Abstract:
Permanent domain refinement of grain oriented electrical steel strip is obtained in a high speed two-stage process. The process removes the glass in narrow regions which just expose the base metal. An electrolytic etch is then used to deepen the region into the base metal and minimize damage to the remaining glass film. Control of acid concentration and temperature in the electrolytic bath allows a greater increase in productivity. A further feature of the process is the use of permeability measurements to optimize the depth of the etched regions. The improved core loss produced by the process will survive a stress relief anneal.

Description:
This is a continuation of copending application(s) Ser. No. 07/173,696 filed on Mar. 25, 1988, now abandoned. 
    
    
     BACKGROUND OF THE INVENTION 
     The present invention relates to a high speed electroetching method to provide permanent domain refinement for electrical steels to yield improved magnetic properties. 
     The core loss properties of electrical steel may be improved by metallurgical means such as better orientation, thinner gauge, higher volume resistivity and smaller secondary grain sizes. Further improvements in core loss are obtainable by non-metallurgical means which reduce the wall spacing of the 180 degree magnetic domains. High-stress secondary coatings impart tension which decreases the width of the domain. The domain refinement of most interest has been the creation of a substruture which regulates the domain wall spacing. Various means to subdivide the domains have included: (1) narrow grooves or scratches by mechanical means such as shotpeening, cutters or knives (2) high energy irradiation such as a laser beam, radio frequency induction or electron beam and (3) chemical means to act as a grain growth inhibitor diffused or impregnated onto the steel surface such as a slurry or solution of sulfide or nitride compounds. All of these means are generally discussed in U.S. Pat. No. 3,990,923. Grooves or scratches have been applied to electrical steels resulting in internal stresses and plastic deformation which subdivides the large domains typically found in large grains into regions of smaller domain sizes. U.S. Pat. No. 3,647,575 uses a knife, metal brush or abrasive powder under pressure to form grooves less than 40×103 mm deep and spaced between 0.1 and 1 mm. The grooves may be transverse to the rolling direction and are applied subsequent to the final anneal. A stress relief anneal of about 700°C. is optional. The Mar. 1979, No. 2, Vol. MAG-15, pages 972-981, from IEEE TRANSACTIONS OF MAGNETICS discussed the effects of scratching on grain oriented electrical steel in an article entitled &#34;Effects of Scratching on Losses in 3-Percent Si-Fe Single Crystals with Orientation near (110) [001]&#34; by Tadao Nozawa et al. The optimum spacing between scratches was from 1.25 mm to less than 5 mm. The benefits of tensile stresses were noted. All of the samples were chemically and mechanically polished prior to scratching to obtain bare, uniformly thick and smooth surfaces for good domain observations using the scanning electron microscope. Scratching was conducted after the final anneal using a ball-point pen loaded with a 300 gram weight to produce a groove which was about 0.1 mm wide and 1 mm deep. 
     U.S. Pat. No. 4,123,337 improved the surface insulation of electrical steels having an insulative coating by electrochemical treatment to remove metallic particles which protrude above the insulative coating. 
     U.S. Pat. No. 3,644,185 eliminated large surface peaks by electropolishing while avoiding any significant change in average surface roughness. 
     The prior art has not optimized the groove depth for permanent domain refinement in a manner which avoids damage to the surface conditions. The prior art has been limited regarding line speed to produce the series of grooves for domain refinement. By using a process which combines grooving techniques with an electrolytic etch, the problems with depth control and surface damage may be overcome. The line speed for this combined process becomes commercially attractive. The present invention provides grooves or rows of pits of sufficient depth to penetrate the coating thickness and then electroetches the exposed base metal to a critical depth to obtain permanent domain refinement. 
     BRIEF SUMMARY OF THE INVENTION 
     This invention relates to a high speed, permanent domain refinement process for electrical steels having up to 6.5% silicon and the electrical steel having improved magnetic properties. 
     Permanent domain refinement is obtained by providing bands of treated areas which penetrate through the mill glass surface. These treated bands could be a continuous line or closely spaced spots. The electrical steel strip is then subjected to an electrolytic etch to deepen the groove or pits. After etching the treated bands, the electrical steel strip is recoated to provide a good surface for an insulative coating which imparts tension. 
     It is a principal object of the present invention to provide a process which produces permanent domain refinement with improved productivity/lower cost over prior art. 
     It is a further object of the present invention to provide an electrical steel with improved magnetic properties which may be given a stress relief anneal while maintaining excellent magnetic properties. 
     It is a still further object to provide a control process for electroetching which monitors the &#34;as-grooved&#34; permeability to optimize the core loss improvement through a feed back control loop. 
    
