CN108746642A - A kind of preparation method of the rare earth-transition metal nitride Magnaglo through surfacecti proteon processing - Google Patents
A kind of preparation method of the rare earth-transition metal nitride Magnaglo through surfacecti proteon processing Download PDFInfo
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
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- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
- C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
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- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/032—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of hard-magnetic materials
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- H01F1/053—Alloys characterised by their composition containing rare earth metals
- H01F1/055—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5
- H01F1/0551—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0552—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 in the form of particles, e.g. rapid quenched powders or ribbon flakes with a protective layer
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Abstract
The present invention provides a kind of preparation method of the rare earth-transition metal nitride Magnaglo handled through surfacecti proteon, and the Magnaglo preparation method includes mainly that rare earth-transition metal alloy is smelted, presets the processes such as dusting in atmosphere, Nitrizing Treatment, Mechanochemical Effect surface treatment.Method provided by the invention can make rare earth-transition metal nitride magnetic powder ensure that nitriding is sufficient not oxidized in preparation process, powder obtained produces protecting film more significantly more efficient than conventional mixed processing by Mechanochemical Effect, the rare earth-transition metal nitride Magnaglo handled through surfacecti proteon finally obtained has excellent magnetic property and significant moisture-proof thermal environment, the performance of high temperature resistant processing environment, can be directly used for carrying out mixed refining process with macromolecule resin.
Description
Technical field
The invention belongs to magneto-electric functional material fields, are related to a kind of rare earth-transition metal nitridation handled through surfacecti proteon
The preparation method of object Magnaglo.
Background technology
It is reported from nineteen ninety Coey et al. in Sm2Fe17Middle introducing gap N atoms find intermetallic compound
Sm2Fe17Nx(x ≈ 3) has grasp magnetic property in excellent since, rare earth-transition metal nitride Magnaglo has excellent
Different magnetic performance is concerned.For example, Sm2Fe17Nx(x ≈ 3) compound has anisotropy more higher than " magnetic king " neodymium iron boron
Field and Curie temperature, meanwhile, inoxidizability and corrosion resistance are superior to neodymium iron boron compounds.Further, since current neodymium iron boron
A large amount of uses, the rare earth elements such as Nd largely consume, and other rare earths of association then relative surplus, the utilization of different rare earth elements
Rate is extremely uneven, balancedly utilizes rare earth element, while reducing rare earth element consumption as magnet industry and rare-earth trade
One of focus of attention, and usually rare earth ratio contained in rare earth-transition metal nitride magnetic material is significantly less than neodymium iron
The exploitation of boron magnet, preparation method can promote the balanced of rare earth resources to utilize.However, since rare earth element is this kind of material
Big electronegativity is provided, it is made easily to be aoxidized in preparation process, leads to the deterioration of magnetism of material energy；Meanwhile in reality
In the application of border, magnetic powder would generally mixing granulator prepares bonding magnetic at a temperature of 100~350 DEG C with macromolecule resin bonding agent
Body, therefore, magnetic powder also need to meet the requirement of high-temperature mixing other than needing to meet the requirement of room temperature storage.Currently, the prior art
In measure that usually such problem is taken be not enough.For example, Hebei University Of Engineering Zheng Li permit et al. application patent CN
102816991 B, disclose a kind of low temperature nitriding preparation method of iron-based rare-earth permanent magnetism powder, by master alloy ball milling in technique
Nitriding is carried out to it again to nano-sheet powder, although reducing nitriding temperature, the powder specific-surface area detection of nano-scale is big, living
Property it is high, easily aoxidize, while anti-oxidation processing is not carried out to the powder after nitriding, be easy during use and storage oxidation from
And reduce magnetic property.University of Science & Technology, Beijing Sun Guang fly et al. application 1254338 C of patent CN disclose a kind of reduction-diffusion process
The method for manufacturing Sm-Fe-N permanent magnetic alloy powders includes Chemical Decomposition and metal powder in reaction product water in technical process
