Summary of the invention
One of purpose of the present invention be to provide have concurrently excellent high frequency performance, strong amorphous formation ability, cheaply, the amorphous powdered alloy of low oxygen content that can be by the atomization method preparation and preparation method thereof.
Two of purpose of the present invention be to provide adopt above-mentioned amorphous powdered alloy preparation, have excellent high frequency performance magnetic core and preparation method thereof.
In order to achieve the above object, the present invention is achieved in that
One aspect of the present invention has provided a kind of amorphous powdered alloy with good high-frequency soft magnetic performance, and its alloying component atomic percent composition satisfies relational expression: (Fe
1-xM
x)
100-a-b-cP
aT
bD
cWherein, M is at least a among Co, the Ni; T is the two or more and Al among C, B, the Si; D is at least a among Sn, Cr, Mn, Mo, W, V, Nb, Ta, Ti, Zr, Hf, Pt, Pd, the Au; X is 0.01-0.16; A is 8-15; B is 10-25; C is 0.5-6.Preferably, x is 0.01-0.12; A is 9-12; B is 10-23; C is 1-5.22≤(a+b+c)≤38。
Reduction glass transformation temperature Trg 〉=0.53 of this amorphous powdered alloy, Trg=Tg/Tm wherein, Tg is a glass transformation temperature, Tm is an alloy melting point.Supercool liquid phase region Δ Tx 〉=20K, Δ Tx=Tx-Tg wherein, Tx is a crystallization temperature.Oxygen content in power is below 4000ppm.
Another aspect of the present invention has provided a kind of preparation method with amorphous powdered alloy of good high-frequency soft magnetic performance, alloy with mentioned component, adopt atomizing type to prepare alloy powder, described atomizing type is water atomization or aerosolization, and described aerosol turns to vacuum aerosolization, antivacuum aerosolization, regulate a kind of in the aerosolization.
The apparent density of powder ρ that this method obtains satisfies: ρ 〉=2.4g/cm
3
A third aspect of the present invention has provided a kind of non-crystaline amorphous metal powder magnetic core with good high-frequency soft magnetic performance, comprise following components in weight percentage: insulating compound 0.2%-7%, bonding agent 0.01-5%, lubricant 0.01-2%, all the other are above-mentioned non-crystaline amorphous metal powder.
Wherein, described insulating compound is selected from following at least a or its combination of respectively organizing in the material:
Be selected from SiO
2, CaO, Al
2O
3, TiO
2Oxide powder;
Be selected from the salt of silicates, phosphoric acid salt;
Be selected from mica powder, kaolinic mineral powder.
Described bonding agent is organic bonding agent and/or inorganic adhesive, and wherein: the organic bonding agent is selected from least a in the epoxylite, and inorganic adhesive is selected from least a in the phosphoric acid salt.
Described lubricant is selected from stearate, talcum powder is at least a or its combination.
The magnetic property of this magnetic core satisfy following at least one:
Magnetic permeability is more than 35;
Quality factor q is not less than 30 under 1MHz;
Under 100kHz, be not less than 98% than magnetic permeability, under 1MHz, be not less than 90%;
Maximum field is the pairing coercive force H of the static hysteresis loop of 2000A/m
cBelow 70A/m.
A fourth aspect of the present invention has provided a kind of preparation method with non-crystaline amorphous metal powder magnetic core of good high-frequency soft magnetic performance, and this method may further comprise the steps:
(a), insulating compound, the 0.2-7% that adopts above-mentioned amorphous powdered alloy and percentage by weight to be 0.2-7%
Bonding agent and the mix lubricant of 0.01-5% and be dried to dry powder;
(b), above-mentioned dried powder is made the magnetic core under 500MPa-3000MPa pressure;
(c), the magnetic core with press forming carries out annealing in process below the amorphous crystallization temperature.
After described step (c), further may further comprise the steps: (d), the processing of spraying paint of magnetic core; (e), the magnetic core performance detects.
In the described step (c), described magnetic core annealing in process temperature is at (T
x-100 ℃) to T
xBetween, T
xBe the amorphous crystallization temperature; Be annealed into 5 minutes to 300 minutes; Atmosphere is a kind of in vacuum, nitrogen, the argon gas atmosphere.
In the described step (c), annealing temperature is at (T
x-70 ℃) to (T
x-20 ℃) between, T
xBe the amorphous crystallization temperature.
The magnetic property of the magnetic core that this preparation method obtains satisfy following at least one:
Magnetic permeability is more than 35;
Quality factor q is not less than 30 under 1MHz;
Under 100kHz, be not less than 98% than magnetic permeability, under 1MHz, be not less than 90%;
Maximum field is the pairing coercive force H of the static hysteresis loop of 2000A/m
cBelow 70A/m.