    
     BRIEF DESCRIPTION OF THE DRAWING 
     FIG. 1 shows a schematic illustration of a laser system to produce grooves on moving electrical strip, 
     FIG. 2 shows the effect of groove depth on magnetic improvement (deterioration) in percent for grain oriented electrical steel, 
     FIG. 3 shows the relationship between permeability and optimum core loss improvement by grooving high permeability grain oriented electrical steel. 
    
    
     DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT 
     Domain refinement which will survive a stress relief anneal has not been previously obtainable at normal commercial line speeds. The present invention provides 8-10% core loss improvements after stress relief annealing using a process which can operate at line speeds above 100 feet per minute (30 meters per minute) and typically around 300 feet per minute (90 meters per minute). The reason for this is that the invention produces the permanent domain refinement effect in a matter of seconds as opposed to minutes for other processes. 
     The steel may have up to 6.5% silicon and may use any of the known grain growth inhibitors. To obtain permanent domain refinement through the thickness of the strip, it is preferable that the gauge be less than 12 mils (30 mm). Heavier gauges will require a domain refinement treatment on each side. However, this is not a problem since the commercial ranges of interest are normally thinner than 12 mils (30 mm). 
     The first stage of the process is to initiate a series of parallel linear regions in the form of grooves or rows of pits to a depth which just penetrates the glass film and exposes the base metal. U.S. Pat. No. 4,468,551 describes an apparatus for developing spots on electrical steel using a laser, rotating mirror and lenses to focus the shape and energy density of the laser beam. The patent, however, was controlling the laser parameters to avoid coating damage. Laser beams may also be focused into lines by using a lens to expand the laser, a lens to collimate the laser beam, and a lens to focus the laser beam. FIG. 1 shows a laser system which can remove the glass film to expose the base metal. 
     In FIG. 1, a laser 10 emits a beam 10a which passes through a beam expander 11 and cylindrical lens 12. Laser beam 10a impinges a rotating scanner or mirror 13 which is reflected through a cylindrical lens 14 and lens assembly 15. Beam 10a contacts strip 16 as a line 17. Line 17 is continuously reproduced at spaced intervals of about 5-20 mm. The energy density of laser beam 10a is sufficient to penetrate through the glass coating on strip 16 and expose the electrical steel. Depending on the width of the strip 16, several of these units could be used in combination to produce the grooves in line 17. 
     Other means to produce the initial groove could also be used, such as discs as taught in EP No. 228,157, or cutters as taught in U.S. Pat. No. 3,647,575, or any of the means in U.S. Pat. No. 3,990,923. 
     It is important to the magnetic properties of the electrical steel that the grooves or rows of pits which initially penetrate the glass film be very shallow. Deep penetration into the base metal will provide permanent domain refinement but will also produce ridges around the penetration and cause metal splatter on the surface of the glass. Both of these have an adverse effect on the glass film properties. Ideally the initial groove or pits should just remove the glass and expose the base metal slightly. While the depth of the affected region should be shallow, the groove width or pit diameter should be about 0.05 to 0.3 mm. 
