CN1092112A - Superfine crystal particle alloy with excellent corrosion resistance - Google Patents
Superfine crystal particle alloy with excellent corrosion resistance Download PDFInfo
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- CN1092112A CN1092112A CN 93117351 CN93117351A CN1092112A CN 1092112 A CN1092112 A CN 1092112A CN 93117351 CN93117351 CN 93117351 CN 93117351 A CN93117351 A CN 93117351A CN 1092112 A CN1092112 A CN 1092112A
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Abstract
The invention provides a kind of alloy of superfine crystal particle, this kind alloy has excellent solidity to corrosion, and at least 50% of alloy structure is a superfine crystal particle.This kind alloy has the upper layer that contains hydroxide composition, and wherein to account for the overall proportion of oxide component be 65% or higher to hydroxide composition.
Description
The present invention relates to a kind of alloy of superfine crystal particle, this alloy has excellent soft magnetism and solidity to corrosion.
Well-known soft magnetic materials such as silicon steel, Fe-Si alloy, amorphous alloy etc., its important properties is to have high relative permeability μ and high saturation flux density Bs.
Except that magnetic property, because of these magneticsubstances will be used for various environment, so its solidity to corrosion also is a kind of important performance.
Yet once thought, and made this magneticsubstance have high saturation flux density Bs simultaneously and high relative permeability μ is difficult.For example, iron-rich amorphous alloys has high saturation flux density, and its soft magnetic property is inferior to the cobalt-based amorphous alloy, though and the cobalt-based amorphous alloy has excellent soft magnetic property, but its saturation flux density Bs can not be satisfactory.
It has been generally acknowledged that high saturation flux density Bs and high relative permeability μ can not have concurrently, but U.S. Patent No. 4,881,989 have disclosed a kind of iron-base soft magnetic alloy of tool superfine crystal particle, and it has high saturation flux density Bs and has high relative permeability μ simultaneously again.The average grain size of this ferrous alloy is 500
Or littler, prepare by its rapid quenching to amorphous state then being carried out again the crystallization processing.The ferrous alloy of this superfine crystal particle is because of containing elements such as niobium, so its corrosion resisting property is good in some cases, but in different environments for use, its solidity to corrosion may not be satisfactory.
A target of the present invention provides a kind of alloy of superfine crystal particle, and this alloy has the solidity to corrosion of having improved.
As for addressing the above problem the result of the further investigation of carrying out, the contriver finds to have a kind of alloy of special upper layer, and its solidity to corrosion can greatly be improved.
According to the present invention, in the structure of this superfine crystal particle alloy, have at least 50% to be superfine crystal grain, and in the upper layer of this alloy, the total amount of oxyhydroxide account for oxide amount 65% or more than, thereby show excellent solidity to corrosion.
Brief description of drawings
Fig. 1 is the 1S electron energy spectrogram of the thin peritectic alloy upper layer of the present invention Sauerstoffatom;
Fig. 2 is the 2p 3/2 electron energy spectrogram of the thin peritectic alloy upper layer of the present invention iron atom;
Fig. 3 is the 2p electron energy spectrogram of Siliciumatom in the thin peritectic alloy upper layer of the present invention;
Fig. 4 is the 1S electron energy spectrogram of Sauerstoffatom in the thin peritectic alloy upper layer of the present invention;
Fig. 5 is the 2p 3/2 electron energy spectrogram of iron atom in the thin peritectic alloy upper layer of the present invention;
Fig. 6 is the 2p electron energy spectrogram of Siliciumatom in the thin peritectic alloy upper layer of the present invention;
Fig. 7 is the 1S electron energy spectrogram of the thin peritectic alloy of the present invention surface Sauerstoffatom in the upper layer that anodizing forms.
To carry out detailed narration to the present invention below.
Can identify with x-ray photoelectron spectroscopy ESCA the superficial layer of the thin peritectic alloy of the present invention. ESCA is a kind of analytical method of chemical element, is that X ray is put on sample, thereby and surveys photoelectron that sample emissions goes out identifies element by the chemical deviation value of bond energy chemical bond. In this invention, owing in the ESCA spectrum, observe the peak of hydroxide, thus determined the existence of hydroxide. Some peak then is the peak of oxide. Can obtain more deep understanding by following example.
