CN1038007C - Gallium-containing rare earth-iron-based permanent magnet carbide and preparation method thereof - Google Patents
Gallium-containing rare earth-iron-based permanent magnet carbide and preparation method thereof Download PDFInfo
- Publication number
- CN1038007C CN1038007C CN 93105618 CN93105618A CN1038007C CN 1038007 C CN1038007 C CN 1038007C CN 93105618 CN93105618 CN 93105618 CN 93105618 A CN93105618 A CN 93105618A CN 1038007 C CN1038007 C CN 1038007C
- Authority
- CN
- China
- Prior art keywords
- iron
- preparation
- gallium
- permanent magnet
- carbide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 18
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000010791 quenching Methods 0.000 claims abstract description 19
- 230000000171 quenching effect Effects 0.000 claims abstract description 15
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 20
- 150000002910 rare earth metals Chemical class 0.000 claims description 18
- 238000002844 melting Methods 0.000 claims description 14
- 230000008018 melting Effects 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052735 hafnium Inorganic materials 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 42
- 239000000843 powder Substances 0.000 abstract description 19
- 238000005245 sintering Methods 0.000 abstract description 13
- AWWAHRLLQMQIOC-UHFFFAOYSA-N [Fe].[Sm] Chemical compound [Fe].[Sm] AWWAHRLLQMQIOC-UHFFFAOYSA-N 0.000 abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 20
- 229910045601 alloy Inorganic materials 0.000 description 18
- 239000000956 alloy Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 11
- 229910052786 argon Inorganic materials 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 239000004615 ingredient Substances 0.000 description 8
- 229910052772 Samarium Inorganic materials 0.000 description 7
- 238000000498 ball milling Methods 0.000 description 7
- 229910001172 neodymium magnet Inorganic materials 0.000 description 7
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 description 6
- 239000003708 ampul Substances 0.000 description 6
- 238000000137 annealing Methods 0.000 description 6
- 239000000696 magnetic material Substances 0.000 description 6
- 230000005389 magnetism Effects 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000003723 Smelting Methods 0.000 description 5
- 230000006698 induction Effects 0.000 description 5
- 238000003825 pressing Methods 0.000 description 5
- 230000004224 protection Effects 0.000 description 5
- -1 rare earth nitride Chemical class 0.000 description 5
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910017112 Fe—C Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- PRQMIVBGRIUJHV-UHFFFAOYSA-N [N].[Fe].[Sm] Chemical compound [N].[Fe].[Sm] PRQMIVBGRIUJHV-UHFFFAOYSA-N 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000003746 solid phase reaction Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000013467 fragmentation Methods 0.000 description 3
- 238000006062 fragmentation reaction Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910000859 α-Fe Inorganic materials 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JZQOJFLIJNRDHK-CMDGGOBGSA-N alpha-irone Chemical compound CC1CC=C(C)C(\C=C\C(C)=O)C1(C)C JZQOJFLIJNRDHK-CMDGGOBGSA-N 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000005347 demagnetization Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910001337 iron nitride Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 206010028347 Muscle twitching Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 229910000938 samarium–cobalt magnet Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Images
Landscapes
- Hard Magnetic Materials (AREA)
Abstract
The invention relates to a rare earth-iron-based permanent magnet carbide containing gallium and a preparation method thereof. The method is characterized in that a proper amount of gallium is added into a samarium-iron-based material, and the samarium-iron-gallium-based material with a 2: 17 type structure is smelted, and the preparation method adopts powder sintering and rapid quenching processes to prepare the anisotropic or high-coercivity isotropic permanent magnet material with high magnetic energy product.
Description
The present invention relates to rare-earth iron-based permanent magnet that contains gallium and preparation method thereof.
The first generation and second generation rare-earth permanent magnet all with cobalt as material of main part, price is expensive.Therefore, prepare the research emphasis that rare earth permanent-magnetic material is people always with iron for cobalt.Up to the present, a most successful example is third generation rare earth permanent-magnetic material-neodymium iron boron, and succeeding in developing of it produces huge economic benefit, but owing to shortcomings such as temperature are low in its office, temperature coefficient is big, makes to use to be restricted.Therefore, explore the target that rare-earth iron-based permanent-magnetic material of new generation has become countries in the world to pursue.
