Research progress on sintering additive used for high thermal conductivity silicon nitride ceramics
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摘要:
氮化硅被认为是综合性能最好的陶瓷材料，良好的导热性和优异的力学性能使其成为大功率电子器件用陶瓷基板的主流材料，在纯电动/混合电动汽车中得到广泛应用。烧结助剂对氮化硅烧结活性、微观组织和第二相成分及含量影响较大，进而影响陶瓷导热性能，选择合适的烧结助剂对制备高导热氮化硅陶瓷非常重要。本文整理了目前制备高导热氮化硅陶瓷用烧结助剂研究现状，分析了烧结助剂对氮化硅陶瓷导热性及力学性能的影响，并对烧结助剂未来的研究方向和发展趋势提出了展望。
Abstract:Silicon nitride (Si3N4) is considered to be the best ceramic material for the comprehensive properties. High thermal conductivity and the excellent mechanical properties make it widely used as the ceramic substrate in electric vehicles and hybrid electric vehicles (EV/HEV). Sintering additives have the great influence on the sintering activity, microstructure, and the second phase composition of silicon nitride, and then affect the thermal conductivity of ceramics. Selecting the suitable sintering additives is very important for the preparation of high thermal conductivity silicon nitride ceramics. The research status of sintering additives used for the preparation of high thermal conductivity silicon nitride ceramics was summarized in this paper, the influence of sintering additives on the thermal conductivity and mechanical properties of silicon nitride ceramics was analyzed, and the future research direction and development trend of sintering additives were put forward.
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Keywords:
- silicon nitride /
- ceramics /
- sintering additives /
- thermal conductivity /
- mechanical properties
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H11钢是欧洲压铸行业中最常用的三种热作模具钢之一，其耐冷热疲劳性能好，抗溶蚀性能好，冷热加工性能好，可用于高速锤锻模，应用领域较广[1−2]。H11钢在加工时会产生返回料（如车削屑），通过固态再生技术[3]对其回收可以有效减少资源的浪费，通过粉末冶金工艺可以节约金属，降低成本，具有一定的经济意义[4]。除此之外，粉末冶金工艺还可以解决传统工艺生产钢铁中存在的元素偏析等问题[5]。薛松等[6]对H13钢进行了等温球化退火热处理，通过该方法得到的退火后碳化物组织分布均匀，消除了原始组织中的网状碳化物和网络碳化物等缺陷，降低了退火硬度。张春华等[7]对H13钢进行了新工艺热处理，包括冷却锻造、加热炉加热、空冷、加热和保温，有助于提高H13钢退火组织的均匀性。本课题组前期有学者在研究H11车削屑固态再生工艺时发现，不同粒度车削屑粉末（中位径分别为75、123和144 μm）对再生材料的影响主要有两方面：一是细粉再生材料的表面裂纹较粗粉再生材料的裂纹少且浅，二是细粉比表面积大、表面活性大。三种不同粒度的粉末在768 MPa压力下，经