In sum, the invention provides a kind of technical scheme for preparing amorphous powdered alloy and amorphous magnetic core thereof, wherein by improvement to alloying component, make antioxygenic property, the amorphous formation ability of alloy be improved, therefore can adopt atomization method prepare amorphous powdered alloy, this powder through insulation processing and with the mixed dry powder that is prepared into of a small amount of bonding agent, compression moulding obtains amorphous magnetic core through appropriate heat treatment.Specifically be described below:
The improvement of alloying component
Amorphous powdered alloy of the present invention is a main component with magnetically soft alloy Fe, contains a spot of Co, Ni, so soft magnet performance is better, and the adding of Co, Ni can improve the antioxygenic property of powder; The present invention simultaneously contains more amorphous forming element P, Al, C, B, Si, therefore can form amorphous powdered alloy; And the present invention can contain more than one in the elements such as Sn, Cr, Mn, Mo, W, V, Nb, Ta, Ti, Zr, Hf, Pt, Pd, Au, can further improve alloy amorphous formation ability and antioxygenic property.The amorphous formation ability that the adding of element such as Sn, Zr can effectively raising powder for example; And the adding of elements such as Cr, Mo can improve the antioxygenic property of powder when improving amorphous formation ability.
Amorphous powdered alloy of the present invention, its alloying component atomic percent satisfies following formula:
(Fe
1-xM
x)
100-a-b-cP
aT
bD
c
Wherein, M is at least a among Co, the N i; T is the two or more and Al among C, B, the Si;
D is at least a among Sn, Cr, Mn, Mo, W, V, Nb, Ta, Ti, Zr, Hf, Pt, Pd, the Au; X is 0.01-0.16; A is 8-15; B is 10-25; C is 0.5-6.
For amorphous powdered alloy of the present invention, Co, the preferred 1at% of Ni content are to 12at%; The preferred 9at% of P content is to 12at%; Al, C, the preferred 10at% of B, Si are to 23at%; Sn, Cr, Mn, Mo, W, V, Nb, Ta, Ti, Zr, Hf, Pt, the preferred 1at% of Pd, Au are to 5at%.
For amorphous powdered alloy of the present invention, preferred Fe, Co, Ni element sum are that 62at% is to 78at%; Preferred P, Al, C, B, Si, Sn, Cr, Mn, Mo, W, V, Nb, Ta, Ti, Zr, Hf, Pt, Pd, Au element sum are that 22at% is to 38at%.
Alloy of the present invention can contain a small amount of inevitably O and other impurity, and the content sum of other impurity is not more than 0.5wt%.
Atomization prepares amorphous powdered alloy
Amorphous powdered alloy of the present invention has strong amorphous formation ability, can prepare amorphous powdered alloy by atomization method; Its supercooling liquid phase region Δ T
x〉=20K (Δ T
x=T
x-T
g, T wherein
xExpression crystallization temperature, T
gThe expression glass transformation temperature), reduction glass transformation temperature T
Rg〉=0.53 (T
Rg=T
g/ T
m, T wherein
mThe expression alloy melting point).
Amorphous powdered alloy of the present invention can prepare under antivacuum state by the water atomization method, and its amorphous powdered alloy particle size can reach more than the 75 μ m, and oxygen content in power is below 4000pp.This water atomization amorphous powdered alloy apparent density has following feature: between positive 300 orders (about 49 μ m), apparent density of powder is greater than 2.7g/cm at negative 200 orders (about 74 μ m) for particle size
3To between positive 400 orders (about 38 μ m), apparent density of powder is greater than 2.6g/cm at negative 300 orders (about 49 μ m) for particle size
3Particle size is for below negative 400 orders (about 38 μ m), and more than the 5 μ m, the apparent density of amorphous powdered alloy is greater than 2.5g/cm
3
Among the present invention, preparation magnetic core water atomization amorphous powdered alloy, its oxygen content is that 4000ppm is following.Too high oxygen level, the powder magnetic property worsens; Adopt this powder preparation magnetic core, the magnetic core performance is not good, shows as that magnetic permeability reduces, coercive force is big.
Among the present invention, preparation magnetic core water atomization amorphous powdered alloy, its apparent density is 2.5g/cm
3More than.If apparent density of powder is too little, it is bad to prepare the magnetic core performance.Because apparent density of powder is too small, normally contains reasons such as increased number of stomata in too little or powder shape complexity or the powder and cause owing to particle size.Adopt the magnetic core of this powder preparation, its density is low excessively, and distributed air gaps is too big in the magnetic core, and powder core magnetic permeability is low, and powder core coercive force is big, and loss is higher.Amorphous powdered alloy apparent density of the present invention is 2.5g/cm
3More than, preferred 2.8g/cm
3More than.