After neodymium iron boron is found, the samarium iron nitrogen of Ireland professor's discovery in 90 years once was considered to most promising novel permanent magnetic material, the samarium iron nitride has uniaxial anisotropy, high saturation and magnetic intensity and high-curie temperature, has possessed the basis of making permanent magnet fully.The most over the past two years, formed samarium iron nitrogen studies climax (patent of invention of this respect is seen national patent application number 92103831.3) at world wide.But samarium iron nitrogen also has its fatal shortcoming: it is to pass through the low temperature nitriding with the method for gas-solid phase reaction to obtain, thereby can not obtain by raw-material direct smelting or traditional powder metallurgical technique.Therefore, they are metastable, just are decomposed into α-Fe and rare earth nitride fully in about 700 ℃ or lower temperature, and can not return to the structure of original compound again, thereby be difficult to make high performance magnet.
Before finding rare earth nitride, people were to carry out more research to the rare earth ferrous-carbide.Can prepare the rare earth ferrous-carbide of low carbon content with the method for direct smelting,,, make that temperature is low in the office of magnet, anisotropy field is not high, thereby can not obtain the high-performance magnet because carbon content is low though they also have the basis of preparation permanent magnet.Recently, with preparation samarium iron nitrogen with the quadrat method samarium ferrous-carbide of high-carbon content that has been prepared into merit, its room temperature anisotropy field reaches 15 ± 0.5T, the anisotropy field that is higher than neodymium iron boron magnetic body far away, but owing to adopt the preparation of gas-solid phase reaction method, the carbide of Huo Deing is the same with nitride like this is unsettled, has brought serious difficulty for the preparation of high-performance permanent magnet.
In March, 92, the method for Chinese science worker by rapid quench is successfully to have prepared the high stable rare earth ferrous-carbide of high-carbon content.The fast quenching rare-earth ferrous-carbide has excellent intrinsic magnetic properties, its Curie temperature, saturation magnetization and the anisotropy field all performance in the corresponding rare-earth-iron-nitride of gas-solid phase reaction preparation or carbide are suitable, and be better than neodymium iron boron magnetic body, its outstanding advantage is to be stable at the high temperature more than 1000 ℃, the preparation that helps permanent magnet (has been applied for national patent, application number: 92114793.7).Just the advantage of quick-quenching method is to prepare isotropic magnet.
The objective of the invention is to overcome above-mentioned shortcoming and defect, in the Sm-Fe-C compound of high-carbon content, add an amount of gallium, make it to become 2: 17 type compounds of Sm-Fe-Ga-C base, go out high-performance permanent magnet through powder metallurgy or rapid quench prepared then.
The object of the present invention is achieved like this:
One is by the component adjustment, and it consists of:
(Sm
1-xR
x)
α(Fe
1-yM
y)
100-α-β-γGa
βC
γ
Wherein R is single or more than one element:
Y、Ce、Pr、Nd、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu；
M is single or more than one following element:
Ti、V、Cr、Mn、Co、Ni、Cu、Zr、Nb、Mo、Hf、Ta、W、B、
Al、Si；
α is the 5-15 atomic percentage;
β is the 0.1-14 atomic percentage;
γ is the 5-15 atomic percentage;
X is 0-0.2;
The scope of y is as follows:
Co is 0-0.3; Mn, Ni, Al are respectively 0-0.2; All the other are respectively 0-0.1;
All compositions in above each scope all can be implemented.