The dehydration and drying at end and etc., alloy powder easily gets rusty during being contacted with water, aoxidizes, it is made to be easy in nitriding process
It decomposes and generates α-Fe phases harmful to magnetic property, magnetic property is caused to reduce.Peking University poplar answers the patent CN of prosperous et al. application
100437841 C disclose the manufacturing method of a kind of anisotropic rare-earth permanent-magnet material and its magnetic powder and magnet, prepare sheet magnetic
Powder is to utilize rolling anisotropic, and technique is by the way of direct ball milling or airflow milling crush again after rapid hardening alloy sheet nitriding,
In the program by the way of not broken, the direct nitriding of rapid-hardening flake, although the oxidation in magnetic powder preparation process can be avoided as possible,
But because alloy size is larger before nitriding, the problem that nitriding is insufficient inside alloy is easily caused；In addition, the powder after nitriding only leads to
The mode for crossing mixing is added to coupling agent, antioxidant etc., is just directly used in and is kneaded and then prepares magnet, easily in this process
Making magnetic powder that oxidation occur reduces magnetic property.The rare earth-transition metal nitride powder being prepared usually is adopted in the prior art
Mixed refining process is carried out with conventional being stirred after mode carries out surface cladding processing, although place can be made as possible by mixing by stirring
Reason liquid comes into full contact with magnetic powder and react, but reacts the protective film of generation there are still the problem of not enough densification, still to the protection of powder
It is not enough, further, since coating reaction is usually carried out in organic solvent, and soluble in water do not dissolve in of many inorganic agents has
Solvent causes reaction to be difficult to happen.In this patent, using the protective film of Mechanochemical Effect inductive formation relative to normal
Rule method is more complete, fine and close, can also realize the protecting film for the element containing special metal that conventional method can not obtain, to real
Now more excellent protection effect.
Invention content
The purpose of the present invention is to provide a kind of rare earth-transition metal nitride Magnaglos through surfacecti proteon processing
Preparation method, the rare earth-transition metal nitride Magnaglo ingredient are RxTyMzN100-x-y-z, 5≤x≤12,70≤y≤
85, z≤5, wherein R are one or more of 17 kinds of rare earth elements, and T is at least one of transition metal element, M C, S,
At least one of Cl, Si, Sr, Al, P, Ti, Ca and other contents are less than the foreign atom of 0.2wt.%；In the preparation
Cheng Zhong carries out cladding processing using Mechanochemical Effect after nitriding, makes magnetic by crushing alloy in default atmosphere before nitriding
Powder is all not oxidized during the entire process of being prepared into use, to obtain high magnetic characteristics, and can be obtained in severe use environment
To holding.
The preparation method of the present invention includes mainly that rare earth-transition metal alloy is smelted, presets dusting in atmosphere, at nitriding
Reason, Mechanochemical Effect surface treatment and etc..Particular content is as follows：
(a) rare earth-transition metal alloy is smelted
With the ingredient RxTyMzN100-x-y-zIn other all elements in addition to N element simple substance or alloy be raw material,
Such as the simple substance or alloy of the elements such as metal Fe, Co, Sm, Nd, Ce, Zn, Mn, Ca, after mixing according to the ratio, by induction melting or
The mode of electric arc melting is prepared into alloy melt, in this process, preferably while applying electromagnetic agitation so that each component is in liquid
Be sufficiently mixed under the form of state uniformly, smelting time visual response amount with depending on specification of equipment difference, it is however generally that, material is all molten
It should continue to keep 5min-3h after change, mix and be not enough if it is less than 5min, between component, the component distributing of alloy is uneven,
Cause final product dephasign more, main phase accounting is low；If smelting time is more than 3h, although can ensure that different components uniformly mix
It closes, but time efficiency is low, simultaneously as the simple substance of many elements such as metal Sm, Nd, Mn, Ca is at high temperature with higher full
And vapour pressure, there is volatilization in fusion process, if smelting time is more than 3h, volatilization loss is serious, on the one hand leads to raw material wave
Take, on the other hand, also makes the ingredient substantial deviation desired value of final product.After melting is uniform, by alloy melt down to water cooling
Containing cooled and solidified on copper material, form R-T-M solid alloys, ultimately form the form of ingot casting, ingot bar or slab.