In the following example, when the hydroxide content of fine-grained alloy in its superficial layer compares oxygen When compound content was bigger, this alloy then had excellent corrosion resistance. In this case, when the top layer of ferrous alloy was thin, (in alloy inside) Fe ° can be detected very doughtily under the top layer, then observes Fe in the top layer2+And Fe3+ In addition, concerning the fine-grained alloy that contains Si, contain Si such as its top layer4+, then alloy has excellent corrosion resistance. If Si4+With SiO2Form exist, then the thin peritectic alloy of this kind in most of the cases all demonstrates excellent corrosion resistance.
When the upper layer of thin peritectic alloy contains the oxide compound of at least a element in Ta, Nb and the Cr group, the solidity to corrosion that the alloy tool is excellent especially.In this case, these elements there is no need to be oxide compound state completely, the normally state between oxide compound and metal.When upper layer contained in Zr, Hf and the W group at least a element, the solidity to corrosion of alloy in alkaline environment then was improved.
Average grain size in thin peritectic alloy is less than 500
Or more hour, the solidity to corrosion of alloy is further improved, and its magnetic and mechanical property also improve simultaneously, reaches the glad level that receives of practical application.Special ideal average grain size is 20
To 200
, because the structure of alloy is meticulous and uniform in this average grain size scope.
As an example of fine-grained alloy among the present invention, its composition can be expressed with following general formula:
M
100-x-y-z-alpha-beta-γA
xSi
yB
zM '
αM "
βX
γ(atom %)
M represents at least a element of selecting among Fe, Co and the Ni in the formula; A represents at least a element of selecting among Cu, Ag and the Au; M ' represents at least a element of selecting in Nb, Mo, Ta, Ti, Zr, Hf, V, Cr and the W group; M " represents Mn, Al, platinum family element, Sc, Y, rare earth element, Zn, Sn and Re; X represents at least a element of selecting in C, Ge, P, Ga, Sb, In, Be and the As group; 0≤x≤10,0≤y≤30,0≤z≤25,0≤y+z≤30,1≤α≤20,0≤β≤20, and 0≤γ≤20.
Element M is a kind of ferromagnetic element of selecting from Fe, Co and Ni group at least.
The elements A representative is a kind of element of selecting from Cu, Ag and Au group at least, and this kind element makes the structure refinement effectively of alloy with M ' element.
A kind of element that element M ' representative is selected from Nb, Mo, Ta, Ti, Zr, Hf, V, Cr and W group at least, this kind element makes the structure refinement greatly of alloy with elements A.Among above-mentioned various element, at least a element of selecting from Nb, Ta and Cr will make alloy be easy to form to have the corrosion proof upper layer that has improved.
Si and B be make alloy become amorphous, improve magnetic property and make the effective elements of alloy structure refinement.The Si role is a solidity to corrosion of improving thin peritectic alloy upper layer, as the Si in the upper layer with SiO
2Form exist, then its solidity to corrosion will obtain improvement greatly.
Element M " represents at least a element in Mn, Al, platinum family element, Sc, Y, rare earth element, Zn, Sn and the Re group, M " to the solidity to corrosion of improving alloy and to control its magnetic be effective.
Element X represents at least a element among C, Ge, P, Ga, Sb, In, N, Be and the As, and it is effective to making alloy be amorphous structure and control magnetic property.
Because the existence of above-mentioned upper layer, alloy crystalline is at 0.1Kmol/m
3Sodium-chlor (NaCl) aqueous solution in erosion rate can be reduced to 1 * 10
-8Kg/m
2S, or lower.
