Electrical sheet
The present invention relates to be used for the high-silicon electrical steel sheet of transformer and electric motor core.
Electrical sheet is widely used as the core of electric motor and transformer.Electrical sheet contains the control tissue usually and improves the silicon of resistivity.The iron alloy that contains 6.5wt.% silicon demonstrates soft magnetic property preferably owing to its magnetostriction approaches zero basically.Yet, increase silicone content steel disc is become fragile, and the stalloy that contains 4wt.% or more silicon can not be made stalloy with common rolling.In order to address this problem, some methods of producing high silicon stalloy have been proposed.Wherein one of method is the fast setting direct production method of directly producing high silicon stalloy with molten steel by casting, and for example, discloses this method in the patent announcement communique No.60-32705 that Japan has examined.Another kind method is to use the special rolled method, for example, this method is disclosed in the patent announcement communique No.3-80846 that Japan has examined, the third method is to make silicon be enriched in siliconising method through the rolling low-silicon steel sheet of producing, for example, in the patent announcement communique No.2-60041 that Japan has examined this method is disclosed.In these three kinds of methods, the siliconising method enters commercial stage.
The stalloy of producing with above-mentioned either party's method is being applied to must to carry out punching press, shearing and bending machining before electric motor and the transformer.Yet stalloy exists in punching press or shears corner and causes crackle and cracked fragility problem, certainly will produce fracture in bending machining.
The various suggestions of stalloy processing characteristics have been proposed to be intended to improve.
The patent announcement communique No.61-15136 that Japan has examined discloses the method that a kind of manufacturing has the stalloy of good workability and magnetic properties, this method is grain size to be controlled at the 1-100 mu m range and to control crystal grain have the column crystallization of growing perpendicular to slice surfaces, eliminates ordered lattice simultaneously basically.
The uncensored patent disclosure communique No.62-270723 of Japan discloses the method that a kind of manufacturing has the stalloy of quite high workability, and this method is that the steel that will have rolling structure is processed into finished section bar and anneals subsequently.
The uncensored patent disclosure communique No.4-165050 of Japan discloses a kind of method of steel disc of high silicon crystal grain-orientation of making highly processable, and this method is to add Mn to suppress bad influence of solid solution sulphur and raising grain orientation.
However, increase to 100 μ m or when bigger, the method for the patent announcement communique No.61-15136 that Japan has examined does not reach its target effect yet when crystal grain diameter.For high silicon steel, this method need be used the quenching step, and for example water-the quenching under 900 ℃ or higher high temperature is to eliminate orderly crystalline phase basically.Therefore, this method is faced with difficulty in actual applications.
The method of the patent announcement communique No.62-270723 that Japan has examined will be processed the steel with rolling structure, so that this method need be carried out high temperature annealing after processing.Thereby the shortcoming of this method is to add extra step in transformer and electric motor manufacturing processed.
The method of the uncensored patent disclosure communique No.4-1605050 of Japan need be used high grain-oriented steel.Owing to use the poor stability of the secondary recrystallization of inhibitor, be difficult to reach high grain orientation.In addition, also there is the shortcoming that can not be used for non-oriented electrical steel in this method.
The purpose of this invention is to provide a kind of electrical sheet with high workability.
For achieving the above object, the invention provides the electrical sheet of a kind of 4-10wt.%Si of containing, it comprises:
Described electrical sheet comprises crystalline particle and grain boundary, and described grain boundary has the 30at(atom) % or lower oxygen level.
This electrical sheet also preferably is made up of following principal element:
0.01wt.% or lower C, 4-10wt.%Si, 0.5wt.% or lower Mn, 0.01wt.% or lower P, 0.01wt.% or lower S, 0.2wt.% or lower soluble (Sol.) Al, 0.01wt.% or lower N, 0.02wt.% or lower O, all the other are Fe and unavoidable impurities.
The present invention also provides a kind of 4-10wt.%(si+Al of containing) electrical sheet, it comprises:
Described electrical sheet comprises crystalline particle and grain boundary, and described grain boundary has 30at% or lower oxygen level.
This electrical sheet also preferably is made up of following principal element:
0.01wt.% or lower C, 4-10wt.%(Si+Al), 0.5wt.% or lower Mn, 0.01wt.% or lower P, 0.01wt.% or lower S, 0.01wt.% or lower N, 0.02wt.% or lower O, all the other are Fe and unavoidable impurities.
The present invention also provides the electrical sheet of a kind of 4-10wt.%Si of containing, and it comprises:
Described electrical sheet comprises crystalline particle and grain boundary, and described grain boundary has 30at.% or lower oxygen level and 0.2at.% or lower sulphur content.
This electrical sheet also preferably is made up of following principal element:
0.01wt.% or lower C, 4-10wt.%Si, 0.5wt.% or lower Mn, 0.01wt.% or lower P, 0.01wt.% or lower S, 0.2wt.% or lower soluble Al, 0.01wt.% or lower N, 0.02wt.% or lower O, all the other are Fe and unavoidable impurities.