It is slow slightly that aerosolization method and water atomization method are compared cooling rate.Alloy system of the present invention, also can pass through vacuum aerosolization, antivacuum aerosolization, adjusting aerosolization (employing gas atomization alloy liquation powdered, the atomization method that adopts water that powder particle is cooled off again) etc. atomization method prepares the amorphous powdered alloy of subglobular, its amorphous powdered alloy particle size can reach more than the 50 μ m, and oxygen content in power is below 1500ppm.The apparent density of aerosolization amorphous powdered alloy is greater than 3.5g/cm
3
Prepare the magnetic core with amorphous powdered alloy
Among the present invention, the used aerosolization amorphous powdered alloy of preparation magnetic core, its oxygen content is that 1500ppm is following.Adopt the magnetic core performance of this powder amorphous powdered alloy preparation good, magnetic permeability height, coercive force are low.Compare with water atomized powder, the magnetic core cost of aerosolization powder preparation increases to some extent, and performance increases, and can satisfy the demand of some high-end products.
The magnetic core method of amorphous powdered alloy preparation of the present invention may further comprise the steps:
1, powder and megohmite insulant, bonding mix and greasing substance mixes and is dried to dry powder;
2, powder compaction becomes the magnetic core;
3, the magnetic core is carried out annealing in process;
4, the magnetic core processing of spraying paint;
5, the magnetic core performance detects.
The amorphous powdered alloy that preparation is finished sieves, and can adopt testing sieve, and standard is bounced realizations such as the reciprocating sieve of formula reciprocating sieve, other types and air-flowing type powder classification equipment.Prepare the magnetic ring according to following steps then:
Step 1
In order to improve magnetic core resistivity, reduce eddy current loss, improve the magnetic permeability under the high frequency, the megohmite insulant of the preferred following kind of the present invention and amorphous powdered alloy carry out mix insulation: 1, oxide powder, as SiO
2, Cao, Al
2O
3, TiO
2Deng, the common stable in properties of oxide powder, insulation, heat resistance are good, and cheap.2, silicates, phosphoric acid salt etc.3 other mineral powder are as mica powder, kaolin etc.4, the surface film of chemical method generation or the surface oxidation of generation.
Adopt above-mentioned megohmite insulant that amorphous powdered alloy is insulated, the megohmite insulant percentage by weight should be between the 0.2wt%-7wt% of mixture total weight amount.If megohmite insulant is very few, amorphous powdered alloy is difficult to obtain isolating more fully, contacts more; Perhaps insulating barrier is too thin, the easy breakdown insulating effect that loses under the electromagnetic induction effect, thus the magnetic core loss is big, and the high frequency magnetic permeability is low.If insulation divides too much, the interval between the powder is excessive, and magnetic core magnetic permeability reduces.The preferred weight percentage ranges of megohmite insulant is that 0.5wt% is to 5wt%.
The amorphous powdered alloy processability is relatively poor, especially aerosolization powder, difficult forming, the preferred following kind adhesive substance of the present invention is as adhesives: 1, organic bonding agent, as epoxylite, epoxylite generally uses as adhesives is at present industrial, and especially adhesive effect is better after mixing use with curing agent.2, inorganic adhesive, as phosphoric acid salt etc., the advantage of inorganic adhesive is that thermal endurance is good, and itself has good insulation property, and insulation and bonding double action are arranged, its amount can suitably increase, thereby can sufficient bonding powder.
Adopt above-mentioned adhesives, its bonding dosage accounts for mixture percentage and is no more than 5%.If bonding dosage is too much, the magnetic core performance descends, and magnetic permeability reduces.
The mixing of greasing substance its role is to: 1, make powder the time be easy to flow, thereby improve magnetic core density in compacting, 2, magnet ring and compacting tool set be difficult for taking place bonding, thereby be easy to the demoulding.The preferred stearate profit of the present invention, talcum powder etc. are as greasing substance, and its weight should be not more than the 2wt% of mixture weight.If lubricant is too much, can cause amorphous powdered alloy density decline in the magnetic core, thereby the magnetic core performance worsens, magnetic permeability reduces.
Mix fully in order to obtain insulating, the densification of powder core, the amorphous magnetic core that has excellent magnetic characteristics, the total amount of the preferred megohmite insulant of the present invention, adhesive substance and lubricant accounts for the 0.5wt% of mixture total weight amount to 10wt%; More preferably percentage by weight is that 1wt is to 7wt%.
Step 2
The preferred 500MPa-3000MPa of amorphous powdered alloy briquetting pressure of the present invention.Pressure is less than 500MPa, and powder is difficult to moulding, or has crackle to exist after the moulding, and magnetic permeability is low, and the magnetic core performance is not good.Pressure is greater than 3000MPa, and it is big that mould bears pressure, damage easily, and powder insulation difficulty, powder core loss height, quality factor are not good, and are therefore bad.Magnetic core briquetting pressure more preferably 800MPa to 2500Mpa.