Fine-grained alloy of the present invention can prepare as follows, at first prepare unbodied alloy, can adopt such as liquid phase quenching methods such as single current method, double stream process, rotating liquid high speed rotating methods, also can adopt such as gas phase quenching methods such as sputtering method, vapour deposition processes; Then, amorphous alloy is heat-treated, make at least 50% of alloy structure transform into superfine crystal grain.Though the equilibrium state of alloy structure is normally unbodied, present invention includes the alloy that has in fact the alloy structure of forming by ultra-fine crystallization phases.Thin peritectic alloy of the present invention also can prepare like this, promptly at first utilizes to apply laser and make on alloy on its surface and form the amorphous alloy layer, and then it is heat-treated.Heat-treat as the amorphous alloy that will atomize, also can prepare the alloy of pulverulence among the present invention.
Need have in the technology of heat treatment stages, wish that thermal treatment carries out under 450 ℃ of-800 ℃ of temperature.Be lower than 450 ℃ as thermal treatment temp, even, also be difficult to obtain meticulous crystallization through thermal treatment for a long time.And when thermal treatment temp was higher than 800 ℃, crystal grain will excessively be grown up, and equally also can not get the ideal superfine crystal particle.The thermal treatment temp of recommending is 500-700 ℃.Meanwhile, heat treatment time is generally 1 minute to 200 hours, and the recommendation time is 5 minutes to 24 hours, and concrete thermal treatment temp and time can be determined in above-mentioned scope according to the component of alloy.Above-mentioned thermal treatment can be carried out in inert atmosphere.
The thermal treatment of interalloy of the present invention can be carried out in magnetic field.When on a certain direction, applying a magnetic field, can obtain having the alloy after the thermal treatment of this side up magnetic ununiformity.Moreover as heat-treating in rotatingfield, the soft magnetic performance of material will be further improved.In addition, can also after the thermal treatment of carrying out fine crystallizationization, carry out thermal treatment in the magnetic field again.
Another kind of preparation method is that the alloy of superfine crystal particle can directly prepare without amorphous phase by control quenching condition among the present invention.
Might adopt in the inert atmosphere that contains oxygen and water vapour and heat-treat, or before or after crystallization is handled, carry out anodised method, make thin peritectic alloy of the present invention have the upper layer that contains oxyhydroxide.
When heat-treating in the inert atmosphere that contains oxygen and water vapour, this inert atmosphere should contain the 0.1-3%(volume) oxygen and 10-100PPM water vapour, the oxygen level of recommendation is about 0.5%(volume), the water vapour content of recommendation is 20-50PPM.
Be preferably under 250-700 ℃ and carry out for forming thermal treatment that upper layer carries out.When thermal treatment temp is lower than 250 ℃, can not obtain having good corrosion proof upper layer.And when being higher than 700 ℃, then make the crystal grain in the upper layer of acquisition become too big.
The thermal treatment that forms upper layer can be carried out simultaneously with the thermal treatment that needs for meticulous crystallization, at this moment, can carry out 10 minutes to 24 hours thermal treatment in the inert atmosphere that contains oxygen and water vapour under 450-700 ℃ temperature.
The present invention has also comprised employing sputtering method or vapour deposition process and CVD method (chemical vapour deposition) etc. and has formed those thin peritectic alloy of above-mentioned upper layer.
To be further explained in detail the present invention by following example, rather than limit the scope of the invention.
Example 1
The alloy melt of following three kinds of compositions is become the thick amorphous alloy thin slice of wide, the about 18 μ m of 5mm with the rapid quenching of single current method:
Sample 1:Fe
BelCu
1Si
13.5B
9
Sample 2:Fe
BelCu
1Nb
5Si
13.5B
9
Sample 3:Fe
BelCu
1Nb
7Si
16B
9
" bal " refers to surplus.
Alloy sheet is being contained the 0.5%(volume) under the nitrogen atmosphere of oxygen and 30PPM water vapour, in 570 ℃ of thermal treatments of carrying out 1 hour, the alloy after the thermal treatment has the structure of crystallization, and promptly having in the structure more than 90% or 90% is that average grain size is 100
Superfine crystal particle.
Observe the upper layer of thin peritectic alloy with ESCA.Program and the condition analyzed are as follows: will be cut into each sample that is of a size of 4mm * 4mm and be fixed on the probe of two-sided conductive carbon adhesive tape.Under the condition of 5KV and 30mA, adopt in order to X ray excited Mg-Ka ray, 2 * 10
-7Mmhg or residual voltage more rough vacuum get off to analyze.