(b) dusting in atmosphere is preset
The solid alloy being prepared in step (a) is passed through into mechanical crushing, air-flow crushing, hydrogenation powder in default atmosphere
Powdered, granularity 0.005-1mm is made in the mode of one or more of broken combination.If granularity < 0.005mm, are easy to make
It is aoxidized at powder, while the crystal structure of alloy is easily destroyed；If granularity is more than 1mm, it is insufficient that there may be nitridings
Problem；Meanwhile the granularity of 0.005-1mm also contributes to subsequent mechanical force and chemical surfacecti proteon processing.Default atmosphere be He,
N2、Ar、H2One or more of combine.
The mechanical crushing refers to that material is crushed by hard alloy by external force in above-mentioned default atmosphere, and passes through
Grading is crossed, the master alloy powder that granularity is 0.005-1mm is obtained, it may include two pairs of rollers crush, jaw crushes, hammering crushes
Deng；The air-flow crushing, refers in enclosed system, by the flow at high speed of above-mentioned pre-set gas, drives master alloy phase
Mutually collision obtains the master alloy powder of 0.005-1mm by grading；The hydrogenation crushes, and refers to closing solid-state mother
Gold is placed in default atmosphere, and continues to input H2, the spy of lattice dilatation generation internal stress after hydrogen atom is absorbed using rare earth alloy
Property crush, which can heat at a temperature of less than 600 DEG C to accelerate scrap rates, if be higher than 600 DEG C, rare earth alloy
Dehydrogenation, it is difficult to achieve the purpose that be crushed powder processed.
(c) Nitrizing Treatment
By be put into the alloy powder being prepared in step (b) N atoms can be provided atmosphere in carry out isothermal holding.Institute
N should at least be contained by stating in nitrogen containing atmosphere2、NH3、N2-NH3、N2-H2、NH3-H2In one of which.Usually at 350~550 DEG C
Carry out 3~30h of Nitrizing Treatment.If temperature is less than 350 DEG C, nitrogenizing effect unobvious, nitrogen content is low in product, does not have N originals
The gap effect of son；If temperature is higher than 550 DEG C, on the one hand cause the N atoms penetrated into excessive, occupies between unnecessary lattice
Gap, another aspect excessive temperature are easy that product is made to decompose, and generate and are harmful to dephasign.If nitriding time is shorter than 3h, nitrogenizing effect is not
Obviously, especially inside alloy, nitrogen content is low in alloy powder, cannot reach lattice dilatation, improves the purpose of magnetic property；If oozing
The nitrogen time is longer than 30h, and prolonged high temperature is easy that magnetic powder containing N is made to decompose, generates the dephasigns such as α-Fe, R-N, magnetic property is caused to drop
It is low.
(d) mechanical force and chemical protective treatment
Mechanical force and chemical refers to, using mechanical energy induced chemical reaction, utilizing the group of mechanochemical effect induced material
It knits, the generation variation of structure and performance, to prepare new material or be modified the process of processing to material, this process can lure
The effect that hair normal condition is unable to reach.In this patent, using the protective film of Mechanochemical Effect inductive formation compared to
Conventional method is more complete, fine and close, to obtain more excellent protection effect；Furthermore, it is possible to realize that conventional method can not obtain
The protective film obtained.For example, the phosphatization coating film containing Zn, Mn, Ca etc. has the characteristics that wearability is high, thermal stability is good, simultaneously also
There is antifriction lubrication, these features are highly beneficial, and Zn salt, Mn salt, Ca for the processing of injection molding magnetic material
Salt is generally dissolved only in water, does not dissolve in organic solvent but, not due to rare earth-transition metal nitride magnetic powder described in this patent
Surfacecti proteon is preferably carried out in water, and therefore, conventional method makes it difficult for the elements such as Zn, Mn, Ca to enter in the coating film of surface, and adopts
It then may be implemented the metals such as Zn, Mn, Ca in phosphate member with the mode that mechanical force induced chemical of the present invention reacts
Element enters in the coating film of surface.
