纳米晶复合NdFeCoZrB永磁合金磁性能和温度稳定性的研究

利用熔体快淬法和品化退火工艺制备了纳米晶复合NdFeB永磁粘结磁体,研究了添加Zr元素对磁体室温磁性能和温度稳定性的影响.结果表明,添加3at%Zr元素能明显提高磁体的矫顽力和最大磁能积.在淬速18 m/s、退火温度640℃下制备的Nd_(9.5_Fe_(76)Co_5Zr_3B_(6.5)粘结磁体具有良好的综合磁性能,即剩磁为0.71 T,矫顽力为652 kA/m,最大磁能积为80kJ/m~3.适量添加Zr元素可以有效改善磁体的温度稳定性,在20～150℃,纳米晶复合Nd_95Fe_(76)Co_5Zr_3B_(6.5)粘结磁体的剩磁温度系数为-0.13%/℃,内禀矫顽力温度系数为-0.35%/℃;在150℃时效100h后,不可逆磁通损失为-4.50%.     

Behavior of residual carbon in Sm(Co, Fe, Cu, Zr)z permanent magnets

When sintered Sm(Co, Fe, Cu, Zr)_z permanent magnets are prepared by metal injection molding, some organic binders are added in alloy powder, which leads to much residual carbon in the magnets. The residual carbon decreases magnetic properties and destroys the microstructure of the magnets. In this paper, the behavior of carbon in Sm(Co, Fe, Cu, Zr)_z permanent magnets has been studied. The results indicate that Sm(Co, Fe, Cu, Zr)_z magnets can keep excellent magnetic properties when the carbon content is below 0.1 wt.%: Br ≥ 10 kGs, H_cj ≥ 22 kOe, BH_max ≥ 25 MGOe. When the carbon content is above 0.1 wt.%, Br, H_cj and BH_max decrease with increasing carbon content evidently. Carbon consumes Zr content and forms ZrC, which reduces the volume fraction of the lamella and Sm(Co, Cu)₅ phases. Thus, the cell size increases and the cellular microstructure deteriorates. When the carbon content reaches 0.43 wt.%, there is not enough Sm(Co, Cu)₅ phase to form a uniform cellular microstructure. Br, H_cj and BH_max are approximate to zero. Since carbon has little influence on the content of Sm₂(Co, Fe)₁₇ phase, Ms can keep a high value (≥100 emu/g). ZrC has high melting point (3420 °C) and acts as dispersion particle in the magnets, which prevents the grains of SEM structure growing and reduces the liquid content of green compacts during sintering. Therefore, the density of the magnets decreases.     

ANISOTROPIC THERMAL EXPANSION AND FRACTURE OF RADIALLY ORIENTED TOROIDS OF RE-Co PERMANENT MAGNETS

研究SmCo_5辐向取向烧结环体的断裂机制指出:SmCo_5的强烈各向异性的热膨胀性质决定了辐向环在烧结后的断裂。导出了一个临界断裂取向度的表示式。计算和实验的结果都表明:烧结的SmCo_5辐向环的取向度通常不能大于0.7。实验发现以铜取代部分的钴,以及成分移向富钴的2-17相区,都使热膨胀各向异性特性明显降低,特别是Sm(Co_(0.80)Cu_(0.14)Fe_(0.06)_7和Sm(Co_(0.87)Cu_(0.13)_8二者几乎是完全各向同性的,是制备高性能辐向磁体的理想材料。还讨论了热膨胀各向异性的来源,在Sm(Co,Cu)_5中,铜原子可能部分地优先取代2c晶位。     

EFFECTS OF AS-CAST CRYSTALLINE STRUCTURE AND Cu SEGREGATION ON COERCIVITY OF Sm (Co, Cu, Fe, Mn)_(7.8) PERMANENT MAGNET

本文研究了Sm(Co, Cu, Fe, Mn)_(7.8)永磁体铸造结晶组织及Cu偏析对矫顽力的影响。结果表明,不同冷却速度的铸造合金锭具有不同的结晶组织。在等轴晶组织中,晶内贫Cu,晶界上富集游离Cu,保存有一些Sm_2Co_(17-x)T_x六方结构高温相,造成矫顽力下降;而在细的柱状晶组织中,无严重的成分偏析。经烧结和固溶处理后的磁体,为位错胞状显微组织,胞壁间弥散着脱溶Cu和富Cu的SmCo_(5-x)T_x相,它们在反磁化过程中,可能对畴壁起着钉扎作用,因而具有高矫顽力。     