     The second stage for optimizing the depth of penetration uses an electroetching treatment to increase the depth to about 0.0005-0.003 inches (0.012-0.075 mm). Localized thinning by electroetching improves the domain refinement and does not harm the glass film. The improved magnetic quality does remain after a stress relief anneal which is typically at about 1500°-1600° F. (815°-870° C.) for a period of 1-2 hours. The electrolytic bath must be selected to not attack the glass film while deepening the groove or pits in the base metal. Nitric acid solutions (5-15%) with water or methanol were the most effective of the solutions evaluated. A 5% nitric solution in water at 160 F. (70 C.) with a current of 25 mamps/cm 2  for 10 seconds attacked the base metal very aggressively without harming the resistivity of the glass. For uniform control, the temperature and acid concentration must be maintained relatively constant. 
     FIG. 2 shows the effect of groove depth on the improvement or deterioration of the magnetic quality of high permeability grain oriented steel. 
     The process of scribing and electroetching does have some scatter in the % improvements to magnetic quality. To reduce the scatter and provide a good improvement in core loss, the process may be controlled by monitoring the permeability. A review of FIG. 3 shows the optimum range to be 1870-1890 H-10 permeability (after grooving) to provide minimum scatter in core loss improvement. Before grooving, permeabilities ranged from 1910 to 1940. 
     During electroetching, a feedback control system is provided which monitors the permeability of the as-grooved steel. Regardless of the starting permeability, the most uniform core loss improvement will occur as the permeability drops into the range of 1870-1890. The control system continues the electroetching until the material falls within this range. This process is more accurately controlled than using such means as the amount of material removed or depth of groove. This control range is applicable only for high permeability grain oriented electrical steel. To maintain line speed during electroetching, the current may be adjusted using the permeability data to control the permanent domain refinement process. 
     After electroetching, the strip is rinsed and dried. A corrosion inhibitor coating may be applied by roller coating. Potassium silicate mixed in water (about 50 ml/l) could be used. The coating would be cured at 600° F. (315° C.) and cooled. 
     The width of the scribed line (or spot diameter), time of immersion, current, temperature of the bath, concentration of the acid, initial depth and final depth are all controlled in the process to optimize the permanent domain refinement. 
     The following experiments were conducted to evaluate the process and optimize the conditions for a high permeability grain oriented silicon steel. Slight modifications may further improve the magnetic properties for different chemistries, gauges, glass film and previous processing differences. 
     The magnetic characteristics and features of the present invention will be better understood from the following embodiments. 
     Steel having the following nominal composition (in weight %) was used for these studies: 
     