The erosion rate of fine-grained alloy is also at 0.1Kmol/m
3Sodium-chlor (NaCl) aqueous solution in test.The erosion rate of the thin peritectic alloy of surveying is as follows:
Sample 1:2.02 * 10
-8Kg/m
2S;
Sample 2:8.27 * 10
-11Kg/m
2S;
Sample 3: be almost 0Kg/m
2S.
The 1S electronic spectrum of Sauerstoffatom is shown in Fig. 1 in the above-mentioned thin peritectic alloy upper layer.In the spectrogram of the sample 2 with excellent corrosion resistance and 3, by oxyhydroxide M(OH)
YThe peak of contribution is greatly to 65% or bigger, and wherein M represents a kind of transition metal, and Y represents the valence mumber of M; And little by the peak of oxide M Ox contribution to 35% or littler, wherein x represent M valence mumber 1/2nd.This fact shows, oxyhydroxide M(OH in by the top layer)
YThe total value at peak of contribution account for M all compose the peak integrated value 65% or when above, this thin peritectic alloy will have solidity to corrosion preferably.
The 2p electronic spectrum of Si in these thin peritectic alloy top layers is illustrated in Fig. 3, in the sample 2 and 3 of tool excellent corrosion resistance, mainly observes Si
4+(in Fig. 3, be accredited as SiO
2), and between Si ° and Si
4+(SiO
2) the intermediate oxidation state then do not observe.Along with Si
4+(SiO
2) increase of content, the solidity to corrosion of thin peritectic alloy trends towards improving.
Example 2
Become 5mm wide with the rapid quenching of single current method the alloy melt of following four kinds of compositions, the amorphous alloy thin slice that 18 μ m are thick:
Sample 4:Fe
BalCu
1Si
13.5B
9,
Sample 5:Fe
BalCu
1Nb
5Si
13.5B
9,
Sample 6:Fe
BalCu
1Ta
5Si
13.5B
9, and
Sample 7:Fe
BalCu
1Ti
5Si
13.5B
9
In the nitrogen atmosphere that contains 0.5% oxygen and 30PPM water vapour in 590 ℃ with alloy sheet thermal treatment 1 hour.Alloy after the thermal treatment has the structure of crystallization, promptly have in the structure 90% or more average grain size be 110
Superfine crystal particle.
With the same manner described in the example 1, the upper layer of these thin peritectic alloy is carried out x-ray photoelectron spectrum analysis ESCA.At 0.1Kmol/m
3The NaCl aqueous solution in the test thin peritectic alloy erosion rate, the erosion rate of these alloys of being surveyed is as follows:
Sample 4:2.02 * 10
-8Kg/m
2S;
Sample 5:8.27 * 10
-11Kg/m
2S,
Sample 6:8.24 * 10
-11Kg/m
2S, and
Sample 7:1.01 * 10
-9Kg/m
2S.
The 1S electronic spectrum of the Sauerstoffatom of above-mentioned thin peritectic alloy upper layer is illustrated in Fig. 4.In the sample 5 of tool excellent corrosion resistance and 6 the spectrogram, oxyhydroxide M(OH)
YThe peak is greatly to 65% or bigger, and the peak of MOx is then little of 35% or littler.This fact shows, oxyhydroxide M(OH in by the top layer)
YThe total value at peak of contribution account for M all compose the peak integrated value 65% or when higher, these thin peritectic alloy then have solidity to corrosion preferably.
The 2p electronic spectrum of Si atom is illustrated in Fig. 6 in these thin peritectic alloy top layers, in the sample 5 and 6 of tool excellent corrosion resistance, mainly observes Si
4+(differentiate among Fig. 6 and be SiO
2), and do not observe between Si ° and Si
4+(SiO
2) between the component of intermediate oxidation state.Along with Si
4+(SiO
2) increase of content, the solidity to corrosion of thin peritectic alloy is improved.