Structure and magnetic properties ofhigh-performanced Sm2（Co, Fe, Cu, Zr）17 alloys

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Ni/Co比例及微量Dy对FeCoNiBSiNb块体非晶合金玻璃形成能力和磁性能的影响

采用水冷铜模吸铸工艺制备了一系列的(Fe0.5Co1-xNix)72B19.2Si4.8Nb4(x=0,0.05,0.1,0.15,0.2,0.25,0.3,0.4)块体非晶合金.并采用X射线衍射仪(XRD)、差热分析仪(DTA)、振动样品磁强计(VSM)测试了块体非晶合金的结构、热稳定性和软磁性能.探讨了不同Ni/Co比例及添加稀土元素Dy对FeCoNiBSiNb系合金玻璃形成能力(GFA)、热稳定性及磁性能的影响.结果表明:当x=0.05,0.1,0.15,0.2时可制备出直径2mm的非品合金棒,但不能获得3mm非晶合金棒,x=0.25,0.3,0.4均不能获得直径2mm的非晶合金棒,且随Ni/Co比例的增大,即随Ni含量的增加,热稳定性先增加,后逐渐减小,过冷液相区△Tx逐渐减小,非晶合金的玻璃形成能力呈下降趋势,非晶合金的饱和磁化强度(Ms)下降.添加1 at%Dy后,提高了合金的非晶形成能力,可制备出直径3mm的[(Fe0.5Co0.4Ni0.1)72B19.2Si4.8Nb4]99Dy1非晶合金棒,但合金的Ms下降.     

TEM STUDY OF MECHANISM OF STRAIN-AGE HARDENING OF INITIALLY DISORDERED (Co,Fe)_3V ALLOY

TEM study was made to explore the mechanism of the strain-age hardening of initially-dis-ordered (Co_(78)Fe_(22))_3V,which was found to be attributed to the formation of a special disloca-tion-stacking fault configuration in company with disorder-order transformation-disloca-tions extended to stacking faults on{111}planes and got connected with each other throughpartial dislocation reaction at intersections of{111}planes,leading to dense networks withcells bounded by stacking fault tetrahedrons.The results also indicated that ordered(Co_(78)Fe_(22))_3V has very low stacking fault energy on{111}planes and relative high andisotropie antiphase boundary energy,which implies that it is most likely to be Lomer-Cottrelllocks,not Kear-Wilsdof locks,that are responsible for the high strength at high temperaturesof this alloy.     

Effect of Fe on Microstructure and Coercivity of SmCo-Based MagnetsEI北大核心CSCD

High-temperature permanent magnets have an important application in the aerospace and other high-tech fields, among which 2:17-type SmCo magnets have become the first choice for high-temperature permanent magnets due to the strong magnetic anisotropy and high Curie temperature. Although there are studies on the effect of Fe on the remanence and coercivity, the role that Fe plays on coercivity mechanism of SmCo magnets is still unclear. In this work, Sm(CobalFexCu0.08-0.10Zr0.03-0.033) z (x= 0.10-0.16, z=6.90 and 7.40) magnets are prepared and the magnetic properties under different temperatures are investigated. The magnets with an intrinsic coercivity of 603.99 kA/m and a maximum energy product of 87.30 kJ/m(3) at 500 degrees C. are obtained. It is revealed that at room temperature the coercivity of the magnets increases with increasing Fe content, however, at 500 degrees C. the coercivity shows an opposite dependency on Fe content. Moreover, the effect of Fe on coercivity is more obvious at low z value. The phase structure and composition analyses were characterized by XRD and TEM. The results show that with the increase of Fe content, the size of the 2: 17R cell phase increases, the volume ratio of cell boundary 1: 5H phase decreases, and furthermore, both Fe content in the 2: 17R phase and Cu content in the 1: 5H phase increase. The variations of Fe and Cu contents in both phases lead to the change of the domain wall energy difference. With the increase of Cu content of 1:5H phase, the domain wall energy of 1: 5H phase (gamma(1:6)) drops faster at room temperature, the coercivity is determined by gamma(2:17)-gamma(1:5), so the coercivity increases with increasing Fe content. While at 500 degrees C, due to gamma(1:6) at its Curie temperature, the coercivity is mainly determined by the domain wall energy of 2: 17R phase (gamma(1:17)), which decreases with increasing Fe content. The increase of Fe content at the low z value results in a smaller growth of cell size, which leads to a more significant change in coercivity.     