1180 ℃温度挤压锻后，具有较好的强度和硬度，而塑性较差[8]。万霄等[9]研究了正火冷却和亚温淬火对H13钢微观组织和力学性能的影响，得出正火后采用空冷的冷却方式能够得到均匀性更好的退火态组织的结论。本文以回收的车削屑为原料，经磨粉、粉末压坯、挤压段工艺后制成合格的初级样品，对初级样品进行热处理，并对比了热处理样品与原再生H11钢的力学性能。1. 实验材料与方法
1.1 H11钢物相参数计算
利用JMatPro软件可模拟计算出钢在不同温度下的相组成、奥氏体化过程及过冷奥氏体连续冷却的各项参数，为实际热处理工艺提供依据[10−12]。在JMatPro软件中输入H11钢组成成份（表1），模拟计算出钢在不同温度下的物相含量（质量分数）[13]，结果如图1所示。
表 1 H1钢化学成分（质量分数）Table 1. Chemical composition of the H11 steels% 钢号 C Cr Mo Si V Mn H11（4Cr5MoSiV） 0.33～0.43 4.75～5.50 1.10～1.16 0.80～1.20 0.30～0.60 0.25～0.50 ![]()
图 1 在不同温度下H11钢中物相含量（a）和M(C,N)含量（b）Figure 1. Phase (a) and M(C,N) (b) content in H11 steels at different temperatures由图1可知，当温度在850 ℃以上时，只有奥氏体和极少量MC型碳化物存在，当温度逐渐降低，奥氏体含量也逐渐减少，铁素体和MC型碳化物开始析出。温度825 ℃时，奥氏体相消失，850～825 ℃区间内，MC碳化物含量减少。该合金的珠光体转变为奥氏体温度（A1）为830 ℃，铁素体转变为奥氏体温度（A3）为920.9 ℃。当温度为900 ℃时，M3C型碳化物质量分数为1.1%，随着温度降低，该碳化物含量开始升高；850 ℃时，碳化物质量分数升高到2.5%；在850～820 ℃区间内，碳化物含量升高速度加快；820 ℃时，该碳化物质量分数升高到6.2%[14−15]。
图2和表2给出了H11钢奥氏体化过程曲线和参数，反映了奥氏体化过程中加热速度、温度与奥氏体化程度之间关系。其中，A1线是珠光体转变为奥氏体的临界温度线，该线下方①区域的组织为铁素体+碳化物；A3线是铁素体转变为奥氏体的临界温度线，②区域的组织为奥氏体+铁素体+碳化物；均一化线与A3线之间的③区域组织为奥氏体+碳化物；而均一化线以上的④区域组织为均匀化奥氏体。从图2和表2中可以看出，H11钢的相变温度随加热速度增大而升高，均一化温度也升高，从表2中还可以看出，奥氏体均匀化时间随加热速度增大而减少。根据不同的加热速度选择合适的保温时间，当加热速度小时，要适当延长保温时间。
表 2 不同加热速度对应的奥氏体化过程参数Table 2. Parameters of the austenitizing process at different heating rates加热速度 /
(℃·s−1)A1 / ℃ A3 / ℃ 奥氏体均匀化
温度 / ℃奥氏体均匀化
时间 / s1 816 836 865.0 845.0 10 821 872 924.0 90.4 100 841 956 1011.2 9.9 H11钢过冷奥氏体连续冷却转变（continuous cooling transformation，CCT）曲线如图3所示，反映了过冷奥氏体连续冷却时的转变产物类型以及转变量与冷却速度之间的关系。根据图3可以得到不同冷却速度下合金相组成含量，结果如表3所示。当冷却速度从100.00 ℃/s降低到0.01 ℃/s时，铁素体和珠光体含量逐渐增大，贝氏体和马氏体含量逐渐减少；冷却速度为0.01 ℃/s时，合金组织只由铁素体和珠光体组成；冷却速度在10.00 ℃/s及以上时，合金中组织主要为马氏体。
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图 3 H11钢过冷奥氏体连续冷却转变曲线Figure 3. Continuous cooling transformation curves of the H11 steels表 3 不同冷却速度下H11钢中相组成含量Table 3. Phase composition content in the H11 steels at different cooling rates冷却速度 / (℃·s−1) 质量分数 / % 奥氏体 铁素体 贝氏体 珠光体 马氏体 0.01 0 0.3300 0 99.67 0 0.10 0 0.0623 95.160 1.89 2.88 1.00 0.18 0 15.290 0 84.52 10.00 0.21 0 0.065 0 99.72 100.00 0.21 0 0 0 99.79 1.2 材料与制备工艺