The present invention also provides a kind of 4-10wt.%(Si+Al of containing) electrical sheet, it comprises:
Described electrical sheet comprises crystalline particle and grain boundary, and described grain boundary has 30at.% or lower oxygen level and 0.2at.% or lower sulphur content.
This electrical sheet also preferably is made up of following principal element:
0.01wt.% or lower C, 4-10wt.%(Si+Al), 0.5wt.% or lower Mn, 0.01wt.% or lower P, 0.01wt.% or lower S, 0.01wt.% or lower N, 0.02wt.% or lower O, all the other are Fe and unavoidable impurities.
Fig. 1 is the curve that concerns between the vacuum tightness of expression steel disc of the present invention final heat-treating atmosphere and the three-point bending characteristic;
Fig. 2 is the curve that concerns between oxygen level in the expression steel disc of the present invention grain boundary and the elongation;
Fig. 3 is the curve that concerns between expression steel disc of the present invention grain boundary intensive parameter and the three-point bending characteristic;
Fig. 4 is the curve that concerns between expression steel disc average crystal grain diameter of the present invention and the three-point bending characteristic;
Fig. 5 is the explanation of estimating the three point bending test method of steel disc workability;
Fig. 6 is the curve that concerns between oxygen level and the three-point bending characteristic in the expression embodiment 1 steel disc grain boundary;
Fig. 7 is the curve that concerns between oxygen level and the three-point bending characteristic in the expression embodiment 2 steel disc grain boundaries;
Fig. 8 is the curve that concerns between the fault number that produces on oxygen level and the shearing section in the expression embodiment 3 steel disc grain boundaries;
Fig. 9 is the curve that concerns between oxygen level and the elongation in the expression embodiment 4 steel disc grain boundaries;
Figure 10 is the curve that concerns between oxygen level and the three-point bending characteristic in the expression embodiment 6 steel disc grain boundaries;
Figure 11 is the curve that concerns between sulphur content and the three-point bending characteristic in the expression steel disc of the present invention grain boundary;
Figure 12 is the curve that concerns between sulphur content and the elongation in the expression steel disc of the present invention grain boundary;
Figure 13 is the curve that concerns between sulphur content, oxygen level and the elongation in the expression steel disc of the present invention grain boundary;
Figure 14 is the curve that concerns between expression steel disc average crystal grain diameter of the present invention and the three-point bending characteristic;
Figure 15 is the curve between sulphur content and the three-point bending characteristic in the expression embodiment 7 steel disc grain boundaries;
Figure 16 is the curve that concerns between sulphur content and the three-point bending characteristic in the expression embodiment 9 steel disc grain boundaries.
Because natural the enbrittling of parent phase of stalloy, this steel disc is considered to can't improve its processibility basically always.Simultaneously, the present inventor has carried out a series of tests, be intended to improve in final heat-treating atmosphere the workability of stalloy under the different dew points and oxygen concn, find wherein to have a kind of steel disc, and this steel disc contain the silicon of same percentage with higher workability.Fig. 1 illustrates the test-results of steel disc workability.Change in test vacuum tightness to change the dew point and the oxygen concn of annealing atmosphere.Horizontal axis is represented vacuum tightness, and vertical axis represent in the three point bending test (shown in Figure 5 depress measure the test specimen fracture under the condition before the test of maximum stroke amount) as the test specimen amount of bow of workability index.1200 ℃ of annealing 15 minutes.Test-results shows that vacuum tightness is high more, and the improvement of workability is big more.
Most preferred embodiment scheme-1
Those test samples are studied to understand fully the mechanism of fracture of stalloy, between processing characteristics and surface of fracture state, demonstrated relation closely.Specifically, the stalloy that workability is inferior demonstrates a large amount of transgranular fracture faces, and the stalloy of highly processable demonstrates a large amount of cleavage fracture faces.When utilizing Auger spectroscopy sample high and the low sample of workability to study with the oxygen level on the mensuration transgranular fracture face to workability, the oxygen level that the sample that workability is high provides in the grain boundary is low, and the low sample of workability provides the oxygen level height in the grain boundary.
Further studies show that out of gained Auger spectroscopy not only all exists certain relation between oxygen level in the grain boundary and the workability but also between carbon content in the grain boundary and the workability.Because above-mentioned test does not offer some clarification on the condition of control carbon amount, the variation of carbon amount is considered to the associating phenomenon with oxygen behavior in the crystal grain border in the grain boundary.Yet, be not familiar with its detailed mechanism as yet.In addition, have been found that changing annealing temperature is easy to control particle diameter and changes workability widely.
Therefore, present inventors find, are considered to the very poor stalloy of natural workability, and in fact its workability exists extremely strong mutual relationship between the characteristic with the crystal grain border, and find the stalloy that the characteristic by the control grain boundary just can obtain having fabulous workability.
Now, narrate the present invention in more detail by preferred elemental range.
Carbon is a kind of element that is harmful to soft magnetic property, and when C content surpassed 0.01wt.%, soft magnetism reduced in time, and this phenomenon is called " timeliness worsens (age degrading) ".For fear of this shortcoming, C content is preferably 0.01wt.% or lower.