EFFECT OF HEAT OF MIXING ON FORMATION AND STABILITY OF Zr-BASE METALLIC GLASSES

用熔融自旋技术制备了Zr_(1-x)M_x(M=Fe,Co,Ni,Cu和Pd)和Cu_(67.5)Ti_(32.5)合金玻璃体。用变换转鼓切线速度的方法,确定了上述合金形成玻璃态的临界切线速度为31m/s。所有合金玻璃体经X射线衍射分析证明为玻璃态结构。用示差扫描量热器,以不同的升温速率测量了它们的热行为。在Fe_(24)Zr_(76),Ni_(24)Zr_(76)合金玻璃体中呈现出一个放热峰,而Co_(21)Zr_(79),Pd_(24.5)Zr_(75.5),Cu_(45)Zr_(55)和Cu_(67.5)Ti_(32.5)则有两个或三个放热峰。用Kissinger技术确定了各个合金玻璃的结晶激活能。最后讨论了由Miedema模型计算的二元合金的混合热对合金玻璃体形成和稳定性的影响。     

THE PHENOMENON OF THE LOW TEMPERATURE STRUCTURAL IN AMORPHOUS ALLOY (Fe_(0.1)Ni_(0.5)Co_(0.4))_(78)Si_8 B_(14)

利用磁导率减落的自动测量仪,测量了非晶合金(Fe_(0.1)Ni_(0.5)Co_(0.4))_(78)Si_8B_(14)等温时效时退磁不能恢复的减落。以此考查了低温结构弛豫动力学行为,计算了弛豫激活能和弛豫谱。结果表明,低温结构弛豫是平均激活能低的多弛豫过程,在这个过程中发展了化学短程序(CSRO)。     

Fe含量对高温稀土永磁Sm(CobalFexCu0.1Zr0.03)7.5 (x=0.09～0.21)磁性能的影响

采用粉末冶金工艺制备了高温稀土永磁Sm(CobalFexCu0.1Zr0.03)7.5 (x=0.09～0.21),研究了Fe含量对磁体磁性能的影响.结果表明:随着Fe含量的增加,剩磁Br和最大磁能积(BH)max逐渐增加,在x=0.21时获得最大值,分别为0.96 T和176.7 kJ/m3;内禀矫顽力Hci先增加后降低,在x=0.15时获得峰值2276.6 kA/m.最佳工艺制备(x=0.15)的磁体温度稳定性良好,B-H退磁曲线在温度为500 ℃时保持为直线;内禀矫顽力温度系数β为-0.16%/℃,最高使用温度(OT)max达到533 ℃.     

微量稀土Dy及Fe/Co比例对FeCoBSiNb块体非晶合金玻璃形成能力和磁性能的影响

采用铜模吸铸工艺成功制备了一系列的[(Fe_xCo_(1-x))_(0.72)B_(0.192)Si_(0.048)Nb_(0.04)]_(100-y)Dy_y(x=0.5,0.6,0.7,0.8,0.9;y= 0,1,2,3)块体非晶合金,并采用X射线衍射仪(XRD)、示差扫描量热分析仪(DSC)、振动样品磁强计(VSM)测试块体非晶合金的结构、热稳定性和软磁性能;分析了稀土元素Dy以及不同Fe/Co比例对FeCoBSiNb系合金玻璃形成能力(GFA)、热稳定性及磁性能的影响。结果表明:添加2at%的Dy后,合金的非晶形成能力提高,可制备出φ3mm的[(Fe_(0.5)Co_(0.5))_(0.72)B_(0.192)Si_(0.048)Nb_(0.04)]_(98)Dy_2非晶合金棒,但合金饱和磁化强度(M_s)下降;[(Fe_xCo_(1-x))_(0.72)B_(0.192)Si_(0.04)8Nb_(0.04)]_(98)Dy_2非晶合金随Fe/Co比例从5∶5增加至8∶2时,均能形成φ2 mm的非晶棒,但合金的非晶形成能力呈下降趋势,而其饱和磁化强度随铁含量的增大而提高。     