It is as follows to the specific implementation process of the step：
(1) it will be placed in organic liquid by the alloy powder of Nitrizing Treatment in step (c), the dosage of organic liquid is at least
Making powder during Ying Ben, all to completely cut off air, organic liquid type is the hydro carbons such as kerosene, gasoline, ethyl alcohol, propyl alcohol for submergence
Equal alcohols, one or more of ketones such as acetone mixing liquid.Meanwhile it should contain in the system or add in subsequent step
Enter in molecule and there is the compound of "-P-OH " structure or "-P-H " structure as main chemical reactions agent, such as orthophosphoric acid, Asia
Phosphoric acid, polyphosphoric acid, organic phospho acid, phosphoric acid salt and lipid etc., additive amount should be the 0.05-10wt.% of magnetic powder.If additive amount is low
In 0.05wt.%, then cladding film thickness, the integrity degree generated is insufficient；If additive amount is higher than 10wt.%, unnecessary, raw simultaneously
At coating film it is too thick, occupy more volume fraction, magnetic property caused to reduce.In addition, oleic acid, oleyl amine, silane can be aided with simultaneously
At least one of coupling agent, titanate coupling agent, phosphate coupling agent, boric acid ester coupler, aluminate coupling agent are used as table
Face modifying agent, to improve mechanics and dispersibility, additive amount is the 0.05-5wt.% of magnetic powder, if additive amount is less than 0.05wt.%,
Then coat integrity degree deficiency；If additive amount is higher than 5wt.%, unnecessary, while occupying larger volume score, lead to magnetic property
It reduces.
(2) mechanical force transfer medium is added in the mixed system of above-mentioned powder and solution, the mechanical force, which is transmitted, to be situated between
Matter is graininess hard alloy or ceramics, such as bearing steel, agate of each dimension 0.1-50mm etc., is not limited shape
System, can be positive sphere, spheroid, polyhedron, irregular shape etc..If size be less than 0.1mm, no matter using screening or
The mode of Magneto separate is finally difficult to that it is made to detach with magnetic powder product, simultaneously as undersized, it is difficult to transmit machinery well
Power；If size is more than 50mm, since specific surface area is small, while own wt is big, and the efficiency that mechanical force is transmitted substantially reduces.
(3) apply mechanical force to promote reaction to start, applying mode can be a kind of or several in overturning, rolling, agitation, vibration
Kind combination.In general, sustainable or intermittent application mechanical force, total mechano-chemical reation time is 5min-5h.If time <
5min then reacts insufficient, and protective film forms imperfect, and protection effect is undesirable；If time > 5h, reacted end,
New protective film is not had to generate, meanwhile, the protective film generated before this is constantly worn under force, is gradually lost
Lose protection effect.
Advantages of the present invention is：Prepare the rare earth-transition metal nitride Magnaglo handled through surfacecti proteon
RxTyMzN100-x-y-zDuring, the R-T-M alloys dusting in default atmosphere for obtaining melting before nitriding reaction is ensureing
While abundant nitriding, the generation of the harmful phases such as oxidation and the α-Fe during powder processed, nitridation etc. is avoided, it is pure to obtain
Net nitriding powder, and surfacecti proteon is carried out using Mechanochemical Effect to it, inductive formation is more compared to conventional method
Whole, fine and close protective film is added, to obtain more excellent protection effect, can also induce and realize that conventional method can not obtain
Protective film (i.e. the phosphatization coating film containing Zn, Mn, Ca etc.), than commonly infiltrate agitating mode acquisition protective film have it is more excellent
Different protection effect.It can the rare earth-transition metal nitride Magnaglo that uses of safe and stable, high temperature resistant to obtain.It is logical
It crosses the rare earth-transition metal nitride Magnaglo that mode of the present invention is prepared, is used in magnetic powder from being prepared into
All not oxidized in whole process, magnetic property is high, and can be maintained in the high severe use environment such as damp and hot, inoxidizability and
Excellent corrosion resistance can be directly used for the processes such as high-temperature mixing and injection molding and prepare magnet.