Its two method that the rare earth iron carbon permanent magnet that a kind of preparation contains gallium is provided.One of main step of preparation process is as follows:
1. melting
For obtaining the foundry alloy of uniform ingredients, earlier Fe and C are smelted into the Fe-C alloy, use Fe again, Ga, Fe-C and rare earths material are put into vacuum arc furnace ignition and are evacuated to 2 * 10 earlier by the weighing of said ratio composition
-1Pa above (be anti-oxidation, vacuum degree is high for well) charges into the individual atmospheric inert gas (argon etc.) of 0.5-1.5 then and carries out melting, and smelting temperature is 1400-2000 ℃, and the time is 1-30 minute; Also can adopt induction melting, vacuum degree, smelting temperature and time are identical with electric arc melting.The fusion process middle rare earth volatilizees easily than other element.Therefore, rare earths material is added rare earth during proportioning should 2% of weight, and wherein Sm adds 5-20%.
2. annealing
Through step 1, melted alloy has been monophase materials, anneals 0-10 days down at 950-1150 ℃ then, can make the chemical analysis homogenizing of material.Be anti-oxidation, annealing can be carried out under vacuum or inert gas (as argon Ar) protection.
3. broken
For ease of the material pressing under magnetic field, must carry out fragmentation through the material of step 2.At first the material coarse crushing is arrived extremely several millimeters granule of hundreds of micron, adopt means such as ball milling, airflow milling or swing crushing then, directly be crushed to the 0.5-20 micron.Because the easy oxidation of powder, the shattering process powder must carry out under Buchholz protections such as vacuum or nitrogen, argon, or carries out under the protection of organic solvents such as gasoline, acetone, benzinum.
4, magnetic field orientating moulding
Through the broken powder that obtains good single phase property is arranged, the purpose of pressing under magnetic field is that powder is orientated along the C axle.Adding magnetic field intensity in the forming process is 8-20KOe, and briquetting pressure is 0.5-10 ton/square centimeter.Forming process adds magnetic field plus-pressure more earlier, can in magnetic field, once finish, also can with powder in magnetic field with after the lower pressure orientation, take out magnetic field, use the press compacting.
5, sintering
Through the material after the pressing under magnetic field, general density lower (5-6 gram/cubic centimetre), internal voids is big, intensity is low, increases the necessary high temperature sintering operation of passing through for making density of material and intensity.Sintering process can divide for two steps carried out, at first with material at 850-950 ℃ of sintering 0.1-1 hour, so that the gas in the material void discharges as far as possible, and then at 1000-1250 ℃ of high temperature sintering 0.1-5 hour, allly in above each sintering temperature and time range, all can implement, so that the intensity of material and density increase.Can put an amount of samarium metal powder in the sintering process, make it form the samarium vapour pressure, volatilize with the samarium in the control material.Magnet behind oversintering, density can increase to 6.5-7.5 gram/cubic centimetre, and sintering process must have vacuum or inert gas shielding.
6, subsequent heat treatment
Through oversintering, become fine and close magnet, but magnetic property is not high.Yet after heat treatment 0.5-5 hour, the remanent magnetism of magnet, coercive force and magnetic energy product all obviously improve in 500-900 ℃ of vacuum.Step of preparation process two as follows:
1, fast quenching
Getting melted foundry alloy is placed in quartz ampoule or the boron nitride crucible, the bottom of crucible has aperture (aperture 0.1-1.0 millimeter, also twitching one's mouth of 0.1-0.5 mm wide 0.5-10 millimeters long), crucible is put in the middle of the induction coil, below crucible aperture and coil, by putting a metallic roll, roller diameter 10-50 centimetre, roller can be to use Cu, Fe, and Cr or their alloy are made; Another sealing of raw material, crucible, coil and roller is 2 * 10 in vacuum degree in a vacuum
-1When Pa is above, charge into inert gas (as argon) protection; Then raw material is carried out induction heating, heating-up temperature is that 1100-1500 ℃ of time is 0.1-5 minute; After treating that raw material melts substantially, start motor, make roller turn, rotating speed is the 2-60 meter per second, can be selected according to composition proportion and material property; When the roller rotating speed reaches necessary requirement, blow out with the aperture of argon gas being fused into liquid material from crucible bottom, blow gas pressure is the 0.01-2 kg/cm, the liquid that blows out directly is sprayed onto the roller surfaces of rotation, make it solidify cooling very soon, form the 1-20 mm wide, the belt of 10-50 micron thickness.The roller rotating speed is directly controlled the cooldown rate of fast quenching material, and with material property bigger relation is arranged.Samarium iron gallium C-base alloy, control roll rotor speed directly obtain the permanent magnetic material of high-coercive force by fast quenching when the 10-30 meter per second.(＜5at.%) rare-earth iron-based carbide except that principal phase 2: 17, also has α-iron to exist mutually with some impurity after melting to low gallium content, by fast quenching, not only makes α iron and dephasign disappearance formation monophase materials, and makes material have high coercive force.