Co、Ni添加对FeBYNb块体非晶合金玻璃形成能力和磁性能的影响

采用铜模吸铸工艺成功制备了一系列的(Fe_(1-x-y)Co_yNi_x)_(68.4)B_(23)Y_(4.6)Nb_4块体非晶合金,并采用X射线衍射仪(XRD)、差热分析仪(DTA)、振动样品磁强计(VSM)测试块体非晶合金的结构、热稳定性和磁性能.探讨了不同Co、Ni含量对(Fe_(1-x-y)Co_yNi_x)_(68.4)B_(23)Y_(4.6)Nb>.4>系合金玻璃形成能力(GFA)及磁性能的影响.结果表明:合金(Fe_(0.5)Co_(0.5))_(68.4)B_(23)Y_(4.6)Nb_4、(Fe_xNi_(1-x)_(68.4)B_(23.6)Nb_4(x=0.05、0.1、0.15、0.2)、(Fe_(1-x-y)Co_yNi_x)_(68.4)B_(23)Y_(4.6)Nb_4(x=0.15、0.3、0.45,y=0.1、0.2)均可制得直径为3 mm的非晶棒.该系列合金均具有良好的软磁性能,但随着Co、Ni含最的增加,其饱和磁化强度均下降.     

PREPARATION OF HIGH COERCIVE Sm-Fe-N PERMANENT MAGNET

Using pure Sm and Fe powders as starting materials,high coercive Sm-Fe-N mag-nets have been prepared by mechanical alloying in combination with beat treatmentand nitriding.The best result is:_iH_c=33.1 kA/cm(41.6 kOe)and(BH)_(max)=98.7kJ/cm~3(12.4 MGOe).The phases formed in the specimens during mechanical alloying,crystallizing and nitriding processes were examined by X-ray diffraction technique.Themagnetic properties of the specimens were measured with the pulsed magnetometer infield up to 12 T.Experimental results show that mechanical alloying is an efficient ap-proach for preparing high coercive magnets.As an important factor for obtaining a highcoercivity,the grain sizes of magnets are about tens of nanometer.The presence of somesoft magnetic phases in the specimens leads to a neck on the demagnetization curve.     

APPROACH TO TRANSITION OF NON-CRYSTALLINE METAL GLASSES WITH AID OF METHOD OF POLYMER TRANSITION RESEARCH

对某些金属和类金属按一定比例在高温下熔融混合,并急速冷却,可以得到性能极为特殊的非晶态金属。我们根据高聚物转变理论,用研究高聚物的扭辫仪、线膨胀仪,再结合DSC和X射线衍射仪,对非晶态金属[Fe_(0.1)Ni_(0.35)Co_(0.55)]_(78)Si_8B_(14),[Fle_(0.1)Ni_(0.30)Co_(0.55)Mo_(0.05)]_(78)Si_8B_(14)和[Fe_(0.1)Ni_(0.30)Co_(0.55)Nb_(0.05)]_(78)Si_8B_(14)的玻璃化转变及晶化转变的自由体积、激活能、内耗与热效应等进行了研究,观测到玻璃化温度及晶化温度、玻璃化转变激活能及晶化激活能均与合金元素原子半径有关,转变时的热效应与内耗峰值有一定的对应关系。讨论了玻璃化转变及晶化转变的机理,可供设计非晶态金属时参考。     

Effects of oxygen and carbon on the magnetic properties and microstructure of Sm2Co17 permanent magnets

The research on the sintered Sm2Co17 permanent magnets prepared by metal injection molding is still at the exploratory stage. Carbon and oxygen are two key factors that influence the magnetic properties. In this article, the effects of oxygen and carbon on the properties and microstructure of the magnets have been studied. The results indicate that oxygen consumes the effective Sm content of the magnets and forms Sm2O3-the non-magnetism phase, which result in the deterioration of the magnetic properties. Besides, the magnetic properties decrease in evidence with increasing carbon content. The main factor that affects the magnetic properties is the deterioration of the microstructure of the magnets. The Sm（Co, Cu）5 phase decreases, whereas the cell size increases with the increase of the carbon content. When the carbon content is above 0.43 wt.%, the Sm（Co, Cu）5 phase is not enough to form a uniform cellular microstructure. Thus the magnetic properties disappear. ZrC is detected in the magnets by XRD when the carbon content is above 0.21 wt.%. ZrC also reduces the properties of the magnets.     