Specific implementation mode
With reference to specific embodiment and comparative example, the invention will be further described, should not be by involved technical parameter
It is interpreted as limitation of the present invention with process.
Embodiment 1
By raw metal samarium, metallic iron, metallic cobalt according to mass ratio 1:2.66:After 0.14 ratio mixing, in Ar atmosphere
The lower induction melting 1h of protection, makes alloy melt be sufficiently mixed uniformly, and it is solidified as bulk in water cooled copper mould.Alloy is cast
Block is in Ar and H2Mixed gas (volume ratio 1:1) hammering crushes in, obtains alloy average grain diameter D50=0.3mm powder.It will obtain
The alloy powder obtained is in NH3-H2In at 490 DEG C nitriding 6h.It takes the reaction product that 3kg is obtained to immerse in gasoline, it is straight that 3kg is added
The spherical agate bead of diameter Φ=5mm, and 50g phosphoric acid, 50g phosphate dihydrogen manganeses, 30gKH550 is added, 15g oleic acid, using blade with
The rotating speed of 2000rpm applies it mechanical force 2h.By slurry vacuum drying, the rare earth-transition handled through surfacecti proteon gold is obtained
Belong to nitride Magnaglo.The magnetic property of magnetic powder is measured by VSM, and is placed on 85 DEG C, 100h in 85RH% chambers
Magnetic property is tested again afterwards, to characterize the ability of powder moisture-proof thermal environment；In addition, by the macromolecule of magnetic powder obtained and 10wt%
Resin PA12 is molded into magnetism testing mark block and mechanical stretch batten in 230 DEG C of mixing granulators, and in 270 DEG C, to characterize system
The ability of the magnetic powder high temperature resistant processing environment obtained, table 1 are corresponding test result.
Table 1
Embodiment 2
By raw metal samarium, neodymium metal, metallic iron, metallic cobalt, Titanium according to mass ratio 0.95:0.05:2.78:
0.05:0.01 ratio mixing after, the induction melting 1h under Ar atmosphere protections makes alloy melt be sufficiently mixed uniformly, and by its
Bulk is solidified as in water cooled copper mould.By alloy ingot in Ar and H2Mixed gas (volume ratio 1:1) two pairs of rollers crush in, obtain
Average grain diameter D50The powder metallurgy of=0.9mm, and it is obtained into average grain diameter D by air-flow crushing in an ar atmosphere50=
0.09mm powder.By the alloy powder of acquisition in N2-H2In mixed atmosphere at 420 DEG C nitriding 9h.Take the reaction production that 3kg is obtained
Object immerses in gasoline, and the agate bead of 3kg diameter of phi=5mm is added, and 80g phosphoric acid, 20g calcium dihydrogen phosphates, 30gKH550 is added,
Mechanical force 1.5h applies it with the rotating speed of 1500rpm using blade.By slurry vacuum drying, obtain handling through surfacecti proteon
Rare earth-transition metal nitride Magnaglo.The magnetic property of magnetic powder is measured by VSM, and is placed on 85 DEG C, 85RH% examinations
Magnetic property is tested in tryoff after 100h again, to characterize the ability of powder moisture-proof thermal environment；In addition, by magnetic powder obtained with
The macromolecule resin PA12 of 10wt% is molded into magnetism testing mark block and mechanical stretch in 230 DEG C of mixing granulators, and in 270 DEG C
Batten, with the ability of magnetic powder high temperature resistant processing environment made from characterization, table 2 is corresponding test result.