Step 3
Amorphous powdered alloy cooling rate in preparation process is very fast, and unavoidably there is stress in inside; The magnetic core is subjected to the squeezing action of stirring action, press in preparation process, magnetic in-core portion also exists stress, the performance of these stress influence magnetic cores.By amorphous magnetic core is carried out annealing in process, can reach the purpose of eliminating powder internal stress, magnetic in-core portion's stress and improving magnetic property.Amorphous magnetic core annealing in process temperature should satisfy following condition: 1, annealing temperature should be carried out below the amorphous crystallization temperature.Because magnetic property worsens rapidly after the amorphous powdered alloy crystallization, show as that magnetic permeability reduces rapidly, loss increases.2, annealing temperature should not be lower than (T
x-100 ℃), T wherein
xBe the amorphous crystallization temperature.3, the preferred (T of powder annealing temperature
x-70 ℃) to (T
x-20 ℃) between.Because powder core annealing temperature is low excessively, thermal agitation is less, the amorphous core internal stress is difficult to fully be eliminated, and magnetic property is difficult to fully be promoted.The amorphous core annealing time should satisfy following condition: 1, powder core annealing time should be less than 3 hours.Because annealing time is long, efficient is low, increases manufacturing cost.2, powder core annealing time should because annealing time is too short, be difficult to reach the purpose of uniform treatment greater than 5 minutes during batch process, and the powder core performance is difficult to homogeneous.3, between preferred 30 minutes to 90 minutes of the powder core annealing time.Above-mentioned annealing process, the present invention preferably carries out under protective atmosphere, and protective atmosphere can be vacuum state, hydrogen state, nitrogen state or argon gas state.
Step 4
For reaching the erosion that protection magnetic core is avoided the dry linting phenomenon occurring and is subjected to air etc., cause magnetic property to worsen, need be to the protection of spraying paint of magnetic core, the epoxy resin that the material preferred consolidation of spraying paint stress ratio is less or epoxy resin and polyester mixture.The preferred 50 μ m of coating thickness are to 300 μ m.
Step 5
Following method is adopted in the detection of each parameter of amorphous magnetic core performance of the present invention respectively: 1, the detection method of inductance and quality factor q, and adopting diameter is the copper enamelled wire of 0.2mm, uniform winding 10 circles are measured with the accurate electric impedance analyzer of Agilent 4294A; The magnetic permeability through type of magnetic core
Calculate, wherein l (is unit with cm) is the average length of magnetic path, and N is a coil turn, and A is that the magnetic circuit area is (with cm
2Be unit).2, the measurement of magnetic core static hysteresis loop adopts the simulation ballistic method to measure, and maximum field is 2000A/m.
Adopt alloy powder of the present invention, the magnetic core of using method for preparing has good soft magnet performance under high frequency.Particularly, amorphous magnetic core performance satisfies: under the frequency of 500kHz, quality factor is greater than 50, and magnetic permeability is greater than 40; Under the frequency of 1MHz, quality factor are greater than 30, and magnetic permeability is greater than 40; Under the frequency of 3MHz, magnetic core quality factor are greater than 20, and magnetic permeability is greater than 40; In the 1M scope, magnetic permeability descends less than 10% magnetic permeability at 100K.
Non-crystaline amorphous metal according to technical scheme preparation of the present invention has high amorphous formation ability and good antioxygenic property.This alloy has characteristics such as amorphous formation ability is strong, antioxygenic property good, soft magnet performance is superior concurrently, the amorphous powdered alloy that can prepare low oxygen content by atomization method obtains having high-gradient magnetism energy, low oxygen content, amorphous powdered alloy and corresponding magnetic ring thereof cheaply.
Specific embodiments
Embodiment 1
Present embodiment adopts the Fe of water atomization method preparation
69Ni
5Al
4Sn
2P
10C
2B
4Si
4(the composition sequence number is 1) amorphous powdered alloy, raw material selection Fe, Ni, Al, Sn, P-Fe alloy, B-Fe alloy, graphite and Si.
The pattern photo of powder is seen Fig. 1.As seen from the figure, small particle powder is spherical substantially, and the bulky grain powder is that ellipsoid is capable, and small quantities of powder is an irregular powder.
Powder x-ray diffraction the results are shown in Figure 2.As seen from the figure, there is tangible wide collection of illustrative plates in X-ray diffraction, and does not have significant crystallization peak to exist, and illustrates that alloy powder is an amorphous structure, so Fe
72Ni
2Al
4Sn
2P
10C
2B
4Si
4Series can prepare amorphous powdered alloy by the water atomization method.