Can to make magnetostriction be zero to silicone content and demonstrate soft magnetic property preferably near 6.5wt.%.When Si content was lower than 4wt.%, siliconized plate did not have the magnetic property of hope, and specific question does not appear in the workability of steel disc.When Si content surpassed 10wt.%, saturation magnetic flux density obviously descended.Therefore, Si content is defined in the 4-10wt.% scope.
Part Si can be replaced by Al.In the case, the total amount of essential regulation (Si+Al).When the total amount of (Si+Al) is lower than 4wt..%, can not obtain the magnetic properties of requirement of the present invention.And the workability of steel disc specific question can not occur.When Si content surpassed 10wt.%, saturation magnetic flux density obviously descended.Therefore, when part Si replaced with Al, (Si+Al) total amount preferably was defined in the 4-10wt.% scope.
Manganese can improve the hot workability in slab stage with S in conjunction with generating MnS, yet when Mn content surpassed 0.5wt.%, the decline of saturation magnetic flux density was obvious, and this is undesirable.So Mn content is preferably 0.5wt.% or lower.
Phosphorus is a kind of element that reduces soft magnetic property, preferably reduces its content as much as possible.Because 0.01wt.% or lower P content do not produce bad influence basically, be defined as 0.01wt.% or lower from considering best P content economically.
Sulphur is a kind of element that increases hot rolling fragility and reduce soft magnetism.Therefore, preferably reduce its content as much as possible.Because 0.01wt.% or lower S content do not produce bad influence basically, are 0.01wt.% or lower from considering best S content economically.
Aluminium can purify steel by desoxydatoin, and from the magnetic property aspect, it has the function that increases resistance.Steel contains the Si of 4-10wt.%, just can improve magnetic property by Si, realizes desoxydatoin so only require Al.Therefore, soluble Al content preferably is defined as 0.2wt.% or lower.On the other hand, when a part of Si was replaced by Al, as mentioned above, (Si+Al) total amount was defined in the 4-10wt.% scope.
Nitrogen is a kind of element that reduces soft magnetic property and cause magnetic aging to change.So preferably reduce its content as much as possible.Because 0.01wt.% or lower N content do not produce bad influence basically, are 0.01wt.% or lower from considering best N content economically.
Oxygen is a kind of element that reduces soft magnetic property, preferably reduces its content as much as possible.Narrate as the back, the most important factor of the present invention is the oxygen level in the grain boundary, and O content is meant inner the two the total O amount of grain boundary and crystal grain.The O content in the inevitable grain boundary that exists provides good workability in the steel disc by being controlled in the present invention, will narrate this situation afterwards.When the O content in the steel disc surpassed 0.02wt.%, oxygen all had been present in grain boundary and crystal grain inside under the heat-treat condition, and this state is difficult to the oxygen level in the grain boundary is reduced to 30at.% or lower.In other words, only be that 0.02wt.% or lower O content just have the zone (in intragranular or grain boundary) of selectively controlling the oxygen existence.Therefore, O content is defined as 0.02wt..% or lower.On the other hand, the lower limit of not special stipulation O content.Simple minimizing O content can not cause the reduction of O concentration in the grain boundary.Yet, excessively reduce O and can increase production cost.Therefore, consider, O content had better not be reduced to below the 0.0005wt.% from economic cause.
Except above-mentioned each element, the impurity of steel also comprises Cr, Ni, Cu, Sn and Mo.The content of above-mentioned every kind of element is about 0.03wt.% does not influence effect of the present invention.
O content (the O content in the element of the grain boundary of emanating) is the 30at.%(atomic percent in the grain boundary of requirement steel of the present invention) or lower.This is the most important condition of the present invention.The O content at grain boundary place means the O content (at.%) in each element of the grain boundary of emanating.Usually, use Auger spectroscopy to measure oxygen level.According to spectroscopy, test specimen is keeping 1 * 10
-9Holder or lower vacuum chamber implosion are used the auger electron spectroscopy assay method and are observed the transgranular fracture face that is not polluted by atmospheric air simultaneously.This method allows in the clean enterprising row element analysis of transgranular fracture face.
Be to use the auger electron spectroscopy assay method to measure the general method of element (with reference to " Practical Auger Electron Spectroscopy for Users " Kgoritsu Shup-pan, 1989.) later on.When material surface is carried out element determination, with survey Auger electron intensity (it be obtain by energy is differentiated and represent by peak height) and associated sensitivity (index of each element Auger electron emission efficiency) the following formula of substitution:
[X](at.%)={(X/x)/[(A/a)+(B/b)+(C/c)+……+(X/x)+……]}×100
A in the formula, B, C and D ... the Auger electron intensity of each element
A, b, c, and d ... the associated sensitivity of each element
Energy position for each element specifying measurement Auger electron intensity.For example, Fe uses the peak value of the high energy side in three LMM conversions, and O uses the KLL conversion, and C changes with KLL, and S changes with LVV.The associated sensitivity of each element conversion is known, has narrated these numerical value in above-mentioned document.According to Phai unit, the numerical value of Fe is 0.220, and the numerical value of C is 0.140, and the numerical value of O is 0.400, and the numerical value of S is 0.750.In this manner, Auger electron spectrum has been widely used in measuring the element quantitative value.So the present invention also adopts this method to measure the element at place, grain boundary.As mentioned above, present inventors make in this way each material with good workability and inferior workability are measured its grain boundary, carry out the ultimate analysis at place, grain boundary, and have utmost point confidential relation between the easy degree of O content of finding to locate the grain boundary with processibility.