2, heat treatment
Utilize the described rapid quenching technique of step 1, make the roller rotating speed reach the 40-60 meter per second, directly obtain samarium iron gallium carbon back amorphous alloy, can obtain monophase materials then after the above heat treatment of their crystallization temperature, optimum treatment temperature and time are respectively 500-800 ℃ and 0-2 hour.Material after the crystallization demonstrates high coercive force.
3, fragmentation
Through step 1 or 2, be prepared into the isotropic material of high permanent magnetism performance, become bonded permanent magnet for making material, strip must be crushed to the powder of 0.5-50 micron.Crushing process is identical with the crushing process of powdered metallurgical material.
4, bonding
Through the powder of step 3 fragmentation, add adhesive such as epoxy resin at 5-15 ton/cm2 pressure compacted under, be prepared into bonded permanent magnet.The magnetic energy product of bonded permanent magnet is the 50-70% of the preceding material of bonding.
Preparation method's technological process of the present invention can have following three kinds of modes:
(1) batching-melting-annealing (also can omit)-fragmentation-pressing under magnetic field-sintering-subsequent heat treatment;
(2) batching-melting-fast quenching-fragmentation-bonding;
(3) batching-melting-fast quenching-heat treatment-fragmentation-bonding.The effect of invention:
1, the present invention has overcome the shortcoming that can't prepare the single-phase RE Fe-base compound of high-carbon content by direct smelting by adding an amount of gallium, prepares samarium iron gallium carbon back monophase materials;
2, the rare-earth iron-based carbide of gallium that adds of the present invention's preparation is stable at high temperature, overcome rare-earth iron-based carbide by gas-solid phase reaction preparation fully in the unsettled shortcoming of high temperature, therefore, can adopt traditional powder metallurgical technique to carry out high temperature sintering, prepare anisotropic high performance permanent magnetic materials;
3, the present invention adopts the method for fast quenching or fast quenching after-baking, makes the grain refinement of samarium iron gallium carbon group compound, directly forms high coercive force permanent-magnetic material, and work simplification, cost are reduced;
4, the present invention has high anticorrosion properties with the material of quick-quenching method preparation, and corrosion resistance obviously is better than neodymium iron boron magnetic body;
5, the present invention uses iron to be material of main part, and the magnet cost of preparation is significantly less than traditional samarium cobalt magnet;
6, the samarium iron gallium carbon compound of the present invention's preparation, its Curie temperature and anisotropy field are higher than neodymium iron boron magnetic body, have the thermal stability higher than neodymium iron boron magnetic body.
Below in conjunction with embodiment the present invention is described in further detail.
Accompanying drawing 1a represents melting Sm
9.76Fe
68.29Ga
14.63C
7.32The x x ray diffration pattern x of alloy.
The x x ray diffration pattern x of sample powder behind ball milling of accompanying drawing 1b presentation graphs 1a.
Accompanying drawing 1c represents to be orientated the x x ray diffration pattern x of powder sample.
Accompanying drawing 1d represents the x x ray diffration pattern x of sintered sample.
Accompanying drawing 2 expression Sm
9.76Fe
68.29Ga
14.63C
7.32The demagnetization curve of sintered magnet.
Accompanying drawing 3 expression fast quenching Sm
9.76Fe
68.29Ga
14.63C
7.32The x x ray diffration pattern x of sample.
