CN103117143B - A kind of neodymium iron boron magnetic body of neodymium iron boron nickel plating waste material sintering - Google Patents
A kind of neodymium iron boron magnetic body of neodymium iron boron nickel plating waste material sintering Download PDFInfo
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- CN103117143B CN103117143B CN201310039135.4A CN201310039135A CN103117143B CN 103117143 B CN103117143 B CN 103117143B CN 201310039135 A CN201310039135 A CN 201310039135A CN 103117143 B CN103117143 B CN 103117143B
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Abstract
The invention discloses the neodymium iron boron magnetic body of a kind of neodymium iron boron nickel plating waste material sintering, it solve neodymium iron boron magnetic body performance in prior art low, the problems such as waste utilization rate is low.The neodymium iron boron magnetic body of the present invention is that the compound formed by neodymium iron boron nickel plating waste material and rich rare earth formulation is prepared from by sintering process, the remanent magnetism (Br) of neodymium iron boron magnetic body is >=1.2T, HCJ (Hcj) >=13.3KOe, coercivity (Hcb) >=11.6KOe, magnetic energy product (BH (max)) is >=34.8MGOe, squareness is 0.97～0.98 for (HK/Hcj), and weight-loss ratio is 0.19-1.10mg/cm2, Br temperature coefficient is-0.090～-0.11% DEG C.Its preparation method is: roasting neodymium iron boron nickel plating waste material；Prepare neodymium iron boron nickel plating waste powder；Preparation compound；Compressing；Sintering.The method is simple, effective, environmental protection, low cost.
Description
Technical field
The present invention relates to a kind of neodymium iron boron magnetic body, be specifically related to the neodymium iron boron magnetic body of a kind of neodymium iron boron nickel plating waste material sintering, belong to Rare-Earth Magnetic field of material technology.
Background technology
In recent years, along with the rapid expansion of neodymium iron boron magnetic body application, raw-material demand has been become increasing, but because of the relatively costly of rare earth mining and along with the increasing of national regulation and control dynamics, its material cost has also been gradually increased.When present price amount of increase is excessive, the price endurance ratio of Downstream Market is relatively limited, portion downstream enterprise have selected the rare earth using the material such as relatively inexpensive ferrite or aluminum nickel cobalt, SmCo to replace in neodymium iron boron magnetic body raw material, and this brings bigger unstability to neodymium iron boron magnetic body market.Additionally, Nd-Fe-B magnetic material fragility is high, specification is assorted, very easily occurs unfilled corner and the problem such as size is bad in electroplating process.And the learies of neodymium iron boron magnetic body is very big after electroplating, be only the scrappage of finished appearance and size just between 2～5%, because of the otherwise requirement of client also time often result in and occur bad to scrap phenomenon.Therefore the cost reducing Sintered NdFeB magnet is one of problem demanding prompt solution.
In neodymium iron boron nickel plating waste material, 80% is the plating Ni waste material being coated with Ni or NiCuNi layer, plating Ni waste material can because coating processes unclean in utilizing process, pore, oxidation spots etc. affect the problem of performance to cause product surface to occur, reduce the recovery utilization rate of nickel plating waste material simultaneously.Prior art is generally adopted first with acid solution or alkali liquor carry out strip process again nickel plating waste material is recycled.But the matrix phenomenon by acid solution or alkali liquid corrosion very easily occurs in strip process, cause that the response rate is low, additionally, the pollution of environment can be brought because of problems such as discharge of wastewater in strip process.Neodymium iron boron nickel plating waste material is recycled relatively costly, waste utilization rate, also easy contaminated environment hence with strip method.
And Chinese patent application (notification number: CN1076853C) discloses a kind of method that leftover bits and pieces of material prepares Nd-Fe-B series permanent magnet, neodymium iron boron magnetic body waste material is converted with neodymium iron boron magnetic body virgin material after mixing and is mixed by the method according to a certain percentage, adopt traditional handicraft and legacy equipment, such as intermediate frequency furnace, melting obtains neodymium iron boron magnetic body.But, in this approach, described neodymium iron boron magnetic body waste material mass percent in compound is generally below 50%, and neodymium iron boron waste material utilization rate is not high, and the poor-performing of obtained neodymium iron boron magnetic body, it is difficult to meet the application scenario of high request.
Summary of the invention
Present invention aims to the deficiencies in the prior art, it is provided that a kind of high performance neodymium iron boron magnetic body utilizing neodymium iron boron nickel plating waste material to sinter into.
The purpose of the present invention is achieved through the following technical solutions, a kind of neodymium iron boron magnetic body of neodymium iron boron nickel plating waste material sintering, this neodymium iron boron magnetic body is that the compound formed by neodymium iron boron nickel plating waste material and neodymium iron boron formulation is prepared from by sintering process, the mass percent of wherein said neodymium iron boron nickel plating waste material and neodymium iron boron formulation respectively 50%～98% and 2%～50%.Containing mass percent in described neodymium iron boron nickel plating waste material is the nickel element of 0.01%～0.1%, when neodymium iron boron magnetic body test temperature after making is 20 DEG C, performance is as follows: remanent magnetism (Br) >=1.2T, HCJ (Hcj) >=13.3KOe, coercivity (Hcb) >=11.6KOe, magnetic energy product (BHmax) is >=34.8MGSOe, squareness (HK/Hcj) is 0.97～0.98, and weight-loss ratio is 0.19～1.10mg/cm2, Br temperature coefficient is-0.090～-0.11% DEG C.
Relative to prior art, the neodymium iron boron magnetic body in the application is by selecting suitable neodymium iron boron nickel plating waste material to mix with neodymium iron boron formulation, and can obtain high-performance, low weight-loss ratio, the neodymium iron boron magnetic body that temperature stability is good by sintering process.The main performance of described neodymium iron boron magnetic body all reaches higher level, as common low weightless neodymium iron boron magnetic body 132 DEG C, 3atm, 168h when weight-loss ratio be >=5mg/cm2.And the weight-loss ratio of neodymium iron boron magnetic body is≤2mg/cm in the present invention2.And for example each trade mark maximum operating temperature Br temperature coefficient of former pure material preparation is-0.1～-0.12% DEG C, and the temperature coefficient of the neodymium iron boron magnetic body in the present invention is-0.09～-0.11% DEG C.And the mass percent that described neodymium iron boron waste material is in compound reaches 98%, substantially increase the utilization rate of neodymium iron boron waste material, greatly reduce the cost processing waste material Sintered NdFeB magnet, save cost and be about 10%～50%.Other heretofore described elements, mean non-rare earth.
In the neodymium iron boron magnetic body of described neodymium iron boron nickel plating waste material sintering, in described neodymium iron boron nickel plating waste material, each composition and mass percent thereof are: PrNd:28%～30%, B:0.95%～1.05%, Al:0.35%～0.5%, Nb:0.20%～0.25%, Ni:0.05%～0.1%, Cu:0.16%～0.18%, Gd or Dy:2.8%～3.5%, surplus is Fe and inevitable impurity.In described neodymium iron boron formulation, each composition and mass percent thereof are: PrNd:25%～28%, B:1.0～1.2%, in Gd, Dy, Co one or both: 4%～40%, Al:0.4%～2.0%, Nb:0.2%～0.3%, Cu:0.18%～0.2%, surplus is Fe and inevitable impurity.
Further, in described neodymium iron boron nickel plating waste material, each composition and mass percent thereof are: PrNd:28%, B:0.99%, Gd:3.5%, Al:0.5%, Nb:0.2%, Ni:0.1%, Cu:0.18%, and surplus is Fe and inevitable impurity.In described neodymium iron boron formulation, each composition and mass percent thereof are: PrNd:28%, B:1%, Gd:4%, Al:0.4%, Nb:0.2%, Cu:0.18%, and surplus is Fe and inevitable impurity.When described neodymium iron boron magnetic body test temperature is 20 DEG C, remanent magnetism (Br) is 1.249T, HCJ (Hcj) is 13.34KOe, coercivity (Hcb) is 11.82KOe, magnetic energy product (BHmax) is 37.62MGSOe, when test temperature is 80 DEG C, remanent magnetism (Br) is 1.173T, HCJ (Hcj) is 7.17KOe, and coercivity (Hcb) is 7.032KOe, and magnetic energy product (BHmax) is 32.16MGSOe；The squareness (HK/Hcj) of described neodymium iron boron magnetic body is 0.97, and weight-loss ratio is 0.85～1.10mg/cm2, Br temperature coefficient is-0.101% DEG C.
Further, in described neodymium iron boron nickel plating waste material, each composition and mass percent thereof are: PrNd:29.1%, B:0.99%, Dy:2.8%, Al:0.35%, Nb:0.21%, Ni:0.09%, Cu:0.17%, and surplus is Fe and inevitable impurity.In described neodymium iron boron formulation, each composition and mass percent thereof are: PrNd:25%, B:1.2%, Dy:40%, Al:2.0%, Nb:0.2%, Cu:0.2%, Co:20%, and surplus is Fe and inevitable impurity.When described neodymium iron boron magnetic body test temperature is 20 DEG C, remanent magnetism (Br) is 1.203T, HCJ (Hcj) is 21.24KOe, coercivity (Hcb) is 11.76KOe, magnetic energy product (BHmax) is 34.86MGSOe, when test temperature is 150 DEG C, remanent magnetism (Br) is 1.038T, HCJ (Hcj) is 6.131KOe, and coercivity (Hcb) is 5.86KOe, and magnetic energy product (BHmax) is 25.07MGSOe；Described squareness (HK/Hcj) is 0.98, and weight-loss ratio is 0.19～0.25mg/cm2, Br temperature coefficient is-0.106% DEG C.
Further, in described neodymium iron boron nickel plating waste material, each composition and mass percent thereof are: PrNd:29.2%, B:0.99%, Dy:0.8%, Al:0.25%, Nb:0.25%, Ni:0.08%, Cu:0.16%, and surplus is Fe and inevitable impurity.In described neodymium iron boron formulation, each composition and mass percent thereof are: PrNd:25%, B:1%, Dy:40%, Al:0.5%, Nb:0.2%, Cu:0.18%, Co:20%, and surplus is Fe and inevitable impurity.When described neodymium iron boron magnetic body test temperature is 20 DEG C, remanent magnetism (Br) is 1.349T, HCJ (Hcj) is 18.48KOe, coercivity (Hcb) is 12.86KOe, magnetic energy product (BHmax) is 43.06MGSOe, when test temperature is 120 DEG C, remanent magnetism (Br) is 1.203T, HCJ (Hcj) is 7.242KOe, coercivity (Hcb) is 7.041KOe, and magnetic energy product (BHmax) is 33.22MGSOe；Described squareness (HK/Hcj) is 0.97, and weight-loss ratio is 0.28～0.53mg/cm2, Br temperature coefficient is-0.108% DEG C.
The present invention also aims to provide a kind of simple, effectively, the method sintering above-mentioned neodymium iron boron magnetic body with neodymium iron boron nickel plating waste material of low cost, described method comprises the following steps:
S1, roasting neodymium iron boron nickel plating waste material: neodymium iron boron nickel plating waste material is carried out roasting in sintering furnace, after being filled with nitrogen, cooling, come out of the stove.
S2, prepare neodymium iron boron nickel plating waste powder: the neodymium iron boron nickel plating waste material after roasting is put into melting in vacuum rapid hardening furnace, after waste material is completely melt, pours into rejection tablet.It is placed in hydrogen crushing furnace by rejection tablet to carry out hydrogen broken, after hydrogen is broken, carries out composition measurement, then rejection tablet is put into fine grinding in air-flow grinding machine form neodymium iron boron nickel plating waste powder.
S3, preparation compound: according to rejection tablet composition measurement result, prepare neodymium iron boron formulation, described neodymium iron boron nickel plating waste powder is mixed and stirred for being formed uniformly compound with the neodymium iron boron formulation powder being made up of neodymium iron boron formulation.
S4, compressing: to enter in moulding press mould to be pressed into green compact at the protection down of nitrogen by described compound, green compact are put into isostatic pressing machine pressurization, pressurize obtains blank.
S5, sintering: at glove, described base substrate is shelled stripping oil in fuel tank, and stripping oil is placed in vacuum sintering furnace and carries out high temperature sintering, tempering, use after tempering that nitrogen is air-cooled comes out of the stove prepared neodymium iron boron magnetic body to room temperature.
In the method for described neodymium iron boron nickel plating waste material Sintered NdFeB magnet, the sintering temperature described in step S1 is 1100～1150 DEG C, and roasting time is 1～6 hour, and the vacuum of roaster is lower than 10-1Pa, tapping temperature is lower than 80 DEG C.Under this sintering temperature, roasting time and vacuum, the comprehensive utilization ratio of neodymium iron boron nickel plating waste material will be enhanced.
As preferably; in the method for described neodymium iron boron nickel plating waste material Sintered NdFeB magnet; smelting temperature described in step S2 is 1350～1550 DEG C, and described air-flow grinding machine powder process under the oxygen content nitrogen protection less than 200ppm, the powder particle mean size made is 2～5 μm.Under this smelting temperature, melting neodymium iron boron nickel plating waste material can make the neodymium iron boron magnetic body of sintering obtain good performance and higher productivity.Under this nitrogen protection, neodymium iron boron nickel plating waste material is made the powder that particle mean size is 2～5 μm; when neodymium iron boron nickel plating waste powder can be made to mix with neodymium iron boron formulation powder, contact area increases; it is easier to mix homogeneously, thus improving the comprehensive utilization ratio of neodymium iron boron nickel plating waste material.
Further, in the method for described neodymium iron boron nickel plating waste material Sintered NdFeB magnet, described step S2 concrete steps put into melting in vacuum rapid hardening furnace after comprising the steps: the mixing of the neodymium iron boron nickel plating waste material after by roasting, air in stove is evacuated to vacuum when being 0.4Pa, starts melting of heating.When expecting rubescent in stove, it is filled with argon, and is warming up to 1450 DEG C and carries out melting, until neodymium iron boron nickel plating waste material is completely melt.Refine poured into rejection tablet after 10 minutes, and rejection tablet is carried out ICP composition measurement, was then placed in hydrogen crushing furnace by rejection tablet, logical hydrogen in hydrogen crushing furnace.Carrying out hydrogen after product inhales hydrogen completely broken, then rejection tablet is put into fine grinding formation neodymium iron boron nickel plating waste powder in airflow milling machine under the oxygen content nitrogen protection less than 200ppm, the powder particle mean size made controls between 2～5 μm.
The present invention utilizes the hydrogen absorption characteristic of rare earth intermetallic compound, neodymium iron boron nickel plating waste material alloy is placed under hydrogen environment, hydrogen enters neodymium iron boron nickel plating waste material alloy along rich neodymium phase thin layer, so as to expansion explosion and crush, along rich neodymium phase layer place cracking, so that neodymium iron boron nickel plating waste material alloy sheet becomes neodymium iron boron nickel plating waste material alloy coarse powder.And with high pressure draught, the coarse powder after stirring is blown afloat, make dynamics diminish by collision each other, become neodymium iron boron nickel plating waste material alloy fine powder.Hydrogen is broken can improve 2～3 times with airflow milling in conjunction with use by milling efficiency, reaches 120～500KG/HR.
As preferably, in the method for described neodymium iron boron nickel plating waste material Sintered NdFeB magnet, the mixing time described in step S3 is 2～12 hours.
As preferably; in the method for described neodymium iron boron nickel plating waste material Sintered NdFeB magnet; described step S4 specifically includes following steps: put under the oxygen content nitrogen protection less than 5000ppm in moulding press mould by described compound; adding 1～magnetic field of 10T carries out orientation, is pressed into green compact after orientation.Green compact are put into isostatic pressing machine pressurization 100～250Mpa, and pressurize obtains blank in 1～5 minute, and described green density is 3.5～4.5g/cm3。
In the method for described neodymium iron boron nickel plating waste material Sintered NdFeB magnet, described step S5 farther includes following steps: at glove, described blank is shelled stripping oil in fuel tank, stripping oil is placed in vacuum sintering furnace, sinter 3～8h when temperature is 1030～1110 DEG C, the vacuum of high temperature sintering is lower than 10-1Handkerchief.Carry out one-level tempering 1～3h when temperature is 850～950 DEG C, be subsequently cooled to 480～580 DEG C and carry out second annealing 2～4h, adopt that nitrogen is air-cooled obtains neodymium iron boron magnetic body.
In sum, present invention have the advantage that
1, the method recycling neodymium iron boron nickel plating waste material in the present invention simple, effectively, environmental protection, improve the comprehensive utilization ratio of plating wastes, greatly reduce the cost processing plating wastes.
2, the neodymium iron boron magnetic body material combination of present invention sintering is reasonable, and neodymium iron boron magnetic body magnetic property is high, and corrosion resistance is good, and weight-loss ratio is low, and temperature stability is good.
Detailed description of the invention
The following is specific embodiments of the invention, technical scheme is further described, but the present invention is not limited to these embodiments.
Embodiment one:
Neodymium iron boron nickel plating waste material is utilized to produce N38 product:
Roasting neodymium iron boron nickel plating waste material: be placed in sintering furnace by neodymium iron boron nickel plating waste material, is warming up to 1100 DEG C and carries out roasting.Vacuum in sintering furnace is less than 10-1Pa, roasting time is 4 hours, is then charged with nitrogen, and blower fan cools down, and treats that temperature is down to less than 80 DEG C and is come out of the stove.
Prepare neodymium iron boron nickel plating waste powder: the neodymium iron boron nickel plating waste material after 600kg roasting is put into melting in vacuum rapid hardening furnace, the air in stove is evacuated to vacuum when being 0.4Pa, starts melting of heating.When expecting rubescent in stove, it is filled with argon, and is warming up to 1450 DEG C and carries out melting, until neodymium iron boron nickel plating waste material is completely melt.Refine poured into rejection tablet after 10 minutes.Rejection tablet carries out ICP composition measurement, and composition measurement result is in Table 1.Again rejection tablet is placed in hydrogen crushing furnace; logical hydrogen in hydrogen crushing furnace; carrying out hydrogen after product inhales hydrogen completely broken, hydrogen flour is put into fine grinding in airflow milling machine under the oxygen content nitrogen protection lower than 200ppm and forms neodymium iron boron nickel plating waste powder, the powder particle mean size made controls between 2～5 μm.
Table 1: neodymium iron boron nickel plating waste material composition measurement result
Preparation compound: according to rejection tablet composition measurement result, prepares neodymium iron boron formulation, and the component content of neodymium iron boron formulation is in Table 2.Described neodymium iron boron nickel plating waste powder is mixed and stirred for 2h to being formed uniformly compound for 50%:50% by mass percentage with the neodymium iron boron formulation powder being made up of neodymium iron boron formulation.
Table 2: the component content of neodymium iron boron formulation
Compressing: described compound is put in moulding press mould under the oxygen content nitrogen protection lower than 5000ppm; adding 1～magnetic field of 10T carries out orientation, and it is pressed into green compact after orientation, green compact are put into isostatic pressing machine pressurization 100Mpa; pressurize obtains blank in 1 minute, and described green density is 3.5g/cm3。
Sintering: at glove, described blank is shelled stripping oil in fuel tank, and stripping oil is placed in vacuum sintering furnace, sinters 4h when temperature is 1075 DEG C, and the vacuum of high temperature sintering is lower than 10-1Handkerchief.Carry out one-level tempering 2h when temperature is 900 DEG C, be subsequently cooled to 530 DEG C and carry out second annealing 3h, adopt that nitrogen is air-cooled obtains neodymium iron boron magnetic body to less than 80 DEG C.
One, by being cut into D10 × 10mm sample post with after the neodymium iron boron magnetic body surface grinding of neodymium iron boron nickel plating waste material sintering in the present embodiment, carrying out performance test according to GB/T3217 permanent magnetism (Hard Magnetic) magnetism of material test method, the performance test results is in Table 3.
Table 3: neodymium iron boron magnetic body the performance test results
From above-mentioned test result, the neodymium iron boron magnetic body performance of present invention neodymium iron boron nickel plating waste material sintering is ideal, Br temperature coefficient such as neodymium iron boron magnetic body of the present invention is-0.097% DEG C, and the Br temperature coefficient of the N38 neodymium iron boron magnetic body of conventional formulation sintering is at-0.11% DEG C even more than-0.12% DEG C.And the cost of present invention neodymium iron boron nickel plating waste material Sintered NdFeB magnet is lower by 15% than preparing Sintered NdFeB magnet with pure material.
Two, carrying out low weightless test in the present embodiment with the neodymium iron boron magnetic body of neodymium iron boron nickel plating waste material sintering, test condition is 132 DEG C, 3atm, 168h, and low weightless test result is in Table 4.
Table 4: the low weightless test result of neodymium iron boron magnetic body
From above-mentioned test result it can be seen that the weight-loss ratio of the neodymium iron boron magnetic body of present invention neodymium iron boron nickel plating waste material sintering is low, it is 0.85～1.1mg/cm2, and the weight-loss ratio of the N38 neodymium iron boron magnetic body of conventional formulation sintering is generally at 10mg/cm2Above.
Embodiment two:
35SH product is produced with neodymium iron boron nickel plating waste material:
Roasting neodymium iron boron nickel plating waste material: be placed in sintering furnace by neodymium iron boron nickel plating waste material, is warming up to 1120 DEG C and carries out roasting.Vacuum in sintering furnace is lower than 10-1Pa, roasting time is 4 hours, is then charged with nitrogen, and blower fan cools down, and treats that temperature is down to less than 80 DEG C and is come out of the stove.
Prepare neodymium iron boron nickel plating waste powder: after being mixed by the neodymium iron boron nickel plating waste material after 600kg roasting, put into melting in vacuum rapid hardening furnace, the air in stove is evacuated to vacuum when being 0.4Pa, starts melting of heating.When expecting rubescent in stove, it is filled with argon, and is warming up to 1500 DEG C and carries out melting, until neodymium iron boron nickel plating waste material is completely melt.Refine poured into rejection tablet after 10 minutes.Rejection tablet carries out ICP composition measurement, and composition measurement result is as shown in table 5.Then rejection tablet is placed in hydrogen crushing furnace; logical hydrogen in hydrogen crushing furnace; carrying out hydrogen after product inhales hydrogen completely broken, then hydrogen flour is put into fine grinding formation neodymium iron boron nickel plating waste powder in airflow milling machine under the oxygen content nitrogen protection less than 200ppm, the powder particle mean size made controls between 2～5 μm.
Table 5: neodymium iron boron nickel plating waste material composition measurement result
Preparation compound: according to rejection tablet composition measurement result, prepares neodymium iron boron formulation, and the component content of neodymium iron boron formulation is in Table 6.Described neodymium iron boron nickel plating waste powder is mixed and stirred for 12h to being formed uniformly compound for 98%:2% by mass percentage with the neodymium iron boron formulation powder being made up of neodymium iron boron formulation.
Table 6: the component content of neodymium iron boron formulation
Compressing: described compound is put in moulding press mould under the oxygen content nitrogen protection lower than 5000ppm; adding 1～magnetic field of 10T carries out orientation, and it is pressed into green compact after orientation, green compact are put into isostatic pressing machine pressurization 250Mpa; pressurize obtains blank in 5 minutes, and described green density is 4.5g/cm3。
Sintering: at glove, described blank is shelled stripping oil in fuel tank, and stripping oil is placed in vacuum sintering furnace, sinters 4h when temperature is 1060 DEG C, and the vacuum of high temperature sintering is lower than 10-1Handkerchief.Carry out one-level tempering 2h when temperature is 900 DEG C, be subsequently cooled to 520 DEG C and carry out second annealing 3h, adopt that nitrogen is air-cooled obtains neodymium iron boron magnetic body to less than 80 DEG C.
One, by being cut into D10 × 10mm sample post with after the neodymium iron boron magnetic body surface grinding of neodymium iron boron nickel plating waste material sintering in the present embodiment, carrying out performance test according to GB/T3217 permanent magnetism (Hard Magnetic) magnetism of material test method, the performance test results is in Table 7.
Table 7: neodymium iron boron magnetic body the performance test results
From above-mentioned test result, the neodymium iron boron magnetic body performance of present invention neodymium iron boron nickel plating waste material sintering is ideal, Br temperature coefficient such as neodymium iron boron magnetic body of the present invention is-0.106% DEG C, and the Br temperature coefficient of the 35SH neodymium iron boron magnetic body of conventional formulation sintering is more than-0.115% DEG C, and the cost of present invention neodymium iron boron nickel plating waste material Sintered NdFeB magnet is lower by 35% than preparing Sintered NdFeB magnet with pure material.
Two, carrying out low weightless test in the present embodiment with the neodymium iron boron magnetic body of neodymium iron boron nickel plating waste material sintering, test condition is 132 DEG C, 3atm, 168h, and low weightless test result is in Table 8.
Table 8: the low weightless test result of neodymium iron boron magnetic body
From above-mentioned test result it can be seen that the weight-loss ratio of the neodymium iron boron magnetic body of present invention neodymium iron boron nickel plating waste material sintering is low, it is 0.85～1.1mg/cm2, and the weight-loss ratio of the 35SH neodymium iron boron magnetic body of conventional formulation sintering is generally at 10mg/cm2Above.
Embodiment three:
45H product is produced with neodymium iron boron nickel plating waste material:
Roasting neodymium iron boron nickel plating waste material: be placed in sintering furnace by neodymium iron boron nickel plating waste material, is warming up to 1130 DEG C and carries out roasting.Vacuum in sintering furnace is lower than 10-1Pa, roasting time is 4 hours, is then charged with nitrogen, and blower fan cools down, and treats that temperature is down to less than 80 DEG C and is come out of the stove.
Prepare neodymium iron boron nickel plating waste powder: after being mixed by the neodymium iron boron nickel plating waste material after 600kg roasting, put into melting in vacuum rapid hardening furnace, the air in stove is evacuated to vacuum when being 0.4Pa, starts melting of heating.When expecting rubescent in stove, it is filled with argon, and is warming up to 1500 DEG C and carries out melting, until neodymium iron boron nickel plating waste material is completely melt.Refine poured into rejection tablet after 10 minutes.Rejection tablet carries out ICP composition measurement, and composition measurement result is as shown in table 9.Then rejection tablet is placed in hydrogen crushing furnace; logical hydrogen in hydrogen crushing furnace; carrying out hydrogen after product inhales hydrogen completely broken, then hydrogen flour is put into fine grinding formation neodymium iron boron nickel plating waste powder in airflow milling machine under the oxygen content nitrogen protection lower than 200ppm, the powder particle mean size made controls between 2～5 μm.
Table 9: neodymium iron boron nickel plating waste material composition measurement result
Preparation compound: according to rejection tablet composition measurement result, prepares neodymium iron boron formulation, and the component content of neodymium iron boron formulation is in Table 10.Described neodymium iron boron nickel plating waste powder is mixed and stirred for 12h to being formed uniformly compound for 98%:2% by mass percentage with the neodymium iron boron formulation powder being made up of neodymium iron boron formulation.
Table 10: the component content of neodymium iron boron formulation
Compressing: described compound is put in moulding press mould under the oxygen content nitrogen protection lower than 5000ppm; adding 1～magnetic field of 10T carries out orientation, and it is pressed into green compact after orientation, green compact are put into isostatic pressing machine pressurization 250Mpa; pressurize obtains blank in 5 minutes, and described green density is 4.5g/cm3。
Sintering: at glove, described blank is shelled stripping oil in fuel tank, and stripping oil is placed in vacuum sintering furnace, sinters 4h when temperature is 1060 DEG C, and the vacuum of high temperature sintering is lower than 10-1Handkerchief.Carry out one-level tempering 2h when temperature is 900 DEG C, be subsequently cooled to 520 DEG C and carry out second annealing 3h, adopt that nitrogen is air-cooled obtains neodymium iron boron magnetic body to less than 80 DEG C.
One, by being cut into D10 × 10mm sample post with after the neodymium iron boron magnetic body surface grinding of neodymium iron boron nickel plating waste material sintering in the present embodiment, carrying out performance test according to GB/T3217 permanent magnetism (Hard Magnetic) magnetism of material test method, the performance test results is in Table 11.
Table 11: neodymium iron boron magnetic body the performance test results
From above-mentioned test result, the neodymium iron boron magnetic body performance of present invention neodymium iron boron nickel plating waste material sintering is ideal, Br temperature coefficient such as neodymium iron boron magnetic body of the present invention is-0.108% DEG C, and the Br temperature coefficient of the 45H neodymium iron boron magnetic body of conventional formulation sintering is more than-0.115% DEG C, and the cost of present invention neodymium iron boron nickel plating waste material Sintered NdFeB magnet is lower by 30% than preparing Sintered NdFeB magnet with pure material.
Two, carrying out low weightless test in the present embodiment with the neodymium iron boron magnetic body of neodymium iron boron nickel plating waste material sintering, test condition is 132 DEG C, 3atm, 168h, and low weightless test result is in Table 12.
Table 12: the low weightless test result of neodymium iron boron magnetic body
From above-mentioned test result it can be seen that the weight-loss ratio of the neodymium iron boron magnetic body sintered with neodymium iron boron nickel plating waste material the present invention is low, it is 0.28～0.531mg/cm2, and the weight-loss ratio of the 45H neodymium iron boron magnetic body of conventional formulation sintering is generally at 5mg/cm2Above.
In sum, the test result of the magnetic property of neodymium iron boron magnetic body from embodiment one, two, three, high-temperature behavior and low weightlessness, the neodymium iron boron magnetic body of present invention neodymium iron boron nickel plating waste material sintering has higher magnetic property, relatively low weight-loss ratio, good temperature stability.And, described neodymium iron boron magnetic body, in sintering process, can use more than the mass percent neodymium iron boron nickel plating waste material more than 50%, reduce the preparation cost of neodymium iron boron magnetic body, method is simple, effectively, environmental protection, cost low.
Specific embodiment described herein is only to present invention spirit explanation for example.Described specific embodiment can be made various amendment or supplements or adopt similar mode to substitute by those skilled in the art, but without departing from the spirit of the present invention or surmount the scope that appended claims is defined.
Claims (5)
1. one kind utilizes the neodymium iron boron magnetic body that neodymium iron boron nickel plating waste material sinters, it is characterized in that, described neodymium iron boron magnetic body is that the compound formed by neodymium iron boron nickel plating waste material and neodymium iron boron formulation is prepared from by sintering process, the mass percent of wherein said neodymium iron boron nickel plating waste material and neodymium iron boron formulation respectively 50%～98% and 2%～50%；Containing mass percent in described neodymium iron boron nickel plating waste material is the nickel element of 0.05%～0.1%, when neodymium iron boron magnetic body test temperature after making is 20 DEG C, performance is as follows: remanent magnetism (Br) >=1.2T, HCJ (Hcj) >=13.3KOe, coercivity (Hcb) >=11.6KOe, magnetic energy product (BHmax) is >=34.8MGSOe, squareness (HK/Hcj) is 0.97～0.98, and weight-loss ratio is 0.19～1.10mg/cm2, Br temperature coefficient is-0.090～-0.11% DEG C；Wherein, in described neodymium iron boron nickel plating waste material, each composition and mass percent thereof are: PrNd:28%～30%, B:0.95%～1.05%, Al:0.35%～0.5%, Nb:0.20%～0.25%, Ni:0.05%～0.1%, Cu:0.16%～0.18%, Gd or Dy:2.8%～3.5%, surplus is Fe and inevitable impurity；In described neodymium iron boron formulation, each composition and mass percent thereof are: PrNd:25%～28%, B:1.0～1.2%, in Gd, Dy, Co one or both: 4%～40%, Al:0.4%～2.0%, Nb:0.2%～0.3%, Cu:0.18%～0.2%, surplus is Fe and inevitable impurity.
2. the neodymium iron boron magnetic body utilizing neodymium iron boron nickel plating waste material to sinter according to claim 1, it is characterized in that, in described neodymium iron boron nickel plating waste material, each composition and mass percent thereof are: PrNd:28%, B:0.99%, Gd:3.5%, Al:0.5%, Nb:0.2%, Ni:0.1%, Cu:0.18%, surplus is Fe and inevitable impurity；In described neodymium iron boron formulation, each composition and mass percent thereof are: PrNd:28%, B:1%, Gd:4%, Al:0.4%, Nb:0.2%, Cu:0.18%, and surplus is Fe and inevitable impurity；When described neodymium iron boron magnetic body test temperature is 20 DEG C, remanent magnetism (Br) is 1.249T, HCJ (Hcj) is 13.34KOe, coercivity (Hcb) is 11.82KOe, magnetic energy product (BHmax) is 37.62MGSOe, when test temperature is 80 DEG C, remanent magnetism (Br) is 1.173T, HCJ (Hcj) is 7.17KOe, and coercivity (Hcb) is 7.032KOe, and magnetic energy product (BHmax) is 32.16MGSOe；The squareness (HK/Hcj) of described neodymium iron boron magnetic body is 0.97, and weight-loss ratio is 0.85～1.10mg/cm2, Br temperature coefficient is-0.101% DEG C.
