or crystals of iron (body centered cube) up to a certain temperature, beyond which, according to a complex

process, the crystals having an edge parallel to the rollig direction and a diagonal plane parallel to the strip surface (Goss structure) selectively grow.

The second phases, i.e. non-metallic precipitates within the solidified steel matrix, which are utilized to obtain the growth inhibition are mainly sulfides, and/or selenides, particularly of manganese, for the conventional oriented grain steels and nitrides, particularly containing aluminum, for the high-permeability oriented grain steels. The intrinsic complexity of the oriented grain electrical steels production processes is essentially attributable to the fact that said second phases during the relatively slow cooling of the continuously cast slabs precipitate in coarse form, unidoneous for the desired effects, and must be dissolved and reprecipitated in the right form which has to be maintained up to the moment when the grain is obtained having the desired dimensions and orientation, during the final secondary recrystallization step.

From the above, the following idea can be derived, that a quicker cooling during the continuous casting should improve the inclusional state of the slabs, thus rendering less complex the control of the various steps of the slab transformation process into strips. However, it was found that the thin slab continuous casting though having a cooling rate quite higher than the one obtainable in the conventional continuous casting, is not sufficient per se to allow obtaining the necessary quality.

Since long time this Applicant is studying the possibility to utilize the technologies of the thin slab or strip continuous casting, up to

now utilized essentially for carbon steels, also for more sophisticated materials such as silicon electrical steels. In this field, very important results were obtained, both in the field of conventional oriented grain and in the one of high magnetic characteristics oriented grain steels. DESCRIPTION OF THE INVENTION

The present invention aims to improve the conventional grain oriented electrical steel production, utilizing in an innovative way the thin slab continuous casting technology and introducing specific modifications of the transformation process.

In particular, the continuous casting process is carried out in such a way that a particular equiaxic to columnar grains ratio is obtained, as well as specific equiaxic grains dimensions and precipitates of limited dimensions. The present invention refers to a silicon steel strip production process of the kind above identified as conventional, in which a silicon steel is continuously cast, high-temperature annealed, hot rolled, cold rolled in a single step or in a plurality of steps with intermediate annealings, the cold rolled strip so obtained is annealed to perform primary annealing and decarburization, coated with annealing separator and box annealed for the final secondary recrystallization treatment, said process being characterized by the combination in cooperation relationship of:

(i) continuously casting a thin slab of the following composition: 2 to 5-5 wt# Si, 0.05 to 0.4 wt % Mn, < 250 ppm (S + .04 Se), 30 to 130 ppm N, 0.05 to 0.35 wt % Cu, 15 to 300 ppm C, and 200 to 400 ppm Al, remaining being iron and minor impurities, and having a thickness of

between 40 and 70 mm, preferably of between 50 and 60 mm, with a casting speed of 3 to 5 m/min, a steel overheating at the casting lesser than 30 °C, preferably lesser than 20 "C, such a cooling speed as to obtain a complete solidification between 30 to 100 s, preferably between 30 and 60 s, a mould oscillation amplitude of between 1 and 10 mm, and an oscillation frequency of between 200 ans 400 cycles per minute;

(ii) equalizing the thus obtained slabs and hot rolling them, after which the strip cooling is delayed for at least 5 seconds after the strip leaves the last rolling stand;

(iii) direcly sending the strip to the cold rolling, avoiding the usual annealing step;

(iv) cold rolling in a single step or in a plurality of steps if necessary with intermediate annealing, with a reduction ratio in the last step of at least δO % , and maintaining a rolling temperature of at least 200 "C in at least two rolling passes during the last step; (v) continuously annealing the cold rolled strip for a total time of 100 to 350 s, at a temperature comprised between δ50 and 1050 °C in a wet nitrogen/hydrogen atmosphere, with a pH2θ/pH ₂ comprised between 0.3 and 0.7;

(vi) coating the strip with annealing separator, coiling it and box annealing the coils in an atmosphere having the following compositions during the heating-up: hydrogen mixed with at least 30 % vol nitrogen up to 900 "C, hydrogen mixed with at least 40$ vol nitrogen up to 1100-1200 °C, then maintaining the coils at this temperature in pure hydrogen. In the hot rolling, the slabs are treated with a rolling starting

temperature of 1000 to 1200 "C and a finishing temperature of 8 0 to

1050 °C.

The steel composition can be different from the conventional one, in that very low carbon contents can be contemplated, between 15 and 100 ppm.

There can be also a copper content of between 800 and 2000 ppm. During the continuous casting, the casting parametres are chosen to otain an equiaxic to columnar grains ratio of between 35 and 75 % . equiaxic grain dimensions lesser than 1.5 mm, mean second phases dimensions not higher than 0.06 micrometers.

Such an intermediate product is of paramount importance for a trouble- free development of the remaining of the process and for the final product quality. If during the decarburization annealing the temperature is maintained below 950 °C, the nitrogen content in the atmosphere of the subsequent box-annealing can be so controlled as to allow a nitrogen quantity lesser than 50 ppm to diffuse into the strip.

Such nitrogen absorption can also be obtained in the continuous furnace, after the decarburization annealing, maintaining the strip at a temperature comprised between 900 and 1050 °C, preferably over 1000 "C, in a nitriding atmosphere, e.g. containing NH up to 10 % volume. In this case water vapour must be present in a quantity comprised between 0.5 and 100 g/πH. The above steps of the process can be interpreted as follows. The steel treatments after the slab formation as well as the results obtainable with such treatments strongly depend on the way in which the steel solidifies, defining type and dimensions of steel grains as

well as distribution and dimensions of non-metallic precipitates. For instance, very slow cooling rates enhance the segregation of the elements more soluble in molten iron than in solified iron, establishing concentration gradients for such elements, and the formation of coarse and not well distributed non-metallic precipitates, adversely influencing the electrical steel sheet final properties .