It is as follows that the present invention prepares the embodiment that adds the rare-earth iron-based carbide of gallium:
Embodiment 1:
Press Sm
2Fe
14Ga
3C
1.5(be 9.76at%Sm, 68.29at%Fe, 14.63at%Ga, and 7.32at%C) ingredient composition uses material purity to be 99.5%Sm, 99.8%Fe, 99.9%Ga and 99.8% Fe-C alloy, the weight ratio of batching sees Table 1, and wherein Sm adds 20% of Sm total amount.The weighing total weight is 25 grams.
Confected materials is put into arc furnace, is evacuated to 3 * 10
-3Pa fills an atmospheric argon gas then, and melting is 4 times under 1400-1700 ℃ (arc current 250-320A), each 1 minute, becomes the uniform button-type alloy of composition after the cooling.X-ray diffraction experiment proves that the sample after the melting is Th
2Zn
17The monophase materials of type structure, as shown in Figure 1a.
Alloy after the melting is put into vacuum annealing furnace, is evacuated to 3 * 10
-3Pa, annealing is 14 hours in 1050 ℃ vacuum, alloy is broken into pieces after being cooled to room temperature, becomes the particle of granularity 0.5-1.0 millimeter.And then carry out ball milling, and ratio of grinding media to material is 25: 1, and the ball milling time is 1 hour, and sample is protected with benzinum in the mechanical milling process, and the average diameter of the good back of mill powder is the 1-3 micron, still is good monophase materials, shown in Fig. 1 b.
Get wherein 2 gram powder, put into the non-magnetic rustproof steel mold, mould is placed between electromagnet two cartridges again, add magnetic field to 18KOe, powder pressing.Remove magnetic field then, take out mould, with the press pressurization, the intensity of pressure is 5 tons/square centimeter again, and the material that presses is along C axle orientation, and density is 5.5 gram/cubic centimetres.Fig. 1 c is the X-ray diffraction spectrum of orientation sample.
The material that presses places vacuum sintering furnace (at a small amount of Sm powder of sample placed around), is evacuated to 3 * 10
-3Pa, annealing is 0.5 hour in 900 ℃ vacuum, charges into 1 atmospheric argon gas again, and sintering is 1 hour in 1160 ℃ argon gas, and the density of magnet is 7.4 gram/cubic centimetres behind the sintering.Fig. 1 d is the X-ray diffraction spectrum of sintered magnet.
Sintered magnet is heat-treated in a vacuum again, and vacuum degree is 3 * 10
-3Pa, heat treatment temperature and time are respectively 750 ℃ and 1 hour.Fig. 2 is the demagnetization curve of magnet, and corresponding agnetic property at room temperature m and density see Table 1.
Embodiment 2-12:
Press table 1 ingredient composition, preparation technology is with embodiment 1, and the agnetic property at room temperature m and the density of magnet see Table 1.
Embodiment 13:
Press embodiment 1 ingredient composition, alloy melting is with embodiment 1.Melted alloy is broken into pieces, got wherein 5 grams, in the quartz ampoule of 10 millimeters of the diameters of packing into, it is 0.5 millimeter that hole diameter is left in the quartz ampoule bottom, and quartz ampoule is placed on the induction coil center, and pipe aperture and roll surface are evacuated to 8 * 10 then apart from being 1 millimeter
-3Pa charges into 1 atmospheric argon gas, and alloy is liquid to about 1600 ℃ of one-tenth through induction heating, starts motor and makes roller turn, and roller diameter is 20 centimetres, and 1910 rev/mins of rotating speeds are equivalent to 20 meter per seconds.Fill the argon gas of 0.7 kg/cm pressure then fast at the other end of quartz ampoule, the alloy that makes fusing is ejected into the roller surfaces of rotation by the quartz ampoule aperture, solidifies into about 1 mm wide, 20-30 micron thickness, the long metal tape that does not wait.Zhi Bei belt is Th like this
2Zn
17The type monophase materials, its X-ray diffraction spectrum such as Fig. 3.Corresponding agnetic property at room temperature m and density see Table 2.