Example 3
Three kinds of alloy melts that will have following composition become wide 5mm with the rapid quenching of single current method, the amorphous alloy thin slice of thick 18 μ m:
Sample 8:Fe
BalCu
1Nb
5Si
13.5B
9,
Sample 9:Fe
BalCu
1Ta
5Si
13.5B
9, and
Sample 10:Fe
BalCu
1Ti
5Si
13.5B
9
With amorphous thin slice in containing the 0.001%(volume) in the nitrogen atmosphere of oxygen and 10PPM water vapour 590 ℃ of following thermal treatments 1 hour, the alloy after the thermal treatment is the crystallization structure, promptly wherein have 90% or more average grain size be 100
Superfine crystal particle.After the thermal treatment, this thin peritectic alloy is carried out anodizing under the following conditions to form oxide layer:
Sample 8: under 298 ° of K in 0.1Kmol/m
3In the NaCl aqueous solution ,-the relative Ag/AgCl of 0.2V() handled 1 hour down,
Sample 9: under 298 ° of K in 0.1Kmol/m
3In the NaCl aqueous solution ,+the relative Ag/AgCl of 0.3V() handled 1 hour down,
Sample 10: under 298 ° of K in 0.1Kmol/m
3In the NaCl aqueous solution ,-the relative Ag/AgCl of 0.2V() handled 1 hour down.
The 1S electronic spectrum of above-mentioned thin peritectic alloy top layer Sauerstoffatom is shown in Fig. 7.In the sample 8 of tool excellent corrosion resistance and 9 the spectrogram, its oxyhydroxide M(OH)
YThe peak can be as big as 65% or bigger, and oxide M Ox peak is then little of 35% or littler.This fact table understands, in the top layer by oxyhydroxide M(OH)
YThe total value at peak of contribution account for all spectrum peaks of M integrated value 65% or when higher, these thin peritectic alloy have solidity to corrosion preferably.
Example 4
The molten state alloy that component such as table 1 is listed is with the rapid quenching of single current method, to obtain wide 5mm, the amorphous alloy thin slice of thick 18 μ m.Then this alloy sheet is carried out 1 hour thermal treatment under 570 ℃ in the nitrogen atmosphere that contains 0.5% oxygen and 30PPM water vapour.Alloy after the thermal treatment is the structure of crystallization, promptly wherein have 90% or more average grain size be 100
Superfine crystal particle.
To the top layer of this thin peritectic alloy, carry out ESCA with the same manner described in the example 1 and observe.The ratio and the Si of oxyhydroxide and oxide compound constituent element in the top layer
4+The ratio of key, peak that can be by every kind of key are determined the ratio of the integrated intensity at this element spectral peak by force.Sauerstoffatom 1S spectrum peak mainly is contribution from four kinds of components in the spectrogram herein, and promptly (1) is from the water (H that is adsorbed in thin peritectic alloy surface
2O); (2) from oxyhydroxide; (3) from the oxidation products SiO of the Si of one of alloying element
2; (4) from the oxide compound of Fe in the alloying element etc.With the 1S spectrogram of viewed Sauerstoffatom and various keys via Gauss-Lorenz(Gauss-Lorentz lorentz) mixed distribution the approximate and synthetic spectral line of every kind of key spectrum obtaining compares, just can determine each key attitude of Sauerstoffatom.
The ratio of hydroxide composition and oxide component can be defined as the ratio of the part of being contributed by oxide component in the part contributed by hydroxide composition in (a) Sauerstoffatom integral spectrum and (b) Sauerstoffatom integral spectrum.Simultaneously, since from the peak of the 1S electronic energy spectral line of the Sauerstoffatom of oxyhydroxide with from Si
4+(SiO
2) the peak closer to each other, so be difficult to every kind of spectral line is separated fully.Like this, strong in the 1S spectral line of Sauerstoffatom by peak that MOx contributed, suppose think from the 2p spectral line of Si by Si
4+The peak of being contributed is strong.