Table 2
Embodiment 3~13
By raw metal samarium, neodymium metal, metallic iron, metallic aluminium according to mass ratio 0.95:0.05:2.83:0.005 ratio
After mixing, the induction melting 45min under Ar atmosphere protections makes alloy melt be sufficiently mixed uniformly, and by it in water-cooled copper roller
It is frozen into slab.By alloy casting piece in N2And H2Mixed gas (volume ratio 1:1) two pairs of rollers are crushed to the small pieces less than 0.5cm in,
And it is placed on Ar and H2Mixed gas (volume ratio 1:1) in, 350 DEG C are heated to, it is lasting to mend as alloy sheet sucks H atom
Fill H2, 2h is maintained, D is obtained after cooling50The powder of=0.07mm.By the alloy powder of acquisition in N2It is oozed at 500 DEG C in atmosphere
Nitrogen 8h.It takes the reaction product that 3kg is obtained to immerse in isopropanol, the agate bead of 3kg diameter of phi=5mm is added, and institute in table 3 is added
The mechanical force and chemical treatment additive stated applies it mechanical force 1.5h using blade with the rotating speed of 1300rpm.By slurry vacuum
Drying, obtains the rare earth-transition metal nitride Magnaglo handled through surfacecti proteon.The magnetic property of magnetic powder is measured by VSM,
And be placed on 85 DEG C, test magnetic property again after 100h in 85RH% chambers, to characterize the energy of powder moisture-proof thermal environment
Power；In addition, by the macromolecule resin PA12 of magnetic powder obtained and 10wt% in 230 DEG C of mixing granulators, and it is molded into magnetic in 270 DEG C
Performance test mark block and mechanical stretch batten, with the ability of magnetic powder high temperature resistant processing environment made from characterization, table 3 is corresponding test
As a result.
Table 3
Comparative example 1
The alloy ingot obtained in embodiment 1 is placed in the air of 0.1MPa pressure and carries out hammering crushing, rather than by its
It is placed in preset Ar and H2In mixed-gas environment, it is placed directly within NH3-H2In at 495 DEG C nitriding 3h.3kg is then taken to obtain
Reaction product immerses in isopropanol, and carries out the anti-oxidation processing processing of mechanical force and chemical in the same manner as in Example 1.Pass through VSM
The magnetic property of magnetic powder is measured, and is placed on 85 DEG C, tests magnetic property again after 100h in 85RH% chambers, to characterize powder
The ability of body moisture-proof thermal environment；In addition, by the macromolecule resin PA12 of magnetic powder obtained and 10wt% in 230 DEG C of mixing granulators,
And it is molded into magnetism testing mark block and mechanical stretch batten in 270 DEG C, with magnetic powder high temperature resistant processing environment made from characterization
Ability, table 4 are corresponding test result.
Table 4
Comparative example 2
By the alloy ingot obtained in embodiment 1 without crushing, it is placed in NH3-H2In nitriding 3h under the conditions of 495 DEG C.Then
It takes the reaction product that 3kg is obtained to immerse in isopropanol, and carries out at the anti-oxidation processing of mechanical force and chemical in the same manner as in Example 1
Reason.The magnetic property of magnetic powder is measured by VSM, and be placed on 85 DEG C, test is magnetic again after 100h in 85RH% chambers
Can, to characterize the ability of powder moisture-proof thermal environment；In addition, by the macromolecule resin PA12 of magnetic powder obtained and 10wt% 230
DEG C mixing granulator, and it is molded into magnetism testing mark block and mechanical stretch batten in 270 DEG C, with magnetic powder high temperature resistant made from characterization
The ability of processing environment, table 5 are corresponding test result.