Embodiment 14-20:
Press table 2 ingredient composition, preparation technology is with embodiment 13.Corresponding agnetic property at room temperature m and density see Table 2.
Embodiment 21-26:
Press embodiment 1 ingredient composition, alloy melting is with embodiment 1, and rapid quenching technique is with embodiment 13, but change roller rotating speed V
a, from V
a=15 meter per seconds change to V
a=30 meter per seconds, the agnetic property at room temperature m and the density of gained material see Table 3.
Embodiment 27:
Press embodiment 1 ingredient composition, alloy melting is with embodiment 1, and rapid quenching technique is with embodiment 13, but the roller rotating speed is 47 meter per seconds, and the belt of preparation becomes amorphous state platform gold, heat treatment 20 minutes in 700 ℃ vacuum then, Th
2Zn
17The monophase materials of type structure, corresponding agnetic property at room temperature m and density see Table 4.
Embodiment 28:
Press embodiment 1 ingredient composition; alloy melting is with embodiment 1; rapid quenching technique is with embodiment 13; belt behind the fast quenching carries out ball milling, ratio of grinding media to material 25: 1, ball milling 0.5 hour under the benzinum protection; the particle mean size of powder is 10 microns behind the ball milling; the epoxy resin and the powder that add 1% weight then are even, compression moulding under 6 tons/square centimeter pressure, and performance and density under the bonded permanent magnet room temperature of preparation see Table 4.Table 1
Table 2
Table 3
Embodiment 21-26 constituent atoms percentage is: Sm
9.76Fe
68.29Ga
14.63C
7.32
| The embodiment numbering | Composed atom percentage | Form percentage by weight | Curie temperature T c(K) | Coercive force H c(kOe) | Remanent magnetism B r(kGs) | Magnetic energy product (BH) max(MGOe) | Density p (g/cm 3) |
| 1 2 3 4 5 6 7 8 9 10 11 12 | Sm 9.76Fe 68.29Ga 14.63C 7.32 Sm 10.26Fe 71.79Ga 15.38C 2.56 Sm 10Fe 70Ga 15C 5 Sm 9.52Fe 66.67Ga 14.29C 9.52 Sm 9.30Fe 65.12Ga 13.95C 11.63 Sm 9.52Fe 60Co 6.67Ga 14.29C 9.52 Sm 9.52Fe 53.33Co 13.33Ga 14.29C 9.52 Sm 9.52Fe 46.67Co 20Ga 14.29C 9.52 Sm 9.76Fe 63.41Ga 19.51C 7.32 Sm 9.76Fe 58.54Ga 24.39C 7.32 Sm 7.80Nd 1.95Fe 68.29Ga 14.63C 7.32 Sm 7.80Gd 1.95Fe 68.29Ga 14.63C 7.32 | Sm 22.96Fe 59.70Ga 1s.97C 1.38 Sm 23.17Fe 60.25Ga 16.12C 0.46 Sm 23.07Fe 59.97Ga 16.04C 0.92 Sm 22.86Fe 59.42Ga 15.90C 1.83 Sm 22.75Fe 59.15Ga 15.82C 2.27 Sm 22.78Fe 53.31Co 6.25Ga 15.84C 1.82 Sm 22.71Fe 47.23Co 12.46Ga 15.79C 1.81 Sm 22.63Fe 41.19Co 18.63Ga 15.74C 1.81 Sm 22.72Fe 54.85Ga 21.07C 1.36 Sm 22.48Fe 50.11Ga 26.06C 1.35 Sm 18.40Nd 4.41Fe 59.81Ga 16.00C 1.38 Sm 18.33Gd 4.79Fe 59.57Ga 15.94C 1.37 | 624 620 623 619 602 606 608 612 570 459 615 636 | 13.1 9.3 12.5 13.0 12.2 11.6 10.5 9.6 8.5 4.7 10.3 10.1 | 9.24 9.55 9.35 8.87 8.53 9.03 8.85 8.89 7.59 5.54 8.95 8.55 | 20.2 15.2 19.8 18.5 18.1 18.6 18.5 14.1 12.3 5.5 16.1 14.3 | 7.4 7.4 7.4 7.3 7.3 7.4 7.5 7.5 7.2 7.0 7.3 7.3 |