Identical with example 1, the erosion rate of thin peritectic alloy is also at 0.1Kmol/m
3The NaCl aqueous solution in test.The ratio of measured erosion rate, hydroxide composition and oxide component and Si
4+Ratio list in table 1 and the table 2.Contain the thin peritectic alloy of Fe, its upper layer contains Fe
2+And Fe
3+Compound.
Table 1
The fast oxyhydroxide of sample volume corrosion/
Number
(1)Form (atom %) rate
(2)Oxide compound
(3)Si
4+Ratio (%)
11 Fe
bal.Cu
1Si
13.5B
9Nb
58.27×10
-11108 93
12 Fe
bal.Cu
1Si
13.5B
9Ta
58.24×10
-11246 91
13 Fe
bal.Cu
1Si
13.5B
9Cr
58.27×10
-11201 97
14 Fe
bal.Cu
1Si
13.5B
9Zr
55.95×10
-11105 91
15 Fe
bal.Cu
1Si
13.5B
9Hf
53.3×10
-1098 90
16 Fe
bal.Cu
1Si
13.5B
9Nb
5W
28.47×10
-11110 92
17 Fe
bal.Cu
1Si
13.5B
9Nb
5Hf
55.12×10
-11208 94
18 Fe
Bal.Cu
1Si
13.5B
9Nb
7Be almost 0 100 94
19 Co
bal.Cu
1Si
13.5B
9Nb
5Zr
15.25×10
-11125 95
20 Ni
bal.Cu
1Si
13.5B
9Nb
5Cr
54.65×10
-11140 96
21 Fe
bal.Au
1Si
10B
6Zr
78.95×10
-1197 86
22 Fe
bal.Cu
1Si
13.5B
9Nb
5Al
37.89×10
-11115 95
23 Fe
bal.Cu
1Si
13.5B
9Nb
5Ge
38.86×10
-1198 90
24 Fe
bal.Cu
1Si
13.5B
9Nb
5Ga
19.26×10
-1196 88
25 Fe
bal.Cu
1Si
13.5B
9Nb
5P
18.36×10
-1192 87
26 Fe
bal.Cu
1Si
13.5B
9Nb
5Ru
27.29×10
-11120 89
27 Fe
bal.Cu
1Si
13.5B
9Nb
5Pd
28.52×10
-11101 88
28 Fe
bal.Cu
1Si
13.5B
9Nb
5Pt
27.94×10
-1199 92
29 Fe
bal.Cu
1Si
13.5B
9Nb
5C
0.28.78×10
-11118 86
30 Fe
bal.Cu
1Si
13.5B
9Nb
5Mo
28.12×10
-11120 88
31 Fe
bal.Cu
1Si
13.5B
9Nb
5Mn
59.46×10
-11105 89
Annotate: (1) example of the present invention
(2) unit is kgm
-2S
-1
(3) ratio of oxyhydroxide and oxide compound (%)
Table 2
The fast oxyhydroxide of sample volume corrosion/
Number
(1)Form (atom %) rate
(2)Oxide compound
(3)Si
4+Ratio (%)
32 Fe
bal.Cu
1Si
13.5B
92.02×10
-864 55
33 Fe
bal.Cu
1Si
13.5B
9Ti
11.58×10
-863 62
34 Fe
bal.Cu
1Si
13.5B
9W
32.04×10
-862 52
35 Fe
bal.Cu
1Si
13.5B
9Mn
52.28×10
-860 51
Annotate: (1) duplicate
(2) unit is kgm
-2S
-1
(3) ratio of oxyhydroxide and oxide compound (%)
From table 1 and table 2, can clearly find out, when hydroxide composition in the upper layer of thin peritectic alloy is 65% or when higher, this thin peritectic alloy then shows excellent solidity to corrosion to the ratio of oxide component.Particularly work as upper layer and contain Si
4+(SiO
2) and work as Si
4+The ratio of the integrated value of the whole 2p spectral line of peak value and Si atom was greater than 55% o'clock, and thin peritectic alloy shows excellent solidity to corrosion (low-down erosion rate).The thin peritectic alloy that contains Ta, Nb and Cr, because the oxide compound of these elements, and have very excellent solidity to corrosion.