As an example, Fig. 2 shows the relation between the O content in the grain boundary of using elongation with the thick stalloy as 0.1mm of chemical ingredients as shown in table 1 and sheet and measuring with the auger electron spectroscopy instrument.According to Fig. 2, include the few steel disc of O amount in the grain boundary and demonstrate elongation preferably.In each steel disc of having tested, demonstrate 3% or the steel disc of bigger elongation be viscous deformation.In addition, surface of fracture is carried out electron microscope scanning observe and to demonstrate, the steel disc with good elongation provides cleavage fracture rather than transgranular fracture, and the steel disc with inferior elongation shows and tends to transgranular fracture.In the past, can not cause the stalloy of viscous deformation be acceptable to this class.Yet, found when the O content in the grain boundary be 30at.% or when low, viscous deformation can take place.Therefore, regulation O content of the present invention is 30at.% or lower.From Fig. 2 as seen, 15at.% or lower O content provide better workability in the grain boundary.
Table 1 (wt.%)
C |
Si |
Mn |
P |
S |
Sol.Al |
N |
O |
0.0023 |
6.65 |
0.15 |
0.0023 |
0.0012 |
0.001 |
0.0032 |
0.0089 |
The effect of O content, this narrated above in the grain boundary, had been found that the carbon in the grain boundary plays an important role to workability undoubtedly.Specifically, even the O content in the grain boundary in 30at.% or lower scope, when the C content in the grain boundary (the C content in each element of the grain boundary of emanating) is 0.5at.% or more for a long time, can further improve elongation and improve workability.Think that the carbon in the grain boundary has inhibit feature to grain-boundary crack, although be not familiar with its detailed mechanism as yet.
So,, find that the oxygen in the restriction grain boundary must be included the effect of carbon in the grain boundary for obtaining the good workability of stalloy.In order to confirm this effect, present inventors have formulated the grain boundary intensive parameter, and this parameter is present in the oxygen at place, grain boundary and the formulate of carbon by following, and are equivalent to the formula of actual results of three.
Grain boundary intensive parameter=(C(284)/(O(531))
Term C(284 in the formula) and O(531) expression is differentiated to Auger spectroscopy and the strength of signal measured, and the numeral in the parenthesis represents to occur the energy at C and O peak value place respectively.
Fig. 3 shows the relation between grain boundary intensity and the three-point bending characteristic.
According to this figure, between the workability shown in the three-point bending characteristic is with above-mentioned grain boundary intensive parameter, exist the utmost point and concern closely.At this moment, when the amount of bow of three point bending test is 5mm or when bigger, compares with the prior art material and to think and improved workability, thus (C/Fe)/(O/Fe) ratio (grain boundary intensive parameter) be 0.5 or bigger just can think improved workability.When the amount of bow of three point bending test is 10mm or when bigger, infer that workability is obviously improved.Therefore, the grain boundary intensive parameter preferably is defined as 1.0mm or bigger.
About the C content in the grain boundary, when the O content in the grain boundary surpasses 30at.%, can not demonstrate the effect of improving workability, when the O content in the grain boundary when 30at.% is following, if the C content in the grain boundary is 0.5at.% or higher, then can improves grain boundary intensity and improve workability.Therefore, the C content in the grain boundary preferably is defined as 0.5at.% or higher.In order further to improve workability, the C content in the grain boundary preferably is defined as 0.8at.% or higher.
This effect of oxygen and carbon, found that also particle diameter also influences workability in finding the grain boundary, from the steel disc surface, 2.0mm or littler median size can further be improved workability.The reason of this effect is considered to, when restriction in the grain boundary O content and C content when strengthening the grain boundary, the intensity of crystal grain inside descends relatively pro rata and the crackle that crosses crystal grain increases, so excessive particle diameter can reduce workability.Has each stalloy (thickness: 0.1mm) of chemical ingredients shown in the table 1, O content in the grain boundary is about the stalloy that C content in 5at.% and the grain boundary is about 1at.% tests, with the median size determining to see from the steel disc surface under the different-grain diameter and the relation between the three-point bending characteristic.Figure 4 illustrates this test-results.According to this figure, can find out owing to median size being defined as 2.0mm or the littler workability of having improved.