Table 5
Comparative example 3
The alloy casting piece obtained in embodiment 3 is directly set into N2In atmosphere at 495 DEG C nitriding 8h.Then in an ar atmosphere
It is further ground into powder using the mode of airflow milling.Then take 3kg obtain reaction product immerse isopropanol in, and carry out with
The identical anti-oxidation processing processing of mechanical force and chemical in embodiment 3.The magnetic property of magnetic powder is measured by VSM, and is placed on
85 DEG C, test magnetic property again after 100h in 85RH% chambers, to characterize the ability of powder moisture-proof thermal environment；In addition, will system
The macromolecule resin PA12 of the magnetic powder and 10wt% that obtain is molded into magnetism testing mark block in 270 DEG C in 230 DEG C of mixing granulators
With mechanical stretch batten, with the ability of magnetic powder high temperature resistant processing environment made from characterization, table 6 is corresponding test result
Table 6
Comparative example 4,5
By alloy powder after the nitriding obtained in embodiment 2,3, (do not apply without the anti-oxidation processing of mechanical force and chemical
Mechanical force does not also add reactant), the macromolecule resin PA12 of magnetic powder and 10wt% directly obtained is in 230 DEG C of mixing granulators
The magnetism testing mark block and mechanical stretch batten being molded into afterwards in 270 DEG C, meanwhile, the magnetic property of magnetic powder is measured by VSM, it will
It is positioned over 85 DEG C, tests magnetic property in 85RH% chambers after 100h again, and table 7 is corresponding test result.
Table 7
Comparative example 6~9
3kg is taken with alloy powder after identical nitriding in embodiment 2,3,5,6, to be dipped in isopropanol, and be added respectively
With embodiment 2,3,5,6 corresponding surface treating additives, but it is added without agate bead, only uses blade and turned with 1300rpm
Speed stirs 1.5h to it, makes alloy powder and inorganic agent is full and uniform contacts.Slurry vacuum drying is obtained at only chemical action
The rare earth-transition metal nitride Magnaglo of reason.The magnetic property of magnetic powder is measured by VSM, and be placed on 85 DEG C,
Magnetic property is tested again after 100h in 85RH% chambers, to characterize the ability of powder moisture-proof thermal environment；In addition, by magnetic obtained
The macromolecule resin PA12 of powder and 10wt% are molded into magnetism testing mark block and mechanics in 230 DEG C of mixing granulators in 270 DEG C
Tensile bars, with the ability of magnetic powder high temperature resistant processing environment made from characterization, table 8 is corresponding test result.5g is taken to compare respectively
The rare earth-transition metal nitride Magnaglo handled through surfacecti proteon obtained in example 6~9 and embodiment 1-6 is with about 1L
After deionized water is washed repeatedly, vacuum drying uses X-ray fluorescence spectrometer (XRF, ZSX Primus II) test specimens
Product ingredient, the results are shown in Table 9.
Table 8
Table 9
Note："×" represents test value < 0.02wt.% in table；" √ " represents test value > 0.1wt.%.
It can be seen that the rare earth-transition handled through surfacecti proteon being prepared through the invention by embodiment 1-14
Metal nitride Magnaglo has excellent magnetic property and significant resistance to high humid and warm environment and high temperature resistant processing environment
Characteristic.By comparing example 1,2 and embodiment 1 and comparative example 3 and embodiment 3, it can be seen that consolidated in pre-set gas
State alloy crushes, and two conditions must simultaneously meet, and can effectively improve and improves rare earth-transition metal nitride magnetic powder
The magnetic property at end.By comparing example 4,5 and embodiment 2,3 as can be seen that carrying out surface treatment ten using Mechanochemical Effect
Divide the moisture-proof thermal energy power and high temperature resistant processing environment ability for considerably improving rare earth-transition metal nitride Magnaglo.It is logical
Cross comparative example 6,7,8,9 and embodiment 2,3,5,6, it can be seen that the surface coating film phase that the reaction of mechanical force induced chemical generates
Has significantly more protecting effect than being stirred the cladding that lower chemical reaction generates in tradition, particularly by comparative example 8,9
With the magnetic property index of embodiment 5,6 and the elemental analysis of table 9 it can be found that when in mechanical force and chemical surface treating additive
Metallic atom in additive can be incorporated in coating film under mechanical force inductive effect and form specific system by when containing metallic atom
Row, the coating film with specific function, and under the conditions of convention stir, due to salt in organic solution the low problem of dissolubility,
Reaction is hardly happened, apparent protecting effect is not had.