含Fe和Mn的Ni_(30)Cu_(70)固溶体团簇模型与耐蚀性研究

提出了一个极限田溶体合金的团簇模型,在此基础上优化设计了添加Fe和Mn的Ni_(30)Cu_(70)(原子分数,%)固溶体合金成分.在该模型中,固溶的Fe和Mn以Ni为第一近邻形成12配位立方八面体原子团簇(Fe_(1-x)Mn_x)Ni_(12)而分散到Cu基体中,因此极限固溶体合金成分为[M_1/_(13)Ni_(12)/_(13)]30Cu_(70)=[(Fe_(1-x)Mn_xNi_(12)]Cua_(30.3),M=(Fe_(1-x)Mn_x).采用X射线衍射和电化学腐蚀测试等方法,研究了[(Fe_(1-x)Mn_x)Ni_(12)]Cu_(30.3)合金的微观组织与耐腐蚀性能的关系.实验结果表明,对应于极限同溶体状念的[(Fe_(0.75)Mn_(0.25))Ni_(12)]Cua_(30.3)合金,在3.5%NaCl溶液中具有相对好的耐腐蚀性能.     

退火温度对(Fe_(0.5)Co_(0.5))_(78.4)Si_9B_9Nb_(2.6)Cu_1软磁合金高频磁性的影响

研究了不同退火温度对(Fe_(0.5)Co_(0.5))_(78.4)Si_9B_9Nb_(2.6)Cu_1纳米晶软磁合金结构和高频磁性的影响。结果表明,在初始晶化温度455℃以上退火,在非晶基体中析出α—FeCo相。随着退火温度的升高,开始出现有序的(Fe,Co)_3Si。当退火温度高于620℃时,出现硼化物硬磁相。490℃退火后合金的初始磁导率最高可达23000,晶粒尺度为19.4 nm。在490~610℃退火,随退火温度的提高,合金复数磁导率下降,但截止使用频率提高。实验观察到该合金的磁谱曲线为驰豫型,截止使用频率f_r为3.14~5.64 MHz,明显高于Fe基纳米晶软磁合金。     

DYNAMICS OF PRECIPITATION AND TRANSFORMATION OF CARBIDES IN A Ni-BASE SUPERALLOY

The quantitative analytical method combining the electrolytic extraction with X-raydiffraction analysis to determine the carbides and TCP in a Ni-base superalloy wasdeveloped.The variation of decomposition of MC and precipitation of M_(23)C_6 and M_6C withhot exposure time at 850—1000℃ is shown to conform to hyperbolic law.The elemental con-stitution of M_(23)C_6 changes continutously during the hot exposure process.At the primarystage the constitution of the precipitates is(Cr_(0.67)Mo_(0.13)Ni_(0.13)Co_(0.07))_(23)C_6.Then with in-creasing Cr and decreasing Mo,Ni and Co it finally becomes(Cr_(0.88)Mo_(0.07)Ni_(0.03)Co_(0.02))_(23)C_6.The higher the hot exposure temperature,the faster the final constitution of M_(23)C_6 may beachieved.     

新型耐高压铸造锡青铜的研制

以ZCuSn3Zn8Pb6Ni1合金为基础,通过添加Fe和Co,开发了耐高压铸造ZCuSn3Zn8Pb6Ni1FeCo合金,研究了Fe和Co对合金组织和性能的影响.结果表明,ZCuSn3Zn8Pb6Ni1FeCo合金显微组织与ZCuSn3Zn8Pb6Ni1的相同之处在于均以α-{ Cu,Sn,Zn }为基体,存在硬脆相δ- Cu10Sn3,Pb以单质形式析出;ZCuSn3Zn8Pb6Ni1FeCo合金中还存在α-Fe和γ-Fe析出相,以及CoCu2Sn 、Fe3Co7、Fe4Zn9等硬质相,这些硬质相和基体之间为共格或半共格关系;ZCuSn3Zn8Pb6Ni1合金铸造组织为典型的枝晶组织,晶粒平均直径约3 mm,抗拉强度为180～230 MPa,而ZCuSn3Zn8Pb6Ni1FeCo合金为等轴晶组织,晶粒平均直径为20～60 μm,抗拉强度为400～450 MPa,伸长率在20%以上;ZCuSn3Zn8Pb6Ni1FeCo合金消除了明显存在于ZCuSn3Zn8Pb6Ni1合金中的Sn的宏观偏析.