| The embodiment numbering | Composed atom percentage | Form percentage by weight | Curie temperature T a(K) | Coercive force H c(kOe) | Remanent magnetism B r(kGs) | Magnetic energy product (BH) max (MGOe) | Density p (g/cm 3) |
| 13 14 15 16 17 18 19 20 | Sm 9.76Fe 73.17Ga 9.76C 7.32 Sm 10Fe 70Ga 15C 5 Sm 9.76Fe 68.29Ga 14 63C 7.32 Sm 9.52Fe 66.67Ga 14.29C 9.52 Sm 9.30Fe 65.12Ga 13.95C 11.63 Sm 9.52Fe 60Co 6.67Ga 14.29C 9.52 Sm 9.52Fe 53.33Co 13.33Ga 14.29C 9.52 Sm 7.80Nd 1.95Fe 68.29Ga 14.63C 7.32 | Sm 23.21Fe 64.64Ga 10.76C 1.39 Sm 23.07Fe 59.97Ga 16.04C 0.92 Sm 22.96Fe 59.70Ga 15.97C 1.38 Sm 22.86Fe 59.42Ga 15.90C 1.83 Sm 22.75Fe 59.15Ga 15.82C 2.27 Sm 22.78Fe 53.31Co 6.25Ga 15.84C 1.82 Sm 22.71Fe 47.23Co 12.46Ga 15.79C 1.81 Sm 18.40Nd 4.41Fe 59.81Ga 16.00C 1.38 | 624 620 623 619 602 606 608 612 | 13.1 9.3 12.5 13.0 12.2 11.6 10.5 9.6 | 9.24 9.55 9.35 8.87 8.53 9.03 8.85 8.89 | 20.2 15.2 19.8 18.5 18.1 18.6 18.5 14.1 | 7.4 7.4 7.4 7.3 7.3 7.4 7.5 7.5 |
| The embodiment numbering | Roller rotating speed V (m/s) | Curie temperature T c(K) | Coercive force H c(kOe) | Remanent magnetism B r(kGs) | Magnetic energy product (BH) max(MGOe) | Density p (g/cm 3) |
| 21 22 23 24 25 26 | 15 18 20 22 25 30 | 624 624 624 624 624 624 | 10.0 13.1 13.5 13.2 13.8 15.0 | 5.81 5.90 5.84 5.71 5.85 5.83 | 6.5 7.1 6.8 6.6 7.2 7.2 | 7.3 7.3 7.3 7.3 7.3 7.3 |
Weight percentages of components is: Sm
22.96Fe
59.70Ga
15.97C
1.38Table 4
Embodiment 27,28 constituent atoms percentages are: Sm
9.76Fe
68.29Ga
14.63C
7.32
| The embodiment numbering | Curie temperature T c(K) | Coercive force H c (kOe) | Remanent magnetism B r(kGs) | Magnetic energy product (BH) max (MGOe) | Density p (g/cm 3) |
| 27 28 | 627 624 | 11.2 10.5 | 5.84 4.50 | 6.7 5.0 | 7.3 5.5 |
Weight percentages of components is: Sm
22.96Fe
59.70Ga
15.97C
1.38
Claims (2)
1. rare-earth iron-based permanent-magnetic carbide that contains gallium with 2: 17 type structures, it consists of: (Sm
1-xR
x)
α(Fe
1-yM
y)
100-alpha-beta-γGa
βC
γ
Wherein R is single or more than one following element:
Y, Ce, Pr, Nd, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu; M is single or more than one following element:
Ti、V、Cr、Mn、Co、Ni、Cu、Zr、Nb、Mo、Hf、Ta、W、B、
Al, Si; α is the 5-15 atomic percentage; β is the 0.1-14 atomic percentage; γ is the 5-15 atomic percentage; X is 0-0.2; The scope of y is as follows:
Co is 0-0.3; Mn, Ni, Al are respectively 0-0.2; All the other are respectively 0-0.1;
2. one kind is used to prepare the described method with rare-earth iron-based permanent-magnetic carbide that contains gallium of 2: 17 type structures of claim 1, it is characterized in that: directly become single-phase compound by melting with preparation permanent magnet basis, adopt rapid quenching technique, the control rotating speed is the 10-30 meter per second.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93105618 CN1038007C (en) | 1993-05-07 | 1993-05-07 | Gallium-containing rare earth-iron-based permanent magnet carbide and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93105618 CN1038007C (en) | 1993-05-07 | 1993-05-07 | Gallium-containing rare earth-iron-based permanent magnet carbide and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1095182A CN1095182A (en) | 1994-11-16 |