Stalloy used in above-mentioned each test certainly will penetrate the place formation ring tissue of the thick direction of sheet at crystalline particle owing to thermal treatment has coarse grained fabulous crystalline particle growth conditions of formation.However, as previously mentioned, from the workability aspect, the particle diameter of steel disc is preferably 2.0mm or littler, and this steel disc need be selected controlled thermal treatment condition so that can not produce too much coarse grain.When the crystal structure formation ring of this stalloy was organized, present inventors found that the growth of crystalline particle stops at the about 3-4 of particle diameter basically doubly to the place of steel plate thickness.Therefore, remain on 2.0mm or littler, should select the thick 0.5mm or thinner of being of sheet for making particle diameter.In the case, nothing notes heat-treat condition.For these reasons, the preferred thickness of steel disc is 0.5mm or thinner.
Obtaining in effect of the present invention and the siliconized plate grain orientation distributes irrelevant.Therefore, the present invention neither is defined as the oriented silicon steel sheet and also is not defined as non-oriented silicon steel sheet.Common electrical sheet will apply insulation film, and the existence of filming is not depended in the present invention.
The present invention does not stipulate to make the method for thin slice, and the present invention can be used for the stalloy by special rolled method, siliconising method (having been previously described) and the manufacturing of other appropriate means.
Embodiment 1
Steel with composition shown in the table 1 is carried out melting, hot rolling and warm-rolling, to produce steel disc with 0.1mm thickness.This steel disc holds in the palm-1 * 10 in 1,200 ℃ 5
-5Carry out 15 minutes thermal treatment (final annealing) in the reduced pressure scopes at different levels of holder.Breadboard envrionment temperature is 27 ℃, and humidity is 80%.With three-point bending machine shown in Figure 5 the gained test specimen is tested, compressed into stroke amount to measure the preceding maximum of fracture.The nubbin of each test specimen placed in the auger electron spectroscopy instrument make it 8 * 10
-10Break in the vacuum of holder.Observe the surface of fracture of each test specimen and analyze the composition that the grain boundary is located.Composition analysis illustrates the C content of whole test specimens in the grain boundary all at 0.5at.% or lower.Fig. 6 shows O content in the grain boundary to the influence of three point bending test amount of bow.This graphic representation illustrates, and O content reduces in the grain boundary increases amount of bow significantly.So just can think that lower O content provides workability preferably in the grain boundary.
Embodiment 2
Use has the steel of identical component among the embodiment 1, heat-treats under some different atmosphere conditions.Those test specimens that make are carried out three point bending test.Produce the sample that is used for Auger spectroscopy by the test specimen of three point bending test remnants.These samples that break under the vacuum condition of auger electron spectroscopy instrument are to measure the composition of O and C in the grain boundary.O content in the crystal grain boundary and the relation between C content and the three-point bending characteristic are studied.For the test specimen of O content more than 30at.% in the grain boundary, there is not any relation between the O content in the grain boundary and C content and the amount of bow.Yet, be 30at.% or lower test specimen for O content in the grain boundary, exist tangible relation between the O content in the grain boundary and C content and the amount of bow.Fig. 7 shows the (median size: the 0.19mm) relation between C content and the three-point bending characteristic in the grain boundary that is about the 10at.% test specimen for the O content in the grain boundary.According to this graphic representation, can find out that the steel that C content reaches to a certain degree in the grain boundary has improved workability significantly.
Embodiment 3:
The use gap is that the shearing test platform of 3 μ m carries out shearing test to the test specimen of being tested among embodiment 1 and the embodiment 2.Opticmicroscope (* 200) observe down shear surface to every 10cm sheared length on the various faults of crackle and so on count.In with the relevant Fig. 8 of the O content in the crystal grain border, this count results has been shown.This graphic representation illustrates the tendency same with results of three, and has clearly illustrated that the effect of O content in the restriction grain boundary.
Embodiment 4
Steel with table 2 ingredients listed is carried out melting, hot rolling and warm-rolling to produce the steel disc that thickness is 0.35mm.In 0~-70 ℃ of scope, have in the nitrogen atmosphere of various dew points, this steel disc carried out 15 minutes thermal treatment, in the grain boundary, contain some steel disc test specimens of different O content with preparation in 1200 ℃.Go up these test specimens of test at tension test platform (using the tensiometer of JIS5 level test specimen).Measure O content in each test specimen grain boundary according to method therefor in embodiment 1, and in the tension testing table the relation between the O content in the elongation of surveying and the grain boundary study.In whole test specimens, all in the 0.2-0.8at.% scope, median size is in the 1-1.4mm scope for the O content in the grain boundary.This results are shown among Fig. 9.This graphic representation demonstrates, and the steel disc that O content is low in the grain boundary provides bigger elongation.
Table 2 (wt.%)
C |
Si |
Mn |
P |
S |
Sol.Al |
N |
O |
0.0051 |
3.03 |
0.25 |
0.0019 |
0.0021 |
2.30 |
0.0021 |
0.0031 |
Embodiment 5
Steel with table 3 ingredients listed is carried out melting, hot rolling and warm-rolling to produce the steel disc of different thickness.At 800-1, under 300 ℃ of various annealing temperatures those test specimens are carried out 15 minutes final annealings.1 * 10
-4Produce the various test specimens of the thick and median size of different sheets in the reduced pressure of holder.With the three-point bending machine gained test specimen is tested.The nubbin of each test specimen is placed in the auger electron spectroscopy instrument to measure the O content and the C content of grain boundary.This Auger spectroscopy demonstrates, and all the O content of test specimen in the grain boundary is 5 ± 2at.%, and the C content in the grain boundary is 0.8-2at.%.Table 4 illustrates the average crystal grain diameter and the results of three of each test specimen.This table demonstrates big median size and has reduced curved characteristic all.Particularly, when median size surpassed 2.0mm, curved characteristic obviously descended.For the test specimen of thickness above 0.5mm, even median size is 2.0mm or littler, this curved characteristic also is inferior.