Fe
72Ni
2Al
4Sn
2P
10C
2B
4Si
4Powder DSC curve is seen Fig. 3.The programming rate that adopts when DSC measures is 10K/ minute.As seen from the figure, alloy glass transformation temperature T
gBe 646K, crystallization temperature T
xBe 695K.Its fusing point of high temperature dsc measurement T
mBe 1209K, thereby can obtain the supercool liquid phase region Δ T of this alloy
xBe 49K, reduction glass transformation temperature T
RgBe 0.54.
Oxygen content in power the analysis showed that oxygen content in power is 3500ppm, illustrates that alloy has stronger antioxygenic property, and oxygen content is lower.
Screening obtains-300 purpose amorphous powdered alloys, at 440 ℃ of isothermal annealing 30min, adopts nitrogen protection in the annealing process.SiO with amorphous powdered alloy and 1.5wt%
2Powder, 1wt% epoxy resin, 0.3wt% zinc stearate evenly mix and oven dry, adopt alcohol as cosolvent during mixing.Adopt the pressure forming magnetic core of 2Gpa.The annealing of magnetic core is carried out under vacuum state, and annealing temperature is 400 ℃, and annealing time is 90 minutes.Adopt epoxy resin and polyester mixture that the magnetic wicking surface is sprayed, coating layer thickness is 100um.
Above-mentioned magnetic core be that static hysteresis loop under the 2000A/m provides in Fig. 4 at maximum field.As seen from the figure, magnetic core basic permanent permeance, its coercive force H of keeping in the test magnetic field range
cBe 45A/m.
Provided the permeability measurement result of above-mentioned magnetic core magnetic property among Fig. 5.As seen from the figure, this magnetic core magnetic permeability is 46.9, and along with the variation magnetic core of frequency is keeping excellent permanent permeance, in the 5MHz scope, magnetic permeability drops to 46.4 by 46.9 at 6.3k, and the percentage of decline is less than 2%.
Provided of the variation of these magnetic core quality factor among Fig. 6, provided the comparing result of Fe NiMo magnetic core as a comparison with frequency.As seen from the figure, amorphous alloy magnetic core has higher quality factor at high-frequency region.
Embodiment 2
Present embodiment adopts the Fe-Ni-Sn-Al-P-C-B-Si series amorphous powdered alloy of water atomization method preparation, raw material selection Fe, Ni, Sn, Al, P-Fe alloy, graphite, B-Fe alloy and Si.
The concrete composition of present embodiment sees Table 1, and the glass transformation temperature of corresponding alloy, crystallization temperature, fusing point, reduction glass transformation temperature, supercool liquid phase region width are also listed in table 1 respectively.By table as seen, this series alloy, except that composition 10 takes place the crystallization, other composition alloys all have high reduction glass transformation temperature, and minimum is 0.54, is 0.58 to the maximum, and alloy supercool liquid phase region width is greater than 20K.
Table 1
Sequence number |
Alloy atom is formed |
T
g/K
|
T
x/K
|
T
m/K
|
T
g/T
m |
(T
x-T
g)/K
|
2 |
Fe
68.5Ni
3Al
7P
11.5C
3B
5 |
650 |
700 |
1209 |
0.54 |
50 |
3 |
Fe
67Ni
7Sn
2Al
4P
10B
4C
2Si
4 |
654 |
694 |
1208 |
0.54 |
40 |
4 |
Fe
70.5Ni
10Sn
1Al
4P
13C
2B
3Si
6 |
665 |
690 |
1204 |
0.55 |
25 |
5 |
Fe
71Ni
4Sn
4Al
1P
10C
4B
2Si
4 |
666 |
698 |
1206 |
0.55 |
32 |
6 |
Fe
72Ni
2Sn
1Al
3P
9C
2B
8Si
3 |
675 |
703 |
1211 |
0.56 |
28 |
7 |
Fe
73Ni
1Sn
2Al
4P
10C
2B
4Si
4 |
668 |
715 |
1202 |
0.56 |
47 |
8 |
Fe
73.5Ni
2Sn
5P
9.5C
2B
5Si
3 |
680 |
702 |
1200 |
0.57 |
22 |
9 |
Fe
74.5Ni
1Sn
2Al
2P
11.5B
4Si
5 |
698 |
729 |
1210 |
0.58 |
31 |
10 |
Fe
77Ni
3Sn
1Al
3P
8C
2B
2Si
4 |
- |
- |
1208 |
- |
- |
Contrast 1 |
Fe
68.5Ni
3Al
7P
11.5C
3B
3Si
2 |
652 |
700 |
1209 |
0.54 |
48 |
The amorphous powdered alloy of mentioned component, the oxygen content and the apparent density of its negative 300 amorphous powdered alloys provide in table 2.By table as seen, this series alloy is except that contrast 1, and apparent density is 2.5g/cm
3More than, oxygen content is below the 3900ppm, illustrates that alloy has stronger antioxygenic property.