| CN1038007C true CN1038007C (en) | 1998-04-08 |
Family
ID=4985841
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93105618 Expired - Fee Related CN1038007C (en) | 1993-05-07 | 1993-05-07 | Gallium-containing rare earth-iron-based permanent magnet carbide and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1038007C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061460C (en) * | 1997-08-01 | 2001-01-31 | 罗阳 | Carbide permanent magnet and its prepn. method |
| CN103276284B (en) * | 2013-06-05 | 2014-11-12 | 南京理工大学 | Preparation method for low dysprosium heat-resistant sintered neodymium-iron-boron |
| CN103475162B (en) * | 2013-07-20 | 2016-05-25 | 南通飞来福磁铁有限公司 | A kind of preparation method of the rare-earth permanent magnet for energy-saving electric machine |
| CN111933375A (en) * | 2020-07-09 | 2020-11-13 | 浙江工业大学 | Novel samarium-iron-carbon-based anisotropic magnetic powder |
-
1993
- 1993-05-07 CN CN 93105618 patent/CN1038007C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1095182A (en) | 1994-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US11791093B2 (en) | Rare earth permanent magnets and their preparation | |
| EP1970924B1 (en) | Rare earth permanent magnets and their preparation | |
| KR960008185B1 (en) | Rare earth-iron system permanent magnet and process for producing the same | |
| JPH01704A (en) | Rare earth-iron permanent magnet | |
| CN1288239A (en) | Multielement gap type permanent-magnet material and production process of magnetic powler and magnet | |
| JPH0974006A (en) | Magnetic material and bonded magnet | |
| JP4314244B2 (en) | Magnetic material powder manufacturing method and bonded magnet manufacturing method | |
| CN1089385A (en) | A kind of high stable rare-earth-iron-permanent-magnetic carbide and preparation method thereof | |
| JPS63114939A (en) | R2t14b-type composite-type magnet material and its production | |
| JPS6393841A (en) | Rare-earth permanent magnet alloy | |
| JPH1187118A (en) | Material and manufacture of magnet and bond magnet using the same | |
| CN1038007C (en) | Gallium-containing rare earth-iron-based permanent magnet carbide and preparation method thereof | |
| JP3135665B2 (en) | Magnetic materials and bonded magnets | |
| JPH0685369B2 (en) | Permanent magnet manufacturing method | |
| JPH0320046B2 (en) | ||
| CN1066146A (en) | The preparation method of rare-earth-iron-boron permanent-magnet powder | |
| US5968289A (en) | Permanent magnetic material and bond magnet | |
| JPH0881741A (en) | Magnetic material and permanent magnet using the same | |
| CN1061163C (en) | Double-phase rare-earth-iron-boron magnetic powder and its prepn. method | |
| JP3469496B2 (en) | Manufacturing method of magnet material | |
| JPH0766021A (en) | Permanent magnet | |
| JP2739860B2 (en) | MAGNETIC MATERIAL, MAGNET COMPRISING THE SAME, AND PROCESS FOR PRODUCING THEM | |
| JP3386552B2 (en) | Magnetic material | |
| JP3037917B2 (en) | Radial anisotropic bonded magnet | |
| JPH023206A (en) | Rare earth-iron system permanent magnet |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |