CN109590461B - 一种3d冷打印制备烧结钕铁硼磁体的方法 - Google Patents
一种3d冷打印制备烧结钕铁硼磁体的方法 Download PDFInfo
- Publication number
- CN109590461B CN109590461B CN201910016347.8A CN201910016347A CN109590461B CN 109590461 B CN109590461 B CN 109590461B CN 201910016347 A CN201910016347 A CN 201910016347A CN 109590461 B CN109590461 B CN 109590461B
- Authority
- CN
- China
- Prior art keywords
- printing
- magnet
- cold
- powder
- preparing
- 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
- 229910001172 neodymium magnet Inorganic materials 0.000 title claims abstract description 67
- 238000007639 printing Methods 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 38
- QJVKUMXDEUEQLH-UHFFFAOYSA-N [B].[Fe].[Nd] Chemical compound [B].[Fe].[Nd] QJVKUMXDEUEQLH-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000005416 organic matter Substances 0.000 claims abstract description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 14
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 238000005245 sintering Methods 0.000 claims abstract description 14
- 239000002002 slurry Substances 0.000 claims abstract description 14
- 238000009694 cold isostatic pressing Methods 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims description 47
- 239000011248 coating agent Substances 0.000 claims description 23
- 238000000576 coating method Methods 0.000 claims description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- 238000010146 3D printing Methods 0.000 claims description 10
- 239000000654 additive Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 230000000996 additive effect Effects 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims description 6
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 4
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 4
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 4
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000005642 Oleic acid Substances 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 4
- 239000002985 plastic film Substances 0.000 claims description 4
- 229920006255 plastic film Polymers 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 229940057995 liquid paraffin Drugs 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- NTYVKAHDPRHELX-RDBSUJKOSA-N (2r,3s,4r)-6-(3,4-dimethylphenyl)hex-5-ene-1,2,3,4,5-pentol Chemical compound CC1=CC=C(C=C(O)[C@H](O)[C@@H](O)[C@H](O)CO)C=C1C NTYVKAHDPRHELX-RDBSUJKOSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 239000006247 magnetic powder Substances 0.000 abstract description 7
- 238000005520 cutting process Methods 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 238000004663 powder metallurgy Methods 0.000 abstract description 2
- 230000005415 magnetization Effects 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910052692 Dysprosium Inorganic materials 0.000 description 2
- 229910052771 Terbium Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 230000003064 anti-oxidating effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
- H01F41/0253—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets for manufacturing permanent magnets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- 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
- H01F1/04—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 metals or alloys
- H01F1/047—Alloys characterised by their composition
- 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
- H01F1/057—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B
- H01F1/0571—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes
- H01F1/0575—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together
- H01F1/0577—Alloys characterised by their composition containing rare earth metals and magnetic transition metals, e.g. SmCo5 and IIIa elements, e.g. Nd2Fe14B in the form of particles, e.g. rapid quenched powders or ribbon flakes pressed, sintered or bonded together sintered
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Hard Magnetic Materials (AREA)
- Manufacturing Cores, Coils, And Magnets (AREA)
Abstract
本发明提供了一种3D冷打印制备烧结钕铁硼磁体的方法,属于粉末冶金的领域。通过在钕铁硼磁粉的表面包覆一层无氧的有机物薄膜,防止磁粉在3D冷打印过程中氧化,同时采用低分子量且低氧的凝胶体系制备打印浆料,通过充磁实现磁体的打印取向成型,经冷等静压、烧结后,最终得到复杂形状的烧结钕铁硼零件。采用无氧的有机物包覆在易氧化的钕铁硼磁粉表面,控制磁粉在成形过程中的氧化问题,并采用低分子量且低氧的凝胶体系制备3D冷打印的钕铁硼料浆,进一步的控制成形过程中磁体增氧的情况。本发明制得的烧结钕铁硼磁体具有良好的磁性能,且可实现各种复杂形状的近净成型,省去了磁体复杂零件的切削加工,大大降低了生产成本且节约了资源。
Description
技术领域
本发明属于粉末冶金的领域,提供了一种3D冷打印制备烧结钕铁硼磁体的方法。
背景技术
烧结钕铁硼永磁材料因具有高的能量密度而被称为“磁王”,在航空航天、生物医学、信息通信、家用电器、风力发电和汽车工业等领域已成为核心功能器件。其中,重稀土Dy或Tb是高性能烧结钕铁硼磁体中常用的元素。而重稀土Dy、Tb元素资源匮乏、价格昂贵。通常采用粉末压制、烧结的工艺制备烧结钕铁硼磁体,但是为了得到理想形状的零件,通常需要对烧结磁体进行一定量的机切削加工,这就造成大量的资源浪费及生产成本增加。因此,需要发展一种可以近净成形、低成本制备高性能功能性磁器件的技术。
3D打印技术,又称为增材制造技术,是一种新型的近净成形技术,可以将金属粉末颗粒或塑料等材料根据计算机输出系统控制,逐层打印成形得到复杂形状的零件。3D打印技术非常适用于钕铁硼磁体的制备,打印得到的磁体不需要进一步的切削加工,有利于减少原料浪费,且无需单独制造模具,大大降低了生产成本。目前研究和应用最广泛的3D打印工艺是采用高能束(如激光束、电子束等)加热熔融预先铺设的金属粉末(球形,且粒径D50=30-35μm)或丝材,逐层堆积制造三维零件,已经实现钛及钛合金、高温合金、镁铝合金等多种金属和合金复杂零件的直接制造。对于烧结钕铁硼磁体,粉末的粒径一般为3-8μm,晶粒过大,磁体的磁性能大幅度降低。因此,高能束烧结快速成型技术并不适用于制备烧结钕铁硼磁体。因此,本发明提出一种3D冷打印技术制备烧结钕铁硼磁体,3D冷打印技术结合凝胶成形技术和3D打印技术,采用打印机将金属料浆直接打印到基板上,同时料浆在一定时间内发生交联固化反应,料浆经层层打印固化成形后,形成金属零件坯体,经脱脂烧结最终得到致密金属零件。
由于烧结钕铁硼的粉末较细,且极易氧化,因此在实现3D冷打印过程中,应考虑如何实现磁粉的防氧化,且由于凝胶体系多为高分子且含量的体系,如何实现钕铁硼磁粉在打印过程中不和凝胶体系中的有机物反应并发生氧化是至关重要的,烧结钕铁硼磁体中氧含量一般不高于4000ppm。因此,本发明提出采用无氧的有机物包覆钕铁硼粉末,不仅可以增加磁粉与凝胶体系中的成型剂或粘结剂的相容性,并且能够被容易去除,通过对钕铁硼粉末进行成形前的预处理,可以有效达到在3D冷打印过程中控氧的作用。同时,采用低分子量及低氧的凝胶体系进一步实现钕铁硼磁体打印过程中的控氧,通过打印取向成型,成功制备得到高性能的复杂形状的钕铁硼磁体。
发明内容
本发明的目的提供了一种3D冷打印制备烧结钕铁硼磁体的方法,该方法在控制易氧化的钕铁硼粉末在3D冷打印过程中的增氧情况取得了令人满意的成果,通过在磁粉表面包覆一层不含氧的有机物,防止钕铁硼磁粉在凝胶体系中氧化,且采用低分子量、低氧且易脱除的凝胶体系实现3D冷打印制备烧结钕铁硼磁体,一方面使打印的坯体具有一定的强度,另一方面即使钕铁硼粉末未完全被包覆,低分子量且低氧的凝胶体系使磁体的增氧情况可控制在一定的范围内,从而不影响其磁性能。同时,通过在打印过程中实现磁体在Z轴方向取向,实现了高性能的烧结钕铁硼磁体的复杂成形。
为了获得上述的3D冷打印制备烧结钕铁硼磁体的方法,本发明采用了以下技术方案,其中所有的操作步骤均在氩气气氛的手套箱或真空气氛的设备下进行,具体步骤如下:
(1)制备包覆溶液:将有机物包覆体溶解在有机溶剂a中,搅拌均匀,配制成有机物包覆溶液,溶液浓度为0.05g/ml-2.5g/ml;
(2)粉末包覆:按照质量百分比,有机物包覆体的质量为钕铁硼粉末质量的0.6-1.5wt.%,量取对应体积的步骤(1)中的有机物包覆溶液,将有机物包覆溶液与钕铁硼粉末混合均匀,使溶液浸润全部的粉末;
(3)粉末处理:将包覆好的粉末放入真空干燥箱中在45-60℃之间烘干30-60min后取出,得到包覆有机物的钕铁硼粉末;
(4)配制打印料浆:按照重量百分比将一定量的凝胶因子和添加剂溶解在有机溶剂b中,并在50-100℃下不断搅拌至完全溶解,配制成预混液。将步骤(3)中包覆后的钕铁硼粉末放入预混液中,并加入0.01-0.5vol.%的油酸,搅拌均匀,其中钕铁硼粉末的固含量为50-70vol.%;
(5)取向打印成型:将所需形状的模型输入3D冷打印机中,并将步骤(4)中的浆料装入3D打印设备的入料口中,打开取向充磁控制系统,在打印过程中打印的坯体在1.2~2.0T的磁场下不断取向,逐层打印出所需形状坯体,实现磁体的取向打印成型;
(6)冷等静压:将步骤(5)中打印好的坯体在40-60℃下真空干燥4-12h,并用塑料薄膜将干燥后的坯体进行密封,在50-500MPa压力下进行冷等静压,保压30-120s;
(7)真空烧结:将步骤(6)中冷等静压后的生坯进行真空烧结,烧结温度为1020~1100℃,真空度为10-2-10-3Pa,保温120-360min,制备得到所需形状的烧结钕铁硼磁体。
进一步地,步骤(1)中所述的有机物包覆体为无氧有机物,如液体石蜡、石蜡、苯乙烯或聚苯乙烯中的一种或几种。
进一步地,步骤(1)中所述的有机溶剂a为无氧溶剂,如甲苯、二甲苯、二氯甲烷、三氯甲烷或环己烷中的一种或几种。
进一步地,步骤(2)中所述钕铁硼粉末为烧结钕铁硼粉末,粉末粒径为3-8μm。
进一步地,步骤(4)中所述凝胶因子为低氧且低分子量的1,3:2,4-二(3,4-二甲基苄叉)-D-木糖醇(C20H22O6),在预混液中的质量百分比为0.5-1.0wt.%。
进一步地,步骤(4)中所述添加剂为无氧或低氧的强度添加剂,如松香或聚乙烯醇缩丁醛,在预混液中的质量百分比为0.5-3.0wt.%。
进一步地,步骤(5)中所述取向充磁控制系统由上、下两个电磁铁及控制单元组成,其中上方的电磁铁固定于打印机的顶端,下方的电磁铁固定于打印基板的底端,并通过电源控制单元实现Z轴方向充磁。
本发明的优点:
1、采用无氧体系的有机物包覆在易氧化的钕铁硼磁粉表面,控制磁粉在成形过程中的氧化问题;
2、采用低分子量且低氧的凝胶体系制备3D冷打印的钕铁硼料浆,进一步的控制成形过程中磁体增氧的情况;
3、在打印过程中实现磁体取向,有利于获得高取向度的磁体;且对3D打印的坯体进行冷等静压,既可以提高坯体的致密度又不破坏磁体的取向度;
4、通过3D冷打印可以制备各种复杂形状的烧结钕铁硼磁体,省去了磁体复杂零件的切削加工,大大降低了生产成本且节约了资源;
5、3D打印的烧结钕铁硼磁体具有应用范围广、工艺稳定、磁性能好的优点,具有良好的工业应用前景。
具体实施方式
实施案例1:
一种3D冷打印制备U形烧结钕铁硼磁体的方法:
(1)将聚苯乙烯溶解在二氯甲烷中,溶液浓度为0.5g/ml,搅拌均匀,配制成有机物包覆溶液。量取10ml的包覆溶液,并称量5μm的钕铁硼粉末500g,将有机物包覆溶液与钕铁硼粉末混合均匀,使溶液浸润全部的粉末;
(2)将包覆好的粉末放入真空干燥箱中在45℃烘干60min后取出,得到包覆有机物的钕铁硼粉末;
(3)将1g凝胶因子和2g松香溶于100g的甲苯中,并在60℃下不断搅拌至完全溶解,配制成预混液。将包覆好的钕铁硼粉末放入预混液中,固含量为60vol.%,并加入0.08vol.%的油酸,搅拌均匀,配制出打印浆料;
(4)将U形的模型输入3D冷打印机中,并将打印浆料装入3D打印设备的入料口中,开始打印,并打开取向充磁控制系统,在打印过程中打印的坯体在1.5T的磁场下不断取向,逐层打印出所需形状坯体;
(5)将打印好的坯体在40℃下真空干燥4h,并用塑料薄膜将干燥后的坯体进行密封,在100MPa压力下进行冷等静压,保压60s。再将冷等后坯体放入真空烧结炉中烧结,烧结温度为1050℃,保温240min,真空度为10-3Pa,冷却后得到U形的烧结钕铁硼磁体。
实施案例2:
一种3D冷打印制备环形烧结钕铁硼磁体的方法:
(1)将液体石蜡和聚苯乙烯溶解在三氯甲烷中,溶液浓度为0.08g/ml,搅拌均匀,配制成有机物包覆溶液。量取75ml的包覆溶液,并称量8μm的钕铁硼粉末400g,将有机物包覆溶液与钕铁硼粉末混合均匀,使溶液浸润全部的粉末;
(2)将包覆好的粉末放入真空干燥箱中在55℃烘干30min后取出,得到包覆有机物的钕铁硼粉末;
(3)将0.8g凝胶因子和1.5g松香溶于100g的甲苯中,并在80℃下不断搅拌至完全溶解,配制成预混液。将包覆好的钕铁硼粉末放入预混液中,固含量为55vol.%,并加入0.2vol.%的油酸,搅拌均匀,配制出打印浆料;
(4)将环形的模型输入3D冷打印机中,并将打印浆料装入3D打印设备的入料口中,开始打印,并打开取向充磁控制系统,在打印过程中打印的坯体在2.0T的磁场下不断取向,逐层打印出所需形状坯体;
(5)将打印好的坯体在50℃下真空干燥6h,并用塑料薄膜将干燥后的坯体进行密封,在200MPa压力下进行冷等静压,保压40s。再将冷等后坯体放入真空烧结炉中烧结,烧结温度为1080℃,保温300min,真空度为10-3Pa,冷却后得到环形的烧结钕铁硼磁体。
Claims (6)
1.一种3D冷打印制备烧结钕铁硼磁体的方法,其特征在于,所有的操作步骤均在氩气气氛的手套箱或真空气氛的设备下进行,且具体按如下步骤制备:
(1)制备包覆溶液:将有机物包覆体溶解在有机溶剂a中,搅拌均匀,配制成有机物包覆溶液,溶液浓度为0.05g/ml-2.5g/ml;
(2)粉末包覆:按照质量百分比,有机物包覆体的质量为钕铁硼粉末质量的0.6-1.5wt.%,量取对应体积的步骤(1)中的有机物包覆溶液,将有机物包覆溶液与钕铁硼粉末混合均匀,使溶液浸润全部的粉末;
(3)粉末处理:将包覆好的粉末放入真空干燥箱中在45-60℃之间烘干30-60min后取出,得到包覆有机物的钕铁硼粉末;
(4)配制打印料浆:按照重量百分比将一定量的凝胶因子和添加剂溶解在有机溶剂b中,并在50-100℃下不断搅拌至完全溶解,配制成预混液;将步骤(3)中包覆后的钕铁硼粉末放入预混液中,并加入0.01-0.5vol.%的油酸,搅拌均匀,其中钕铁硼粉末的固含量为50-70vol.%;
(5)取向打印成型:将所需形状的模型输入3D冷打印机中,并将步骤(4)中的浆料装入3D打印设备的入料口中,打开取向充磁控制系统,在打印过程中打印的坯体在1.2~2.0T的磁场下不断取向,逐层打印出所需形状坯体,实现磁体的取向打印成型;
(6)冷等静压:将步骤(5)中打印好的坯体在40-60℃下真空干燥4-12h,并用塑料薄膜将干燥后的坯体进行密封,在50-500MPa压力下进行冷等静压,保压30-120s;
(7)真空烧结:将步骤(6)中冷等静压后的生坯进行真空烧结,烧结温度为1020~1100℃,真空度为10-2-10-3Pa,保温120-360min,制备得到所需形状的烧结钕铁硼磁体;
步骤(2)中所述钕铁硼粉末为烧结钕铁硼粉末,粉末粒径为3-8μm。
2.根据权利要求1所述的一种3D冷打印制备烧结钕铁硼磁体的方法,其特征在于:步骤(1)中所述的有机物包覆体为无氧有机物,包括液体石蜡、石蜡、苯乙烯或聚苯乙烯中的一种或几种。
3.根据权利要求1所述的一种3D冷打印制备烧结钕铁硼磁体的方法,其特征在于:步骤(1)中所述的有机溶剂a为无氧溶剂,包括甲苯、二甲苯、二氯甲烷、三氯甲烷或环己烷中的一种或几种。
4.根据权利要求1所述的一种3D冷打印制备烧结钕铁硼磁体的方法,其特征在于:步骤(4)中所述凝胶因子为低氧且低分子量的1,3:2,4-二(3,4-二甲基苄叉)-D-木糖醇(C20H22O6),在预混液中的质量百分比为0.5-1.0wt.%。
5.根据权利要求1所述的一种3D冷打印制备烧结钕铁硼磁体的方法,其特征在于:步骤(4)中所述添加剂为无氧或低氧的强度添加剂,包括松香或聚乙烯醇缩丁醛,在预混液中的质量百分比为0.5-3.0wt.%。
6.根据权利要求1所述的一种3D冷打印制备烧结钕铁硼磁体的方法,其特征在于:步骤(5)中所述取向充磁控制系统由上、下两个电磁铁及控制单元组成,其中上方的电磁铁固定于打印机的顶端,下方的电磁铁固定于打印基板的底端,并通过电源控制单元实现Z轴方向充磁。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910016347.8A CN109590461B (zh) | 2019-01-08 | 2019-01-08 | 一种3d冷打印制备烧结钕铁硼磁体的方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910016347.8A CN109590461B (zh) | 2019-01-08 | 2019-01-08 | 一种3d冷打印制备烧结钕铁硼磁体的方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN109590461A CN109590461A (zh) | 2019-04-09 |
CN109590461B true CN109590461B (zh) | 2020-03-31 |
Family
ID=65965833
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910016347.8A Expired - Fee Related CN109590461B (zh) | 2019-01-08 | 2019-01-08 | 一种3d冷打印制备烧结钕铁硼磁体的方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109590461B (zh) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110354314B (zh) * | 2019-07-30 | 2021-11-12 | 东南大学 | 一种磁性增强相改性医用复合材料骨修复支架及制造方法 |
CN111370217B (zh) * | 2020-03-19 | 2021-07-13 | 中国科学院宁波材料技术与工程研究所 | 一种光固化辅助直写3d打印制备永磁体的方法 |
CN111451494A (zh) * | 2020-04-16 | 2020-07-28 | 苏州复浩三维科技有限公司 | 3d模型打印密实方法 |
CN111774561B (zh) * | 2020-06-08 | 2021-10-15 | 北京科技大学 | 一种3d冷打印制备电磁屏蔽用铜铁合金网的方法 |
CN111739729A (zh) * | 2020-08-08 | 2020-10-02 | 江西开源自动化设备有限公司 | 一种烧结钕铁硼的制造方法 |
FR3142367A1 (fr) * | 2022-11-28 | 2024-05-31 | Renault S.A.S | Procédé de fabrication d’une pièce comprenant au moins un aimant par fabrication additive |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103801697A (zh) * | 2014-02-11 | 2014-05-21 | 北京科技大学 | 一种金属浆料3d打印无模凝胶成形方法 |
CN106571219A (zh) * | 2016-10-27 | 2017-04-19 | 北京科技大学 | 磁场取向3d打印各向异性钕铁硼磁体的装置及方法 |
CN106735186A (zh) * | 2016-12-07 | 2017-05-31 | 北京科技大学 | 一种3d打印‑冷等静压制备钛合金多级齿轮的方法 |
CN108465806A (zh) * | 2018-03-12 | 2018-08-31 | 北京科技大学 | 一种有机物包覆合金粉末制备高性能粉末冶金制品的方法 |
CN108480643A (zh) * | 2018-03-05 | 2018-09-04 | 北京科技大学 | 一种3d冷打印制备复杂形状的金属结构件的方法 |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3066705B1 (fr) * | 2017-05-29 | 2022-12-02 | Commissariat Energie Atomique | Particule pour la realisation de pieces metalliques par impression 3d et procede de realisation de pieces metalliques |
-
2019
- 2019-01-08 CN CN201910016347.8A patent/CN109590461B/zh not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103801697A (zh) * | 2014-02-11 | 2014-05-21 | 北京科技大学 | 一种金属浆料3d打印无模凝胶成形方法 |
CN106571219A (zh) * | 2016-10-27 | 2017-04-19 | 北京科技大学 | 磁场取向3d打印各向异性钕铁硼磁体的装置及方法 |
CN106735186A (zh) * | 2016-12-07 | 2017-05-31 | 北京科技大学 | 一种3d打印‑冷等静压制备钛合金多级齿轮的方法 |
CN108480643A (zh) * | 2018-03-05 | 2018-09-04 | 北京科技大学 | 一种3d冷打印制备复杂形状的金属结构件的方法 |
CN108465806A (zh) * | 2018-03-12 | 2018-08-31 | 北京科技大学 | 一种有机物包覆合金粉末制备高性能粉末冶金制品的方法 |
Also Published As
Publication number | Publication date |
---|---|
CN109590461A (zh) | 2019-04-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109590461B (zh) | 一种3d冷打印制备烧结钕铁硼磁体的方法 | |
CN109676125B (zh) | 一种3d打印制备烧结钕铁硼磁体的方法 | |
CN106409497B (zh) | 一种钕铁硼磁体晶界扩散的方法 | |
CN110911149A (zh) | 一种提高钕铁硼烧结永磁体矫顽力的制备方法 | |
CN102103917B (zh) | 一种钕铁硼磁体、制备方法及应用该磁体的器件 | |
CN102903472A (zh) | 一种烧结钕铁硼磁体及其制备方法 | |
KR101165937B1 (ko) | 영구 자석 및 영구 자석의 제조 방법 | |
CN101752074A (zh) | 一种纳米铁基软磁块体的制备方法 | |
CN106158203B (zh) | 一种高矫顽力高稳定性钕铁硼磁体的制备方法 | |
CN111739729A (zh) | 一种烧结钕铁硼的制造方法 | |
CN104599802B (zh) | 稀土永磁材料及其制备方法 | |
CN103785845A (zh) | 一种微细球形Sm-Fe-N系永磁粉的制备方法 | |
CN104637667A (zh) | 一种防氧化的柔性粘贴NdFeB磁条及其制备方法 | |
CN104841938A (zh) | 一种高性能异形铁钴系软磁合金零件的制备方法 | |
CN103805827B (zh) | 纳米非晶低钕复相钕铁硼的制作方法 | |
CN104103414B (zh) | 一种制备高矫顽力各向异性纳米晶钕铁硼永磁体的方法 | |
CN104103415B (zh) | 一种氢化镝纳米粉末掺杂制备各向异性NdFeB稀土永磁体的方法 | |
KR101632562B1 (ko) | 이종금속이 확산된 R-Fe-B계 희토류 자성분말의 제조 방법 | |
JP2019519941A (ja) | 希土類焼結磁石の製造方法 | |
KR102589893B1 (ko) | 소결 자석의 제조 방법 및 소결 자석 | |
CN104576026B (zh) | 高矫顽力钕铁硼磁体的制备方法 | |
CN1411007A (zh) | 稀土-铁-硼永磁材料的制备方法 | |
KR102399418B1 (ko) | 소결 자석 제조 방법 및 이에 따라 제조된 소결 자석 | |
CN106531383A (zh) | 钐钴合金材料、钐钴合金粉末及其制备方法及钐钴基磁体 | |
CN108461272B (zh) | 一种用于形成氢化物纳米颗粒表面涂层的技术 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200331 |