The thin slab continuous casting conditions are selected to obtain a number of equiaxial grains higher than the one (usually around 25 %) obtainable in the traditional continuous casting (slab thickness around 200-250 mm) as well as crystals dimensions and fine precipitates distribution particularly apt to the obtention of a high- quality end product. In particular, the high aluminum content, the precipitates fine dimensions and the thin slab annealing at a temperature up to 1300 "C allow to obtain already in the hot-rolled strip aluminum nitride precipitates apt to somewhat control the grain dimensions .

In this same sense must be considered the possibility to utilize very low carbon contents , preferably lower than the ones necessary to form a gamma phase, to limit the dissolution of aluminum nitride, much less soluble in the alpha phase than in the gamma one.

The cited presence, since the slab formation, of relatively fine aluminum nitride precipitates allows to decriticize a number of subsequent thermal treatments, also permitting to rise the de- carburization temperature without risk of an uncontrolled grain growth; it is also possible to obtain, in a subsequent step, a high- temperature absorpion of nitrogen and a better nitrogen diffusion

throughout the strip a well as the formation, directly in this step, of further aluminum nitride.

This formation of a given amount of aluminum nitride allows to enhance the inhibition effect on the grain growth and, consequently, the quality of the final product, permitting to constantly reach the higher quality levels for this class of products.

BRIEF DESCRIPTION OF THE DRAWINGS

The process according to the present invention will now be described in a strictly exemplificatory an non-limiting way in the following enclosed Drawings, in which:

Fig. 1 is a diagram of the BδOO values obtained according to Example

2, without addition of ammonia;

Fig. 2 is a diagram of the BδOO values obtained according to Example

2, with a 3 % vol ammonia addition; Fig. 3 is a diagram of the BδOO values obtained according to Example

2, with a 10 vol ammonia addition.

The present invention will now be illustrated in a number of examples, which, however, are mere illustrations and do not limit the possibilities and range of application of the invention itself.

EXAMPLE 1

A number of steels were produced, whose composition are shown in Table 1:

TABLE 1

Type Si % C ppm Mn % Cu % S ppm Al _s ppm N ppm

A 3-15 20 0.10 0.17 δO 300 40

B 3.20 100 0.13 O.lδ 70 260 90

C 3-20 250 0.09 0.10 60 320 δO

D 3-15 120 0.10 0.15 70 2δ0 δO

Types A, B and C were continuously cast in thin slabs 50 mm thick, with a casting speed of 4.δ m/min, a solidification time of 60 s, an overheating temperature of 3 ^β C, in a mould oscillating at 260 cycles/min, with oscillation amplitude of 3 mm, obtaining an equiaxic to columnar grains ratio of 39% - The mean dimension of the equiaxic grains was of 1.05 mm. The mean dimension of precipitates (second phases) was of 0.04 micrometres.

Steel D was continuously cast at a thickess of 240 mm, obtaining an equiaxic to columnar grains ratio of 23 % . All the slabs were equalized at 1230 °C for 20 min and hot rolled, without prerolling, at a final thickness of 2.1 mm; some strips were cooled immediately after the las rolling stand, while for all the others the cooling started 7 s after the strip leaving the last rolling stand. No hot rolled strip was annealed. The strips were then cold rolled in a single stage at a final thickness of 0.29 mm, with five rolling passes, with a rolling temperature at the third and fourth passes of 210 °C.

The cold rolled strips were continuously annealed according to the following scheme: decarburization at 870 °C for 60 s in a wet atmosphere having a PH2O/PH2 of 0.50, and second annealing step at 900 "C for 10 s in a hydrogen-nitrogen (75'25) atmosphere with PH2O/PH2 of 0.03.

The strips were then coated with a conventional MgO based annealing separator, and box annealed according to the following scheme: quick heating up to 60 "C, stop at this temperature for 10 h, heating to 1200 °C at 30 °C/h in H ₂ -N ₂ (70:30) atmosphere, stop at this temperature for 20 h in hydrogen.

After the usual final treatments, the magnetic characteristics were measured and are shown in Table 2:

TABLE 2

Type Delayed cooling Immediate cooling according to the invention BδOO (mT) P17 (w/kg) BδOO (mT) P17 (w/kg)

A 1880 1.09 1870 1.16

B lδ50 1.23 1830 1.37

c 1890 1.03 1670 1.19

D 1520 2.35 1530 2.48

EXAMPLE 2

A steel whose composition is shown in Table 3 was continuously cast in thin slabs and transformed in cold rolled strip 0.29 mm thick, as per Example 1.

TABLE 3 Si % C ppm Mn % Cu % S ppm Al _g ppm N ppm 3.10 50 0.08 0.10 100 320 75

Three strips were continuously annealed according to different cycles: decarburization at TI °C in H2-N2 (75:25) atmosphere with a pH2θ/pH ₂ of 0.45; heating at T2 "C in H ₂ ~N ₂ (75:25) with X% NH ₃ and a pH ₂ 0/pH ₂ of 0.03. The thus obtained strips, utilizing three different X values, were box-annealed as per Example 1.

For each X value different values of TI and T2 were utilized; the strips were finished as per Example 1 and the obtained magnetic characteristics were measured; the results are shown in the diagrams of the enclosed drawings in which it can be seen that, introduction of ammonia in the terminal part of the continuous furnace makes it possible to considerably expand the TI and T2 temperature fields, and in the meantime to have a better product. The temperature control criticity is diminshed and the strip quality stability is improved.