通过磨粉机研磨H11钢得到实验用钢粉，先将粗粉过60目筛，后过80目筛，再将过筛后的钢粉重新过200目筛，得到3种不同粒度H11钢粉末。钢粉1为过200目筛后得到的粉，钢粉2为过80目筛的粉，钢粉3为过60目筛的粉。经过测量，挤压后三种钢粉的密度分别为7.132 g/cm3、7.403 g/cm3、7.430 g/cm3。参照课题组前期研究结果，选择挤压锻温度为
1220 ℃，压坯尺寸为ϕ5 mm×55 mm。根据JMatPro软件模拟结果确定球化退火热处理制度，如图4所示，脱模时将模具加热到450 ℃左右，随后样品随炉升温到880 ℃，保温3 h，炉冷到750 ℃，保温4 h，后炉冷到500 ℃以下，出炉空冷[4,14]。将钢粉1、钢粉2和钢粉3经过固态再生工艺制备的样品称为试样1、试样2和试样3。试样1中的杂质粒子分布极不均匀，试样2和试样3中的杂质在基体中总体分布比较均匀。![]()
图 4 H11钢球化退火制度示意图Figure 4. Schematic diagram of the spheroidizing annealing system for the H11 steels1.3 检测方法与表征手段
利用PANalytical型X射线衍射仪（X-ray diffraction analyzer，XRD）对挤压锻样品的进行物相分析。采用金相显微镜观察试样金相组织，选取相同位置取样，利用砂纸磨制+抛光膏抛光+10%硝酸酒精溶液（体积分数）腐蚀得到金相试样。使用硬度计测试退火试样硬度。通过拉伸试验机测试退火试样沿挤压锻方向的拉伸性能。将热处理后的试样用线切割制成片状，将样品沿平行于和垂直于挤压锻方向进行切割，平行于挤压锻方向拉伸样品总长52 mm、厚2 mm，平行段长15 mm、宽3 mm、厚2 mm，夹持段两端各15 mm，过渡弧半径为3.5 mm；垂直于挤压锻方向拉伸样品平行段长度为8 mm、宽3 mm、后2 mm，过渡弧半径为3.5 mm，夹持段两端各长为5 mm。利用扫描电子显微镜（scanning electron microscope，SEM）观察拉伸试样断口形貌，分析试样断裂形式。
2. 结果与分析
2.1 物相分析
挤压锻试样X射线衍射图谱如5所示。由图可知，试样1有明显的氧化物峰，说明钢粉1氧化严重；试样2和试样3中有Fe7C3生成，这对材料性能，尤其是硬度有影响，材料硬度值将会随着其析出量的增加而升高。
图6为球化退火热处理试样的X射线衍射图。由图可知，退火样品基体仍为α-Fe，试样1中Fe3O4峰型变尖，说明结晶度增加[16]，试样2、试样3中Fe7C3相消失[17]，说明该相含量过少，材料硬度值下降；基体铁素体峰型变窄变尖，说明材料中铁素体结晶度和原始再生H11钢相比有所提高，晶粒较大。
2.2 微观组织分析
三种不同粒度试样热处理前金相组织如图7和图8所示。从图7（a）和图7（8）可以看出，由于杂质分布不均，在杂质较少区域，发生了再结晶和晶粒长大，产生了较大的铁素体晶粒，并且从金相图推测，该区域基体发生了脱碳，且氧化物含量越高，基体碳损失越大。
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图 7 热处理前试样沿挤压方向金相组织：（a）试样1；（b）试样2；（c）试样3Figure 7. Metallographic microstructure of the samples along the extrusion direction before heat treatment: (a) sample 1; (b) sample 2; (c) sample 3![]()
图 8 热处理前试样沿垂直挤压方向金相组织：（a）试样1；（b）试样2；（c）试样3Figure 8. Metallographic microstructure of the samples vertical the extrusion direction before heat treatment: (a) sample 1; (b) sample 2; (c) sample 3从图7（a）～图7（b）可以看出，在挤压锻温度
1220 ℃下的样品晶粒为等轴晶，发生了再结晶和晶粒长大，基体主要为粒状贝氏体和铁素体；图7（b）～图7（c）和图8（b）～图8（c）的基体组织为下贝氏体、铁素体；从图7（b）～图7（c）可以看出，压坯在加热到奥氏体温度区间挤压锻后产生了带状组织，这些带状组织在冷却过程以残余奥氏体的形式保留了下来，并沿挤压锻方向呈带状分布。三种试样退火金相组织如图9和图10所示。从图中可以看出，等温球化退火试样的组织较原再生H11样品更均匀，晶粒较挤压锻之前变小，横向和纵向的组织差异较小，纵向组织带状分布消失。图9（a）和图10（a）基体主要组织为铁素体，图9（b）和图10（b）为珠光体和弥散分布的碳化物，图9（c）和图10（c）为珠光体、弥散分布在珠光体上的碳化物和残余奥氏体[18]。