3. the neodymium iron boron magnetic body utilizing neodymium iron boron nickel plating waste material to sinter according to claim 1, it is characterized in that, in described neodymium iron boron nickel plating waste material, each composition and mass percent thereof are: PrNd:29.1%, B:0.99%, Dy:2.8%, Al:0.35%, Nb:0.21%, Ni:0.09%, Cu:0.17%, surplus is Fe and inevitable impurity；In described neodymium iron boron formulation, each composition and mass percent thereof are: PrNd:25%, B:1.2%, Dy:40%, Al:2.0%, Nb:0.2%, Cu:0.2%, Co:20%, and surplus is Fe and inevitable impurity；When described neodymium iron boron magnetic body test temperature is 20 DEG C, remanent magnetism (Br) is 1.203T, HCJ (Hcj) is 21.24KOe, coercivity (Hcb) is 11.76KOe, magnetic energy product (BHmax) is 34.86MGSOe, when test temperature is 150 DEG C, remanent magnetism (Br) is 1.038T, HCJ (Hcj) is 6.131KOe, and coercivity (Hcb) is 5.86KOe, and magnetic energy product (BHmax) is 25.07MGSOe；Described squareness (HK/Hcj) is 0.98, and weight-loss ratio is 0.19～0.25mg/cm2, Br temperature coefficient is-0.106% DEG C.
4. the neodymium iron boron magnetic body utilizing neodymium iron boron nickel plating waste material to sinter according to claim 1, it is characterized in that, in described neodymium iron boron nickel plating waste material, each composition and mass percent thereof are: PrNd:29.2%, B:0.99%, Dy:0.8%, Al:0.25%, Nb:0.25%, Ni:0.08%, Cu:0.16%, surplus is Fe and inevitable impurity；In described neodymium iron boron formulation, each composition and mass percent thereof are: PrNd:25%, B:1%, Dy:40%, Al:0.5%, Nb:0.2%, Cu:0.18%, Co:20%, and surplus is Fe and inevitable impurity；When described neodymium iron boron magnetic body test temperature is 20 DEG C, remanent magnetism (Br) is 1.349T, HCJ (Hcj) is 18.48KOe, coercivity (Hcb) is 12.86KOe, magnetic energy product (BHmax) is 43.06MGSOe, when test temperature is 120 DEG C, remanent magnetism (Br) is 1.203T, HCJ (Hcj) is 7.242KOe, coercivity (Hcb) is 7.041KOe, and magnetic energy product (BHmax) is 33.22MGSOe；Described squareness (HK/Hcj) is 0.97, and weight-loss ratio is 0.28～0.53mg/cm2, Br temperature coefficient is-0.108% DEG C.
5. the method preparing neodymium iron boron nickel plating waste material Sintered NdFeB magnet as claimed in claim 1, it is characterised in that said method comprising the steps of:
S1, roasting neodymium iron boron nickel plating waste material: neodymium iron boron nickel plating waste material is carried out roasting in sintering furnace, after being filled with nitrogen, cooling, come out of the stove；
S2, prepare neodymium iron boron nickel plating waste powder: the neodymium iron boron nickel plating waste material after roasting is put into melting in vacuum rapid hardening furnace, rejection tablet is poured into after waste material is completely melt, it is placed in hydrogen crushing furnace by rejection tablet to carry out hydrogen broken, carry out composition measurement after hydrogen is broken, then rejection tablet is put into fine grinding formation neodymium iron boron nickel plating waste powder in air-flow grinding machine；
S3, preparation compound: according to rejection tablet composition measurement result, prepare neodymium iron boron formulation, described neodymium iron boron nickel plating waste powder is mixed and stirred for being formed uniformly compound with the neodymium iron boron formulation powder being made up of neodymium iron boron formulation；
S4, compressing: to enter in moulding press mould to be pressed into green compact at the protection down of nitrogen by described compound, green compact are put into isostatic pressing machine pressurization, pressurize obtains blank；
S5, sintering: at glove, described blank is shelled stripping oil in fuel tank, and stripping oil is placed in vacuum sintering furnace, sinters 3～8h when temperature is 1030～1110 DEG C, and the vacuum of high temperature sintering is less than 10-1Handkerchief, carries out one-level tempering 1～3h when temperature is 850～950 DEG C, is subsequently cooled to 480～580 DEG C and carries out second annealing 2～4h, adopts that nitrogen is air-cooled obtains neodymium iron boron magnetic body；
Wherein, the sintering temperature described in step S1 is 1100～1150 DEG C, and roasting time is 1～6 hour, and the vacuum of roaster is less than 10-1Pa, tapping temperature is less than 80 DEG C.
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