Table 3 (wt.%)
C |
Si |
Mn |
P |
S |
Sol.Al |
N |
O |
0.0024 |
6.51 |
0.03 |
0.0021 |
0.0009 |
0.001 |
0.0012 |
0.0019 |
Table 4
Sheet thick (mm) |
Median size (mm) |
Amount of bow (mm) |
|
0.10 |
0.31 |
17 |
Sample |
0.10 |
0.68 |
16 |
″ |
0.10 |
0.9 |
13 |
″ |
0.10 |
1.9 |
12 |
″ |
0.35 |
0.92 |
11 |
″ |
0.35 |
1.42 |
8.5 |
″ |
0.35 |
1.90 |
4.9 |
″ |
0.35 |
2.56 |
2.3 |
Control sample |
0.50 |
1.23 |
4.3 |
Sample |
0.50 |
1.59 |
4.2 |
″ |
0.50 |
2.56 |
1.9 |
Control sample |
0.50 |
2.80 |
0.9 |
″ |
0.60 |
1.90 |
1.2 |
″ |
0.70 |
2.42 |
1.1 |
″ |
Embodiment 6:
Siliconized plate (the thickness: 0.3mm) that preparation has the listed chemical ingredients of table 5.It is the siliconized plate of 6.5wt.% to make silicone content that this steel disc is carried out siliconising one DIFFUSION TREATMENT (Si diffusion and osmotic treated).Use two kinds of different mixed gass to carry out siliconising as carrier gas: a kind of is same high pure nitrogen (dew point :-70 ℃) blended mixed gas, and another kind is same ordinary nitrogen (dew point :-30 a ℃) blended mixed gas.The gained test specimen carries out three point bending test, analyzes remaining test specimen to measure the O content in the grain boundary with the auger electron spectroscopy instrument.All test specimens demonstrate, the C content in the grain boundary in the 0.2at.%-1.2at.% scope and median size near 0.89mm.This result is summarized among Figure 10.This graphic representation demonstrates, and also is effective even the O content of restriction in the grain boundary improves spread the stalloy that an osmose process makes with Si.
Table 5 (wt.%)
C |
Si |
Mn |
P |
S |
Sol.Al |
N |
O |
0.0031 |
3.02 |
0.15 |
0.0010 |
0.0010 |
<0.001 |
0.0021 |
0.0025 |
Optimum implementation-2
By research in more detail, present inventors are by having understood the close-up of grain boundary with relevant (the O content in the grain boundary) other factors of workability.Specifically, present inventors use the sample of O content constant in the grain boundary to study the influence of each element of the grain boundary of emanating to workability, and find that sulphur has the tangible influence different with the influence of oxygen to workability.Figure 11 show three-point bending characteristic (in the above-mentioned three point bending test platform test specimen compress into stroke amount) and the S content located with the grain boundary that the auger electron spectroscopy instrument records between relation.Here used test specimen has following composition: 6.49wt.%Si.0.005wt.%Mn, 0.0015wt.%S and 0.0022wt.%O, and its thickness is 0.35mm, and makes it contain 0.1Vol.%H
2The N of S
2Heat-treat in the atmosphere.Each test specimen after the thermal treatment provides the total S that is bordering on equal amts in analytical error.O content is all in the 3-5at.% scope in the grain boundary of the Total Test test specimen that records with the auger electron spectroscopy instrument.According to Figure 11, there is very strong relation in workability with the S content in the crystal grain border, and this just can think that the S in the grain boundary has reduced workability.Although do not recognize S content and the strong detailed mechanism that concerns of workability in the grain boundary as yet, the grain boundary does not contain this fact of element that generates sulfide as Mn and so on, can think that S may be present in the grain boundary with the solid solution form.
Just can control particle diameter at an easy rate by changing annealing temperature.Yet above-mentioned test demonstrates the change annealing temperature can change workability widely.
Be described in detail as above, present inventors find, the workability that is considered to the natural inferior stalloy of processibility for a long time exists utmost point mutual relationship closely with the characteristic on crystal grain border, controls this characteristic the stalloy with fabulous workability can be provided.
As an example, used thickness is 0.1mm, have in the grain boundary of measuring as the listed chemical ingredients of table 6 with the auger electron spectroscopy instrument stalloy of O content much at one, with the relation between the S content in the grain boundary of measuring elongation and recording with the auger electron spectroscopy instrument.This results are shown among Figure 12.This figure demonstrates, and the test specimen that S content is low in the grain boundary has provided high elongation rate.At duration of test, provide 3% or the test specimen of bigger elongation produced viscous deformation.Demonstrate with electron microscope scanning surface of fracture, provide the test specimen generation cleavage fracture rather than the transgranular fracture of high elongation rate, and the inferior steel disc of elongation demonstrates the tendency of transgranular fracture.In the past, can not cause the stalloy of viscous deformation be acceptable to this class.Yet, found when the S content in the grain boundary be 0.2at.% or when lower, viscous deformation can take place.Therefore, regulation S content of the present invention is 0.2at.% or lower.
Table 6 (wt.%)
C |
Si |
Mn |
P |
S |
Sol.Al |
N |
O |
0.0024 |
6.51 |
0.03 |
0.0021 |
0.0009 |
0.001 |
0.0012 |
0.0019 |
The present invention not only needs to stipulate the S content in the grain boundary as mentioned above, and the O content in the grain boundary (the O content in each element of the grain boundary of emanating) need be defined in the 30at.%(atomic percent) or lower.In other words, have only when the O content in the grain boundary is enough low, can realize reducing the effect of S content in the grain boundary.For this purpose, the O content in the grain boundary must be reduced to 30at.% or lower.Figure 13 shows the relation between three-point bending characteristic (test specimen in three point bending test platform as mentioned above compress into stroke amount) and the grain boundary S content.Here used test specimen has following composition: 6.66wt.%Si, 0.001wt.%S, 0.001wt.%Sol.Al and 0.0025wst.%O, and its thickness is 0.35mm, and comprises different O content in the grain boundary.This graphic representation demonstrates, O content has provided the mutual relationship between the S content and three-point bending characteristic in the grain boundary in 30wt.% or the lower grain boundary, the O content that it also shows in the grain boundary surpasses under the 30at.% situation, even the S content in the grain boundary is 0.2wt.% or when lower, the three-point bending characteristic also only demonstrates very little variation.Therefore, the O content in the regulation of the present invention grain boundary is 30at.% or lower, is preferably 15at.% or lower.
The S content in the grain boundary and the influence of O content, find that particle diameter also influences workability.Found that the median size of seeing from the steel disc surface is 2.0mm or more hour, can further improve workability.The reason of inferring this effect is, reducing pro rata with the raising intragranular intensity of grain boundary intensity is because the influence of S in the grain boundary, and this can increase the crackle that crosses crystal grain, so excessive grain reduces workability through meeting.In stalloy, the stalloy of the about 0.05at.% of S content in about lat.% of C content and the grain boundary in the about 5at.% of O content, the grain boundary in the grain boundary is tested with the listed chemical ingredients of table 1.To measure the median size seen from the steel disc surface under the different-grain diameter and the relation between the three-point bending characteristic.This results are shown among Figure 14.Can find out according to this graphic representation, owing to median size being defined as 2.0mm or the littler workability of having improved.
The stalloy that uses in above-mentioned test has the coarse grained crystalline particle growth conditions of fabulous formation, and certainly will penetrate the place formation ring tissue of the thick direction of sheet at crystalline particle.However, as previously mentioned, from the workability viewpoint, the particle diameter of steel disc is preferably 2.0mm or littler, and steel disc need be selected controlled heat-treat condition so that not produce too much coarse grain.When the crystal structure formation ring of stalloy was organized, present inventors found that the growth of crystalline particle stops at the about 3-4 of particle diameter basically doubly to the place of steel plate thickness.Therefore, in order particle diameter to be remained on 2.0mm or littler, the thick 0.5mm or thinner that is chosen in of sheet.In the case, not should be noted that heat-treat condition.In view of these reasons, the preferred thickness of steel disc is 0.5mm or thinner.
Obtaining in effect of the present invention and the siliconized plate grain orientation distributes irrelevant.Therefore, the present invention neither is defined as the siliconized plate of orientation, also is not defined as the siliconized plate of non-orientation.Common electrical sheet need apply insulation film, and the existence of filming is not depended in the present invention.The present invention does not stipulate to make the method for thin slice, but the present invention is applicable to the stalloy of making by special rolled method, siliconising method (former the narration) and other proper method.
Embodiment 7:
Have table 7 ingredients listed stalloy (thickness: 0.1mm) in 1200 ℃, in 5-1 * 10
-5Carry out thermal treatment (final annealing) in 15 minutes in the different reduced pressure of holder.Breadboard envrionment temperature is 27 ℃, and humidity is 80%.With the three-point bending machine gained test specimen is tested, compressed into stroke amount to measure the preceding maximum of fracture.The nubbin of each test specimen is placed in makes it 8 * 10 in the auger electron spectroscopy instrument
-10The vacuum implosion of holder.Observe the surface of fracture of each test specimen and analyze the composition that the grain boundary is located.According to the composition analysis of auger electron spectroscopy instrument, selecting the O content in the grain boundary is that 3-5at.%, C content are that about 0.3at.% and median size are the test specimen of 0.2mm, with the influence of the S content in the mensuration grain boundary to the three point bending test amount of bow.Figure 15 shows this result.This graphic representation demonstrates, and the S content that reduces in the grain boundary increases amount of bow significantly, and this can think that the S content in the grain boundary is low more, and workability is just good more.
Table 7 (wt.%)
C |
Si |
Mn |
P |
S |
Sol.Al |
N |
O |
0.0041 |
4.21 |
0.01 |
0.0015 |
0.0015 |
2.10 |
0.0015 |
0.0021 |
Embodiment 8:
To stalloy with table 8 ingredients listed and different thickness 1 * 10
-4The reduced pressure of holder, carry out 15 minutes final annealings, have the thick test specimen with different average crystal grain diameters of different sheets to produce in 800-1300 ℃ various annealing temperatures.Use the three-point bending machine that the gained test specimen is tested.The nubbin of each test specimen is placed in the auger electron spectroscopy instrument to measure the C content and the S content of grain boundary.This Auger electron spectrum demonstrates, all the O content of test specimen in the grain boundary be C content in 8 ± 2at.%, the grain boundary in the 0.8-2at.% scope, the S content in the grain boundary is in the 0.05-0.10at.% scope.Table 4 shows the average crystal grain diameter and the results of three of each test specimen.This is expressed, and the above median size of 2.0mm has reduced curved characteristic significantly.Surpass the test specimen of 0.5mm for thickness, even median size is 2.0mm or when lower, curved characteristic also is inferior.
Table 8 (wt.%)
C |
Si |
Mn |
P |
S |
Sol.Al |
N |
O |
0.0024 |
6.61 |
0.01 |
0.0019 |
0.0021 |
0.001 |
0.0029 |
0.0052 |
Embodiment 9:
Produce siliconized plate (thickness: 0.3mm) with the listed chemical ingredients of table 9.This steel disc carries out siliconising one DIFFUSION TREATMENT (Si diffusion and osmotic treated) at 1200 ℃.Use two kinds of different mixed gass to carry out siliconising as carrier gas.A kind of is same high pure nitrogen (dew point :-70 ℃) blended SiCl
4Gas, another kind are same ordinary nitrogen (dew point :-30 ℃) blended SiCl
4Gas.The gained test specimen carries out three point bending test, analyzes remaining test specimen with the auger electron spectroscopy instrument, to measure O content, C content and the S content in the grain boundary.In each test specimen of being tested, be chosen in the about 10at.% of O content, the about 0.7at.% of S content in the grain boundary in the grain boundary and the test specimen of the about 0.8mm of median size, to measure the relation between the S content and three point bending test amount of bow in the grain boundary.This results are summarized among Figure 16.This graphic representation demonstrates, even the S content of restriction in the grain boundary improves workability to also being effective by spread the high steel disc that an osmose process makes with Si.
Table 9 (wt.%)
C |
Si |
Mn |
P |
S |
Sol.Al |
N |
O |
0.0035 |
2.99 |
0.02 |
0.0015 |
0.0012 |
<0.001 |
0.0031 |
0.0021 |
Embodiment 10
The steel disc that to produce thickness with rolling be 0.35mm, have table 10 ingredients listed, this steel disc has-10~-70 ℃ of dew points and H
2Under the some kinds of nitrogen atmosphere of S content in the 0-0.1Vol.% scope, carry out thermal treatment in 15 minutes in 1200 ℃.With the three-point bending machine test specimen that these make is tested, analyzed the nubbin of above-mentioned test specimen, measure O content in the grain boundary and S content to determine their influences to the three point bending test amount of bow with the auger electron spectroscopy instrument.This results are summarized among Figure 13, this graphic representation demonstrates, O content is 30at.% or when lower in the grain boundary, S content in the grain boundary and the relation between the amount of bow, when the O content in the grain boundary when 30at.% is above, even the S content in the grain boundary is reduced to 0.2at% or when lower, the variation that the three-point bending characteristic produces is also very little.
Table 10:(wt.%)
C |
Si |
Mn |
P |
S |
Sol.Al |
N |
O |
0.003 |
6.66 |
0.25 |
0.002 |
0.0015 |
0.001 |
0.0018 |
0.0034 |
Table 11
Sheet thick (mm) |
Median size (mm) |
Amount of bow (mm) |
|
0.10 |
0.35 |
16.5 |
Sample |
0.10 |
0.72 |
15.2 |
″ |
0.10 |
0.95 |
14.2 |
″ |
0.10 |
1.93 |
11.9 |
″ |
0.10 |
2.12 |
3.3 |
Control sample |
0.10 |
2.43 |
2.9 |
″ |
0.35 |
0.89 |
11.9 |
Sample |
0.35 |
1.49 |
9.5 |
″ |
0.35 |
1.85 |
4.1 |
″ |
0.35 |
2.49 |
1.9 |
Control sample |
0.50 |
1.19 |
4.1 |
Sample |
0.50 |
1.51 |
4.2 |
″ |
0.50 |
2.41 |
1.8 |
Control sample |
0.50 |
2.42 |
1.9 |
″ |
0.60 |
1.85 |
1.1 |
″ |
0.70 |
2.49 |
1.1 |
″ |