Above-described embodiment is not for the limitation of the present invention, and the present invention is not limited only to above-described embodiment, as long as meeting
The present invention claims all belong to the scope of protection of the present invention.
Claims (9)
1. a kind of preparation method of the rare earth-transition metal nitride Magnaglo through surfacecti proteon processing, described is dilute containing N
Soil-transition metal magnetic powdered ingredients are RxTyMzN100-x-y-z, 5≤x≤12,70≤y≤85, z≤5, wherein R are 17 kinds of rare earths
One or more of element, T is at least one of transition metal element, in M C, S, Cl, Si, Sr, Al, P, Ti, Ca
At least one and other contents are less than the foreign atom of 0.2wt%, which is characterized in that preparation method includes mainly following step
Suddenly：
(a) with the ingredient RxTyMzN100-x-y-zIn other all elements in addition to N element simple substance or alloy it is logical for raw material
The mode for crossing melting prepares alloy melt, and it is made, containing being solidified on copper material, to form solid alloy in water cooling；
(b) alloy block obtained by melting is crushed to 0.005-1mm in default atmosphere；
(c) atmosphere that nitrogen atom is placed in the alloy powder obtained by carries out Nitrizing Treatment；
(d) surfacecti proteon processing is carried out to the powder after nitriding using Mechanochemical Effect.
2. a kind of system of rare earth-transition metal nitride Magnaglo through surfacecti proteon processing according to claim 1
Preparation Method, which is characterized in that the solid alloy grinding mode refer to carried out in default atmosphere mechanical crushing, air-flow crushing,
One or more of hydrogenation crushing combines.
3. a kind of system of rare earth-transition metal nitride Magnaglo through surfacecti proteon processing according to claim 2
Preparation Method, which is characterized in that the default atmosphere is He, N2、Ar、H2One or more of combine.
4. a kind of system of rare earth-transition metal nitride Magnaglo through surfacecti proteon processing according to claim 1
Preparation Method, which is characterized in that should at least contain N in the atmosphere of the nitrogen atom2、NH3、N2-NH3、N2-H2、NH3-H2In
One of which.
5. a kind of system of rare earth-transition metal nitride Magnaglo through surfacecti proteon processing according to claim 1
Preparation Method, which is characterized in that the Mechanochemical Effect carries out in surfacecti proteon processing procedure, and each dimension ruler should be added
The very little transfer medium between the graininess hard alloy or ceramics of 0.1-50mm as mechanical force.
6. a kind of system of rare earth-transition metal nitride Magnaglo through surfacecti proteon processing according to claim 1
Preparation Method, which is characterized in that in the Mechanochemical Effect surfacecti proteon processing procedure, add and there is "-P- in molecule
The compound of OH " structures or "-P-H " structure is as chemical reactor.
7. a kind of system of rare earth-transition metal nitride Magnaglo through surfacecti proteon processing according to claim 6
Preparation Method, it is characterised in that the compound of described "-P-OH " structure or "-P-H " structure includes orthophosphoric acid, phosphorous acid, more
Phosphoric acid, organic phospho acid, phosphoric acid salt and lipid, additive amount are the 0.05-10wt% of magnetic powder.
8. a kind of system of rare earth-transition metal nitride Magnaglo through surfacecti proteon processing according to claim 7
Preparation Method, it is characterised in that the metallic element in phosphate enters rare earth-transition metal nitride by Mechanochemical Effect
The surface coating film of Magnaglo.
9. a kind of system of rare earth-transition metal nitride Magnaglo through surfacecti proteon processing according to claim 5
Preparation Method, it is characterised in that Mechanochemical Effect applying mode is one or more combination in overturning, rolling, agitation, vibration,
Sustainable or intermittent application mechanical force is carried out, and the overall mechanical force-chemical reaction time is 5min-5h.
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