The amorphous powdered alloy of mentioned component sieved obtain-300 purpose amorphous powdered alloys,, adopt vacuum protection in the annealing process at 440 ℃ of isothermal annealing 30min.SiO with amorphous powdered alloy and 1wt%
2Powder, 1.5wt% epoxy resin, 0.3wt% zinc stearate evenly mix and oven dry, adopt alcohol as cosolvent during mixing.Adopt the pressure forming magnetic core of 2Gpa.The annealing of magnetic core is carried out under vacuum state, and annealing temperature is 440 ℃, and annealing time is 60 minutes.Adopt epoxy resin and polyester mixture that the magnetic wicking surface is sprayed, coating layer thickness is 100um.
Adopt the amorphous alloy magnetic core of method for preparing, its performance provides in table 2, wherein contrasts 1 for atomization method is improper, the amorphous powdered alloy with elevated oxygen level, low-apparent-density that obtains.By table 2 as seen, 1 compare with contrast, the alloy magnetic powder core that oxygen content in power is low, apparent density is bigger has better performance, is embodied in that coercive force is low, magnetic permeability is high; Composition 10, because crystallization has taken place, magnetic property worsens; The alloy of other compositions (remove 10, contrast 1) coercive force is less than 60A/m, and magnetic permeability is all greater than 35, than under the magnetic permeability 100kHz greater than 98%, under the 1MHz greater than 90%, quality factor are greater than 40 under the 1MHz.
Table 2
Sequence number |
Oxygen content (ppm) |
Apparent density (g/cm
3)
|
Structure |
H
c (A/m)
|
μ
10kHz |
μ
100kHz |
μ
1MHz |
Q
10kHz |
Q
100kHz |
Q
1MHz |
2 |
3500 |
2.6 |
Amorphous |
53 |
43 |
43 |
41 |
6 |
32 |
72 |
3 |
2600 |
2.7 |
Amorphous |
40 |
60 |
60 |
59 |
8 |
35 |
77 |
4 |
3800 |
2.5 |
Amorphous |
40 |
53 |
53 |
53 |
5 |
29 |
66 |
5 |
3000 |
2.7 |
Amorphous |
26 |
42 |
42 |
42 |
6 |
33 |
75 |
6 |
3300 |
2.6 |
Amorphous |
34 |
39 |
39 |
39 |
4.5 |
30 |
69 |
7 |
2800 |
2.6 |
Amorphous |
35 |
62 |
62 |
60 |
5.5 |
32 |
75 |
8 |
3900 |
2.5 |
Amorphous |
50 |
38 |
38 |
38 |
4 |
27 |
48 |
9 |
3500 |
2.6 |
Amorphous |
47 |
46 |
46 |
44 |
4.5 |
28 |
63 |
10 |
3200 |
2.8 |
Crystallization |
120 |
8 |
8 |
8 |
5 |
7 |
33 |
Contrast 1 |
5200 |
2.3 |
Amorphous |
65 |
35 |
35 |
35 |
4.5 |
27 |
60 |
Embodiment 3
Present embodiment adopts the Fe-Co-Cr-Sn-Al-P-C-B-Si series amorphous powdered alloy of water atomization method preparation, raw material selection Fe, Co, Cr, Sn, Al, P-Fe alloy, graphite, B-Fe alloy and Si.
The concrete composition of present embodiment sees Table 3, and the glass transformation temperature of corresponding alloy, crystallization temperature, fusing point, reduction glass transformation temperature, supercool liquid phase region width are also listed in table 3 respectively.By table as seen, this series alloy, except that composition 20 can not form whole amorphous, other composition alloys all had high reduction glass transformation temperature, and minimum is 0.58, is 0.60 to the maximum, and alloy has supercool liquid phase region width greater than 20K.
Table 3
Sequence number |
Alloy atom is formed |
T
g/K
|
T
x/K
|
T
m/K
|
T
g/T
m |
(T
x-T
g)/K
|
11 |
Fe
70Co
2Cr
2Sn
2Al
4P
10C
2B
4Si
4 |
705 |
744 |
1208 |
0.58 |
39 |
12 |
Fe
68.5Co
2Cr
1Sn
2Al
7P
11.5C
3B
3Si
2 |
715 |
740 |
1197 |
0.60 |
25 |
13 |
Fe
68.5Co
1Cr
5Sn
3Al
2P
11.5C
5B
2Si
2 |
715 |
753 |
1223 |
0.58 |
38 |
14 |
Fe
69.5Co
1Cr
0.5Sn
1Al
4P
13C
2B
3Si
6 |
701 |
738 |
1183 |
0.59 |
37 |
15 |
Fe
69.5Co
2Cr
4Sn
4Al
1P
10C
4B
2Si
4 |
723 |
758 |
1215 |
0.60 |
35 |
16 |
Fe
70Co
2Cr
2Sn
1Al
3P
9C
2B
8Si
3 |
704 |
739 |
1216 |
0.58 |
35 |
17 |
Fe
71Co
2Cr
1Sn
2Al
4P
10C
2B
4Si
4 |
671 |
724 |
1204 |
0.56 |
53 |
18 |
Fe
71.5Co
5Cr
1Al
2P
10.5C
2B
5Si
3 |
698 |
731 |
1201 |
0.58 |
33 |
19 |
Fe
72.5Co
2Cr
2Al
4P
9.5C
1B
4Si
5 |
701 |
732 |
1209 |
0.58 |
31 |
20 |
Fe
75Co
3Cr
3Al
3P
8C
2B
2Si
4 |
- |
- |
1250 |
- |
- |
The amorphous powdered alloy of mentioned component, the oxygen content and the apparent density of its negative 300 amorphous powdered alloys provide in table 4.By table as seen, this series alloy apparent density all is not less than 2.5g/cm
3, oxygen content illustrates that all less than 3300ppm alloy has stronger antioxygenic property.
The amorphous powdered alloy of mentioned component sieved obtain-300 purpose amorphous powdered alloys,, adopt vacuum protection in the annealing process at 440 ℃ of isothermal annealing 30min.SiO with amorphous powdered alloy and 1wt%
2Powder, 1.5wt% epoxy resin, 0.3wt% zinc stearate evenly mix and oven dry, adopt alcohol as cosolvent during mixing.Adopt the pressure forming magnetic core of 2Gpa.The annealing of magnetic core is carried out under vacuum state, and annealing temperature is 440 ℃, and annealing time is 60 minutes.Adopt epoxy resin and polyester mixture that the magnetic wicking surface is sprayed, coating layer thickness is 100um.
Adopt the amorphous alloy magnetic core of method for preparing, its performance provides in table 4, by table 4 as seen, removes composition 20 crystallization takes place, and the magnetic core performance worsens, and all the other compositions all have better magnetic property, and magnetic permeability is not less than 45.
The alloy of other compositions (remove 10, contrast 1) coercive force is less than 60A/m, magnetic permeability all greater than 35,1 than under the magnetic permeability 00kHz greater than 98%, under the 1MHz greater than 90%, quality factor are greater than 60 under the 1MHz.
Table 4
Sequence number |
Oxygen content (ppm) |
Apparent density (g/cm
3)
|
Structure |
H
c (A/m)
|
μ
10kHz |
μ
100kHz |
μ
1MHz |
Q
110kHz |
Q
100kHz |
Q
1MHz |
11 |
2600 |
2.8.0 |
Amorphous |
46 |
48 |
48 |
47 |
7 |
34 |
72 |
12 |
2900 |
2.9 |
Amorphous |
37 |
60 |
60 |
58 |
8 |
38 |
85 |
13 |
2500 |
2.8 |
Amorphous |
40 |
65 |
65 |
64 |
7 |
35 |
80 |
14 |
3000 |
2.8 |
Amorphous |
41 |
65 |
65 |
64 |
6 |
33 |
75 |
15 |
2700 |
2.6 |
Amorphous |
49 |
60 |
60 |
59 |
6 |
30 |
72 |
16 |
2800 |
2.6 |
Amorphous |
50 |
53 |
53 |
52 |
6 |
32 |
75 |
17 |
3300 |
2.5 |
Amorphous |
47 |
49 |
49 |
48 |
5 |
27 |
64 |
18 |
3000 |
2.7 |
Amorphous |
54 |
45 |
45 |
44 |
4.5 |
28 |
68 |
19 |
3200 |
2.7 |
Amorphous |
52 |
46 |
46 |
45 |
4.5 |
28 |
67 |
20 |
2800 |
2.7 |
Crystallization |
118 |
12 |
12 |
12 |
5 |
7 |
34 |
Embodiment 4
Present embodiment adopts antivacuum aerosolization method to prepare Fe-Co-Ni-Cr-Sn-Al-P-C-B-Si series amorphous powdered alloy, raw material selection Fe, Co, Ni, Cr, Sn, Al, P-Fe alloy, graphite, B-Fe alloy and Si.
The concrete composition of present embodiment sees Table 5, and the glass transformation temperature of corresponding alloy, crystallization temperature, fusing point, reduction glass transformation temperature, supercool liquid phase region width are also listed in table 5 respectively.By table as seen, this series alloy, except that composition 25 can not form whole amorphous, other composition alloys all had high reduction glass transformation temperature, and minimum is 0.58, is 0.60 to the maximum, and alloy has supercool liquid phase region width greater than 20K.
Table 5
Sequence number |
Alloy atom is formed |
T
g/K
|
T
x/K
|
T
m/K
|
T
g/T
m |
(T
x-T
g)/K
|
21 |
Fe
71Co
2Sn
2Al
4P
10C
2B
5Si
4 |
703 |
740 |
1208 |
0.58 |
37 |
22 |
Fe
71Ni
2Cr
1Al
4P
11C
2B
6Si
2 |
715 |
745 |
1197 |
0.60 |
30 |
23 |
Fe
72.5Co
1Ni
1Sn
3Al
2P
11.5C
5B
2Si
2 |
708 |
746 |
1223 |
0.58 |
38 |
24 |
Fe
63Ni
3Co
3Cr
0.5Al
4P
13C
2B
3Si
6 |
720 |
743 |
1183 |
0.61 |
23 |
25 |
Fe
63Ni
5Co
3Cr
2Sn
4Al
1P
10C
4B
2Si
4 |
- |
- |
1215 |
- |
- |
The amorphous powdered alloy of mentioned component, the oxygen content and the apparent density of its negative 350 amorphous powdered alloys provide in table 6.By table as seen, this series alloy apparent density all is not less than 3.6g/cm
3, oxygen content is all less than 2000ppm.
The amorphous powdered alloy of mentioned component sieved obtain-350 purpose amorphous powdered alloys,, adopt vacuum protection in the annealing process at 400 ℃ of isothermal annealing 30min.SiO with amorphous powdered alloy and 1wt%
2Powder, 2wt% epoxy resin, 0.3wt% zinc stearate evenly mix and oven dry, adopt alcohol as cosolvent during mixing.Adopt the pressure forming magnetic core of 2.4Gpa.The annealing of magnetic core is carried out under vacuum state, and annealing temperature is 440 ℃, and annealing time is 60 minutes.Adopt epoxy resin and polyester mixture that the magnetic wicking surface is sprayed, coating layer thickness is 100um.
Adopt the amorphous alloy magnetic core of method for preparing, its performance provides in table 6, by table 6 as seen, remove composition 25 crystallization takes place, the magnetic core performance worsens, and the alloy coercive force of other compositions is less than 40A/m, and magnetic permeability is all greater than 60, than under the magnetic permeability 100kHz greater than 98%, under the 1MHz greater than 90%, quality factor are greater than 60 under the 1MHz.
Table 6
Sequence number |
Oxygen content (ppm) |
Apparent density (g/cm
3)
|
Structure |
H
c (A/m)
|
μ
10kHz |
μ
100kHHz |
μ
1MHz |
Q
10kHz |
Q
100kHz |
Q
1MHz |
21 |
1500 |
3.6 |
Amorphous |
32 |
72 |
72 |
70 |
9 |
45 |
98 |
22 |
1200 |
3.7 |
Amorphous |
28 |
70 |
70 |
68 |
9 |
40 |
88 |
23 |
1250 |
3.7 |
Amorphous |
26 |
68 |
68 |
66 |
9 |
40 |
92 |
24 |
1100 |
3.7 |
Amorphous |
25 |
75 |
75 |
73 |
9 |
41 |
96 |
25 |
800 |
3.7 |
Crystallization |
68 |
13 |
13 |
13 |
6 |
9 |
42 |
Embodiment 5
Adopt the method identical with embodiment 1 to prepare amorphous powdered alloy, the magnetic core prepares in each step also identical, and different is to have changed heat treatment temperature.
Provided under the magnetic core 100kHz magnetic permeability among Fig. 7 with the change curve of annealing temperature.As seen from the figure, this magnetic core magnetic permeability raises along with the rising of heat treatment temperature, reaches maximum at 440 ℃ of annexes, and the back reduces along with the rising of annealing temperature, and maximum permeability is about 50.
Quality factor have been provided under magnetic core 100kHz and the 1MHz among Fig. 8 with the change curve of annealing temperature, its Changing Pattern and magnetic permeability Changing Pattern are similar, difference is that it is 380 ℃ of annexes that the maximum quality factor of magnetic core appear at annealing temperature, and maximum quality factor are about 75 during 100kHz; Be about 35 during 1MHz.
Having provided maximum field among Fig. 9 is the pairing coercive force H of 2000A/m magnetic core static hysteresis loop
cChange curve with annealing temperature.As seen from the figure, the variation tendency of coercitive variation tendency and magnetic core magnetic permeability is opposite fully, and minimum coercive force is about 44A/m.