The present invention can provide the thin peritectic alloy with excellent corrosion resistance.
Claims (7)
1, the thin peritectic alloy of tool excellent corrosion resistance has at least 50% to be superfine crystal grain in its alloy structure, this alloy has the upper layer that contains hydroxide composition, and the overall proportion that this oxyhydroxide accounts for oxide component is 65% or higher.
2, according to the alloy of claim 1, wherein this alloy is a kind of ferrous alloy, and has the Fe of containing
2+And Fe
3+The upper layer of compound, and in this alloy, can be observed Fe ° of spectral line with x-ray photoelectron spectroscopy.
3, according to the alloy of claim 1 or 2, wherein this alloy contains Si, and has the Si of containing
4+The upper layer of compound, and Si wherein
4+The peak is by force to the ratio of the integrated intensity of the full 2p electronic spectrum of Si atom, is determined as with x-ray photoelectron spectrometer to be higher than 55%.
4, according to each alloy in the claim 1 to 3, wherein this upper layer contains the oxide compound of at least a element that is selected from Ta, Nb and Cr group.
5, according to each alloy in the claim 1 to 3, wherein this upper layer contains the oxide compound of at least a element that is selected from Zr, Hf and W group.
6, according to each alloy of claim 1 to 5, wherein this alloy is at 0.1Kmol/M
3The NaCl aqueous solution in erosion rate be 1 * 10
-8Kg/m
2S or lower.
7, according to each alloy of claim 1-6, wherein this alloy comprises that to have average grain size be 500
Or littler superfine crystal particle.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP235467/92 | 1992-09-03 | ||
| JP23546792A JPH0681086A (en) | 1992-09-03 | 1992-09-03 | Alloy having ultrafine crystalline-grained structure excellent in corrosion resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1092112A true CN1092112A (en) | 1994-09-14 |
| CN1037534C CN1037534C (en) | 1998-02-25 |
Family
ID=16986525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93117351 Expired - Lifetime CN1037534C (en) | 1992-09-03 | 1993-09-03 | Alloy with ultrafine crystal grains excellent in corrosion resistance |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0585940B1 (en) |
| JP (1) | JPH0681086A (en) |
| CN (1) | CN1037534C (en) |
| DE (1) | DE69319513T2 (en) |
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| CN102867605A (en) * | 2012-09-10 | 2013-01-09 | 任静儿 | Magnetic alloy |
| CN102867604A (en) * | 2012-09-10 | 2013-01-09 | 任静儿 | Magnetically soft alloy |
| CN103123841A (en) * | 2012-09-10 | 2013-05-29 | 顾建 | Magnetic alloy material |
| CN103123842A (en) * | 2012-10-22 | 2013-05-29 | 虞海香 | Magnetic powdered alloy material |
| CN105244132A (en) * | 2015-11-03 | 2016-01-13 | 顾建 | Weakly-magnetic alloy material |
| CN105401041A (en) * | 2015-11-13 | 2016-03-16 | 太仓旺美模具有限公司 | High-abrasion-resistance metal material |
| CN107620015A (en) * | 2017-08-22 | 2018-01-23 | 宁波市鄞州亚大汽车管件有限公司 | Oil filling pipe and its preparation technology |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2234193B (en) * | 1988-03-08 | 1991-11-13 | Secr Defence | Growing semiconductor crystalline materials |
| GB8805478D0 (en) * | 1988-03-08 | 1988-04-07 | Secr Defence | Method & apparatus for growing semi-conductor crystalline materials |
| JPH0845723A (en) * | 1994-08-01 | 1996-02-16 | Hitachi Metals Ltd | Nano-crystalline alloy thin band of excellent insulating property and nano-crystalline alloy magnetic core as well as insulating film forming method of nano-crystalline alloy thin band |