         ______________________________________% C    % Mn       % S    % Si    % Al  % N______________________________________0.055  0.085      0.025  3.00    0.031 0.007______________________________________ 
    
     After conventional processing to obtain cold rolled strip which has been decarburized, given a final high temperature anneal and provided with a glass film and secondary coating, the strip was subjected to the following tests. 
     A YAG laser was used to locally remove the glass in parallel regions perpendicular to the rolling direction. The regions were spaced about 6 mm apart. The data in Table 1 compares the magnetic quality of sample blanks with regions of either continuous lines of 0.25 mm in width, or large spots (ellipsoidal in shape) with dimensions 0.4 mm×0.25 mm and 1.2 mm apart, or small spots (also ellipsoid in shape) with dimensions 0.25 mm×0.2 mm and 1.2 mm apart. 
     The major axis of the ellipsoid spots was perpendicular to the rolling direction. The sample blanks were 0.23 mm thick, 75 mm wide and 300 mm long. 
     The data in Table 1 is coded by (a) line, (b) large spot (0.4 mm×0.25 mm) and (c) small spot (0.25 mm×0.2 mm). Grooving was done in 5% HNO 3  in water at room temperature for about 1 to 2 minutes at 5 amps. 
     
                                           TABLE 1__________________________________________________________________________               Initial Electroetch         Calculated               Core    Core     Weight         Groove               Loss    Loss     Loss         Depth B17 Perm                       B17 Perm                               % Imp.Sample    Scribe     (gm)         (mm)  (w/lb)                   H-10                       (w/lb)                           H-10                               (Det.)__________________________________________________________________________1   line  0.2270         0.026 0.559                   1922                       0.504                           1861                               9.82   line  0.2409         0.028 0.600                   1908                       0.538                           1835                               10.33   line  0.2045         0.024 0.582                   1919                       0.497                           1866                               14.64   large spot     0.0903         0.027 0.553                   1917                       0.513                           1908                               7.25   large spot     0.0724         0.022 0.584                   1905                       0.552                           1901                               5.56   large spot     0.0988         0.030 0.582                   1919                       0.527                           1908                               9.57   large spot     0.1440         0.044 0.594                   1919                       0.518                           1896                               12.88   large spot     0.1883         0.057 0.597                   1919                       0.508                           1883                               14.99   small spot     0.0570         0.032 0.591                   1919                       0.546                           1918                               7.610  small spot     0.0835         0.047 0.557                   1931                       0.496                           1923                               11.0__________________________________________________________________________ 
    
     The influence of time during electroetching was evaluated on samples of the same chemistry which were mechanically scribed or laser scribed on sample blanks 0.23 mm thick, 75 mm wide and 300 mm long. The scribed lines were spaced apart at 6 mm intervals and were perpendicular to the rolling direction. 
     Results are shown in Table 2. 
     
                       TABLE 2______________________________________   Current      Time    Groove DepthSample  (amps)       (min.)  (mm)______________________________________11*     4.5          0.5     0.01312      4.5          1.0     0.02313*     4.5          1.0     0.02514      4.5          2.0     0.02815*     4.5          2.0     0.03816      4.5          3.5     0.03817      4.5          5.0     0.13518*     --           --      0.002______________________________________ *Scribed with a laser. 
    
     Table 3 shows the improvement in core loss with the samples in Table 2 after electroetching. Magnetic properties were measured before scribing and after electroetching followed by a stress relief anneal (SRA) at 1525° F. (830° C.). 
     
                                           TABLE 3__________________________________________________________________________           Core LossInitial         After SRA                   Perm  % Improve-Core Loss   Initial           1525° F.                   After SRA                         ment    B15 B17 Perm.           B15 B17 1525° F.                         B15 B17Sample    (w/lb)   (w/lb)       H-10           (w/lb)               (w/lb)                   H-10  (w/lb)                             (w/lb)__________________________________________________________________________11  0.403   0.547       1928           0.397               0.535                   1924  1.4 2.212  0.398   0.536       1919           0.379               0.507                   1902  4.8 5.413  0.407   0.562       1927           0.390               0.531                   1923  4.2 5.514  0.382   0.532       1906           0.379               0.519                   1863  0.8 2.415  0.400   0.551       1930           0.382               0.511                   1902  4.5 7.216  0.392   0.531       1922           0.374               0.500                   1878  4.6 5.817  0.384   0.538       1904           0.422               0.559                   1611  *9.9                             *3.918  0.384   0.537       1926           0.384               0.530                   1921  --  --__________________________________________________________________________ percent deterioration. 
    
     To determine if this process was adaptable to commercial line speeds, a series of tests were conducted with higher acid concentrations (15% HNO 3 ) and higher bath temperatures. All of the bath temperatures were 170° F. (77° C.) except sample 19 which was 175° F. (80° C.). A 5 amp current was used in all cases and the samples were the same size and of the same chemistry as the previous study. Magnetic quality was tested before scribing and after electroetching and stress relief annealing at 1525° F. (830°C.). 
     
                                           TABLE 4__________________________________________________________________________                    Quality            Initial Quality                    After SRA      Calculated            Core    Core    Etch  Weight      Groove            Loss    Loss    % Improve-    Time  Loss      Depth B17 Perm.                    B17 Perm.                            mentSample    (sec)  (gm)      (mm)  (w/lb)                H-10                    (w/lb)                        H-10                            (Det.)__________________________________________________________________________19  5  0.1657      0.019 0.569                1921                    0.500                        1893                            12.120  4  0.1740      0.020 0.611                1912                    0.528                        1883                            13.621  3  0.1653      0.019 0.536                1932                    0.474                        1902                            11.622  3  0.1582      0.018 0.613                1923                    0.512                        1898                            16.523  2  0.1266      0.015 0.577                1915                    0.503                        1901                            12.824  2  0.2938      0.034 0.581                1906                    0.526                        1833                             9.5__________________________________________________________________________ 
    
     A further study was conducted to optimize the quality improvements to core loss after a stress relief anneal. Mechanical scribing was used to evaluate various depths of grooves through the glass film on the surface of the high permeability grain oriented electrical steel. The scribed lines were spaced 6 mm apart and applied perpendicular to the rolling direction. The electrolytic bath was 5% HNO 3  in water at room temperature. As noted previously, higher bath temperatures and higher acid concentrations would allow commercial line speeds but this study was only designed to optimize the depth of the grooves. The samples were the same size, thickness and chemistry as previously stated. 
     
                                           TABLE 5__________________________________________________________________________                  Electroetch          Initial Qlty.                  &amp; SRA          Core    Core    Etched     Groove          Loss    Loss    % Improve-    Wgt. Loss     Depth          B17 Perm.                  B17 Perm.                          mentSample    (gm)  (mm) (w/lb)              H-10                  (w/lb)                      H-10                          (Det.)__________________________________________________________________________25  0.0891     0.030          0.515              1928                  0.495                      1894                          3.926  0.0991     0.033          0.518              1929                  0.489                      1885                          5.627  0.1328     0.043          0.523              1930                  0.501                      1862                          4.228  0.1852     0.074          0.520              1931                  0.519                      1811                          0.229  0.3245     0.107          0.516              1926                  0.533                      1749                          (3.3)30  0.3570     0.117          0.526              1929                  0.515                      1648                          2.0__________________________________________________________________________ 
    
     Various electrolyte etchants and conditions were evaluated in Table 6 for their effect on the glass film quality of the samples. Scribe lines were made mechanically and aligned perpendicular to the rolling direction at 6 mm intervals. 
     
                       TABLE 6______________________________________Electrolyte Etchants3 cm × 7.6 cm Coupons                Tem-                per-   Cur-                ature  rent  Time  GlassBath Composition     (F.)   (amps)                             (sec.)                                   Film______________________________________1    5% HNO.sub.3 in Methanol                RT     2     300   Pitted2    5% HNO.sub.3 + 10% HC1                150    *     300   Generalin H.sub.2 O                       Attack3    5% HNO.sub.3 in H.sub.2 O                RT     2     300   Pitted4    5% HNO.sub.3 + 10% HC1                150    2     300   Pittedin H.sub.2 O5    5% HNO.sub.3 in H.sub.2 O                150    2     300   Okay6    5% HNO.sub.3 + 5% HC1                RT     2     300   Slightin Methanol                        Attack7    5% HNO.sub.3 in H.sub.2 O                160    2      10   Okay8    5% HNO.sub.3 in H.sub.2 O                160    4      10   Okay9    5% H.sub.2 SO.sub.4 in H.sub.2 O                160    2     120   General                                   Attack______________________________________ *Hot pickle bath, no electrolysis. 
    
     Basically, the damage to the glass film is minimized by keeping times for etching under 10 seconds and using higher currents or bath temperatures to minimize the times. Generally, the preferred composition would be a nitric acid of 5% to 15% concentration in water at 160° F. (70° C.). 
     The present 2-stage process for permanent domain refinement thus provides improved core loss which remains after a stress relief anneal. The process provides an improved glass surface over the other domain refinement processes which rely on grooves, scratches or rows of spots. The process also provides a unique means of controlling the etching process by monitoring the permeability level. The resultant electrical steel has improved magnetic properties which will survive a stress relief anneal as a result of the 2-stage process which provides a better glass surface. 
     Modifications may be made in the invention without departing from the spirit of it.