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图 9 等温球化退火试样沿平行挤压方向金相组织：（a）试样1；（b）试样2；（c）试样3Figure 9. Metallographic microstructure of the samples parallel the extrusion direction after isothermal spheroidized annealing: (a) sample 1; (b) sample 2; (c) sample 3![]()
图 10 等温球化退火试样垂直挤压方向金相组织：（a）试样1；（b）试样2；（c）试样3Figure 10. Metallographic microstructure of the samples vertical the extrusion direction after isothermal spheroidized annealing: (a) sample 1; (b) sample 2; (c) sample 32.3 硬度测试
三种粒度试样在等温球化热处理前后力学性能如表4所示。热处理前，试样1硬度要比试样2和试样3低很多，通过对金相组织和X射线衍射结果分析可知，固溶在热处理前试样1基体中的碳和氧化物发生反应脱出，试样2和试样3基体中生成了弥散分布的Fe7C3，这种类型碳化物的析出使得试样硬度得到明显提升。经等温球化退火热处理后三种试样硬度均出现明显下降，这主要是由于在等温球化退火过程中，材料基体组织发生了改变，珠光体内的片状渗碳体以及先共析渗碳体都变为球粒状，均匀分布于铁素体基体中。样品经过等温球化退火后的组织为球状珠光体和弥散分布的颗粒状碳化物，挤压锻过程中生成的碳化物Fe7C3相消失。碳化物自身硬度、弥散分布状态、大小和相对含量对钢的硬度起着至关重要的作用[6]。
表 4 不同粒度试样热处理前后性能参数Table 4. Performance parameters of the samples in different particle sizes before and after heat treatment力学性能 等温球化热处理前 等温球化热处理后 试样1 试样2 试样3 试样1 试样2 试样3 抗拉强 / MPa 218 815 1127 206 471 541 硬度，Hv 167 451 478 164 185 192 延伸率 / % 0.5 0.7 3.3 0.5 4.5 12.8 2.4 拉伸性能分析
三种试样球化退火后沿挤压锻方向的工程应力-应变曲线如图11所示。从图中可以看出，由于钢粉1颗粒较细，杂质粒子在某些区域发生严重的偏析，造成试样1中杂质粒子聚集，形成尺寸较大的团聚区，分布极不均匀，屈服强度和抗拉强度接近且都较低，几乎没有产生塑性变形，延伸率仅为0.5%；试样2和试样3的屈服强度接近，但抗拉强度和延伸率相差较大，这也是由于氧化物夹杂的影响，试样2所用原料钢粉2杂质含量相对于试样3所用原料钢粉3要高[19]，杂质在局部区域会发生小范围的聚集，这大大增加了材料在杂质聚集区断裂的可能。从表4中退火样品与原再生H11钢对比可知，退火样品抗拉强度降低，延伸率升高，塑性韧性变好。
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图 11 球化退火试样沿挤压锻方向工程应力-应变曲线Figure 11. Engineering stress-strain curves of the samples along the extrusion direction after isothermal spheroidized annealing2.5 断口分析
图12为不同粒度试样退火后平行挤压方向拉伸断口形貌。从图中可以看出，试样1断口形貌呈现明显的砂糖状，氧化物杂质较多，属于晶间断裂的类型。试样2和试样3呈现出准解理断裂的特征，断口表面有大大小小的韧窝，还可以观察到明显撕裂棱[20]。试样3的韧窝要比试样2的韧窝深，撕裂棱更粗，撕裂棱上布满小韧窝，这说明试样3的塑性要比试样2的较好，延伸率更高，这是由于试样3所用原料钢粉3中杂质较少，材料在杂质聚集区断裂的可能减少。这与拉伸试验的结果一致。
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图 12 不同粒度试样球化退火后沿平行挤压方向拉伸断口形貌：（a）试样1；（b）试样2；（c）试样3Figure 12. Tensile fracture morphologies of the samples in different particle sizes after spheroidizing annealing parallel the extrusion direction: (a) sample 1; (b) sample 2; (c) sample 33. 结论