| DE10349339A1 (en) * | 2003-10-23 | 2005-06-16 | Crystal Growing Systems Gmbh | Crystal growing equipment |
| US8480864B2 (en) * | 2005-11-14 | 2013-07-09 | Joseph C. Farmer | Compositions of corrosion-resistant Fe-based amorphous metals suitable for producing thermal spray coatings |
| DE102006024358B4 (en) * | 2006-05-17 | 2013-01-03 | Leibniz-Institut Für Festkörper- Und Werkstoffforschung Dresden E.V. | High-strength, at room temperature plastically deformable shaped body made of iron alloys |
| JP5875159B2 (en) * | 2012-12-19 | 2016-03-02 | アルプス・グリーンデバイス株式会社 | Fe-based soft magnetic powder, composite magnetic powder using the Fe-based soft magnetic powder, and dust core using the composite magnetic powder |
| DE102013224989A1 (en) * | 2013-12-05 | 2015-06-11 | Siemens Aktiengesellschaft | Gamma / Gamma hardened cobalt base superalloy, powder and component |
| JP6294533B1 (en) * | 2017-04-03 | 2018-03-14 | 住友電気工業株式会社 | Manufacturing method of iron boride material and iron boride thin film material |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5151137A (en) * | 1989-11-17 | 1992-09-29 | Hitachi Metals Ltd. | Soft magnetic alloy with ultrafine crystal grains and method of producing same |
| CA2030446C (en) * | 1989-11-22 | 2001-01-23 | Yoshihito Yoshizawa | Magnetic alloy with ultrafine crystal grains and method of producing same |
-
1992
- 1992-09-03 JP JP23546792A patent/JPH0681086A/en active Pending
-
1993
- 1993-09-03 CN CN 93117351 patent/CN1037534C/en not_active Expired - Lifetime
- 1993-09-03 EP EP19930114142 patent/EP0585940B1/en not_active Expired - Lifetime
- 1993-09-03 DE DE1993619513 patent/DE69319513T2/en not_active Expired - Lifetime
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102610348A (en) * | 2012-04-11 | 2012-07-25 | 安泰科技股份有限公司 | Iron-based nanocrystalline soft magnetic alloy material and preparing method thereof |
| CN102610348B (en) * | 2012-04-11 | 2015-04-29 | 安泰科技股份有限公司 | Iron-based nanocrystalline soft magnetic alloy material and preparing method thereof |
| CN102856031A (en) * | 2012-09-10 | 2013-01-02 | 任静儿 | Magnetic powder alloy material |
| CN102867605A (en) * | 2012-09-10 | 2013-01-09 | 任静儿 | Magnetic alloy |
| CN102867604A (en) * | 2012-09-10 | 2013-01-09 | 任静儿 | Magnetically soft alloy |
| CN103123841A (en) * | 2012-09-10 | 2013-05-29 | 顾建 | Magnetic alloy material |
| CN103123842A (en) * | 2012-10-22 | 2013-05-29 | 虞海香 | Magnetic powdered alloy material |
| CN105244132A (en) * | 2015-11-03 | 2016-01-13 | 顾建 | Weakly-magnetic alloy material |
| CN105401041A (en) * | 2015-11-13 | 2016-03-16 | 太仓旺美模具有限公司 | High-abrasion-resistance metal material |
| CN107620015A (en) * | 2017-08-22 | 2018-01-23 | 宁波市鄞州亚大汽车管件有限公司 | Oil filling pipe and its preparation technology |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0585940B1 (en) | 1998-07-08 |
| DE69319513D1 (en) | 1998-08-13 |
| CN1037534C (en) | 1998-02-25 |
| EP0585940A1 (en) | 1994-03-09 |
| JPH0681086A (en) | 1994-03-22 |
| DE69319513T2 (en) | 1999-01-14 |
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Assignee: Aetna Technology Co., Ltd. | Beijing Antai Jing Steel International Trade Co., Ltd. | Shanghai Aetna high-Amorphous Metal Co., Ltd. Assignor: Hitachi Metals Co., Ltd. Contract fulfillment period: From September 19, 2005 to September 3, 2013 Contract record no.: 051000030096 Denomination of invention: Ultrafine grained alloy with excellent corrosion resistance Granted publication date: 19971129 License type: General permission Record date: 20051101 |
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