（1）粉末粒度与杂质对H11车削屑固态再生钢强韧性的影响具有双重作用：一方面，粉末粒度越小，高温挤锻压后强度和硬度越好，但杂质粒子越易出现偏析，发生聚集，分布不均，韧性较差；另一方面，粉末粒度越小，高温挤锻压后等温球化热处理过程中氧化越严重，强度和硬度变差，韧性较好。
（2）等温球化退火处理后样品的组织为球状珠光体和弥散分布的颗粒状碳化物。
（3）等温球化退火处理后，材料的塑性变好，采用粒度为144 μm的钢粉制备的样品延伸率从3.4%升高到12.8%，但抗拉强度和硬度分别下降了52%和60%。
（4）粉末粒度过小容易发生氧化且杂质不易去除，后续实验应选择粒度合适的车削屑进行。
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表 1 各种陶瓷基板的物理性能
Table 1 Physical properties of the ceramic substrates
材料 热导率 /
（W m−1·K−1）热膨胀系数 /
（×10−6 K−1）介电常数
（1 MHz）电场强度 /
（kV·mm−1）断裂韧性 /
（MPa·m1/2）抗弯强度 /
MPa可靠性* /
次Al2O3 30 7.2 9.7 10 3.0 400 300 BeO 200～250 7.5 6.7 10 3.3 250 — AlN 150～200 3.5 8.9 15 2.7 350 200 Si3N4 90 3.2 9.4 ＞20 6.0～8.0 600～800 ＞5000 *注：可靠性是指在−40～+150 ℃条件下循环，材料不破坏次数。 
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烧结助剂 烧结时间 / h 物相（强度）* La2O3 4 β-Si3N4(s), α-Si3N4(s), La20N4Si12O48(m), La2SiO5(w) 16 β-Si3N4(vs), La20N4Si12O48(m), La2SiO5(w) Nd2O3 4 β-Si3N4(vs), Nd2Si3O3N4(w), Nd4Si3O12 (w) 16 β-Si3N4(vs), Nd2Si3O3N4(w), Nd4Si3O12 (w) Gd2O3 4 β-Si3N4(vs), Gd20N4Si12O48(m), Gd2Si3O3N4(vw) 16 β-Si3N4(vs), Gd20N4Si12O48(m), Gd2Si3O3N4(w) Y2O3 4 β-Si3N4(vs), Y20N4Si12O48(m), Y2Si3O3N4(w) 16 β-Si3N4(vs), Y20N4Si12O48(m), Y2Si3O3N4(w) Yb2O3 4 β-Si3N4(vs), Yb2Si2N2O7(s) 16 β-Si3N4(vs), Yb2Si2N2O7(s) Sc2O3 4 β-Si3N4(vs), Sc2SiO5(vw) 16 β-Si3N4(vs), Sc2SiO5(vw) *注：vs为非常强，s为强，m为中等，w为弱，vw为非常弱
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表 3 不同稀土氧化物烧结助剂对氮化硅陶瓷性能的影响[29]
Table 3 Properties of the Si3N4 ceramics with the different sintering additives[29]
烧结助剂 离子半径 / nm 烧结时间 / h 密度 / (g·cm−3) 热导率 / (W·m−1·K−1) 晶格氧质量分数 / % 平行 垂直 La2O3 0.106 4 3.35 28.1 31.6 0.279±0.037 16 3.33 51.1 64.9 0.116±0.006 Nd2O3 0.100 4 3.39 64.1 81.6 0.094±0.005 16 3.38 72.2 97.9 0.092±0.013 Gd2O3 0.094 4 3.42 78.7 100.7 0.076±0.002 16 3.42 81.6 106.9 0.069±0.013 Y2O3 0.089 4 3.25 82.9 104.6 0.076±0.001 16 3.28 82.7 105.8 0.063±0.002 Yb2O3 0.086 4 3.46 86.1 115.0 0.061±0.002 16 3.44 88.6 114.7 0.080±0.006 Sc2O3 0.073 4 3.21 84.9 100.8 0.085±0.004 16 3.19 89.6 106.3 0.077±0.003
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