WO2016082288A1 - 粉体烧结装置 - Google Patents

粉体烧结装置 Download PDF

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Publication number
WO2016082288A1
WO2016082288A1 PCT/CN2014/095750 CN2014095750W WO2016082288A1 WO 2016082288 A1 WO2016082288 A1 WO 2016082288A1 CN 2014095750 W CN2014095750 W CN 2014095750W WO 2016082288 A1 WO2016082288 A1 WO 2016082288A1
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WIPO (PCT)
Prior art keywords
unit
rotating shaft
reaction unit
sintering
sintered
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PCT/CN2014/095750
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English (en)
French (fr)
Inventor
何向明
张建利
王莉
李建军
罗晶
尚玉明
Original Assignee
江苏华东锂电技术研究院有限公司
清华大学
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Application filed by 江苏华东锂电技术研究院有限公司, 清华大学 filed Critical 江苏华东锂电技术研究院有限公司
Publication of WO2016082288A1 publication Critical patent/WO2016082288A1/zh
Priority to US15/603,979 priority Critical patent/US20170252802A1/en

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    • 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
    • B22F3/003—Apparatus, e.g. furnaces
    • 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
    • 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
    • B22F3/1039—Sintering only by reaction
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS, OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B17/00—Furnaces of a kind not covered by any preceding group
    • F27B17/0016—Chamber type furnaces

Definitions

  • the present invention relates to a powder sintering apparatus, and more particularly to a rotatable powder sintering apparatus.
  • the sintering process is one of the important links. From the perspective of the sintering state, it is mainly divided into static sintering and dynamic sintering. Dynamic sintering can realize the side mixing and sintering of a variety of materials, and it is easier to achieve a local stoichiometric ratio of the material and avoid the formation of miscellaneous phases. From the point of view of dynamic sintering equipment, industrial furnaces are mainly mainly rotary furnaces, which rotate while sintering during the sintering process. However, the disadvantage is that the dynamic sealing effect of the rotary kiln is poor, and the gas leakage cannot be effectively sealed. For sulfur, phosphorus, etc., which generate some toxic gases during the sintering process, it is necessary to develop new sintering equipment.
  • a powder sintering apparatus comprising: a support unit, a driving unit, a sintering unit, and a reaction unit.
  • the driving unit is disposed in the supporting unit; the reaction unit is disposed inside the sintering unit and can be heated by the sintering unit, and the reaction unit is fixed to the driving unit, and the driving unit can be driven by the driving unit Rotate.
  • a method for preparing a composite material by using the above powder sintering device comprising the following steps:
  • the powder sintering device provided by the present invention and the method for preparing the composite material by using the powder sintering device rotate while sintering in the sintering process, and the dynamic sealing effect of the sintered body is good, and the gas can be effectively sealed. Leak.
  • FIG. 1 is a cross-sectional structural view showing a powder sintering apparatus according to a first embodiment of the present invention.
  • FIG. 2 is a cross-sectional structural view showing a powder sintering apparatus according to a second embodiment of the present invention.
  • Fig. 3 is a view showing the performance of a sulfur positive electrode composite material prepared by using the powder sintering apparatus provided in the first embodiment of the present invention.
  • Powder sintering device 10 20 Support unit 11 Drive unit 12 Sintering unit 13 Reaction unit 14, 24 First beam 110 Second beam 111 First vertical beam 112 Second vertical beam 113 Third vertical beam 114 First bearing 115 Second bearing 116 Bearing housing 117 Motor 120 Reducer 121 Conveyor belt 122 Sprocket 123 First axis of rotation 124 Second axis of rotation 125 Furnace body 130 Heating element 131 Thermocouple 132 Upper wall 1301 Lower wall 1302 Side wall 1303 Sintered tank 141 Outer sheath 142 Sinter tube 241 Flange 242
  • a first embodiment of the present invention provides a powder sintering apparatus 10 including a support unit 11 , a driving unit 12 , a sintering unit 13 , and a reaction unit 14 .
  • the driving unit 12 is disposed on the supporting unit 11
  • the reaction unit 14 is disposed inside the sintering unit 13 .
  • the support unit 11 includes a first beam 110, a second beam 111, a first vertical beam 112, a second vertical beam 113, a third vertical beam 114, a first bearing 115, and a second bearing 116.
  • the first beam 110 is supported by a first vertical beam 112 and a second vertical beam 113 supported by a first vertical beam 112 and a third vertical beam 114.
  • the first bearing 115 is disposed at a top end of the first vertical beam 112 through a bearing housing 117
  • the second bearing 116 is disposed at a top end of the second vertical beam 113 through a bearing housing 117 .
  • the driving unit 12 includes a motor 120, a speed reducer 121, a conveyor belt 122, a sprocket 123, a first rotating shaft 124, and a second rotating shaft 125.
  • the motor 120 and the speed reducer 121 are disposed on the second beam 111, and the speed reducer 121 is coupled to the motor 120.
  • the first rotating shaft 124 and the second rotating shaft 125 are opposite and spaced apart.
  • the sprocket 123 is disposed on the first rotating shaft 124.
  • One end of the conveyor belt 122 is disposed on the reducer 121, and the other end is disposed on the sprocket 123.
  • the speed reducer 121 can decelerate the rotation of the main shaft of the motor 120, and the conveyor belt 122 can drive the sprocket 123 to rotate. Therefore, the sprocket 123 can drive the first rotating shaft 124 to rotate, and This rotational speed is lower than the rotational speed of the motor 120.
  • the rotation speed of the first rotating shaft 124 is preferably greater than 0 r/min and less than or equal to 10 r/min.
  • the first rotating shaft 124 and the second rotating shaft 125 are respectively disposed at the first bearing 115 and the second bearing 116, and the first bearing 115 and the second bearing 116 support the first rotating shaft 124 and the role of the second rotating shaft 125.
  • the sintering unit 13 includes a furnace body 130, a heating element 131 disposed within the furnace body 130, and a thermocouple 132.
  • the furnace body 130 is composed of an upper wall 1301, a lower wall 1302 and four side walls 1303, and forms a reaction chamber (not shown).
  • the lower wall 1302 is disposed in the first beam 110 of the supporting unit 11, wherein the upper wall 1301 and the lower wall 1302 are respectively provided with a heating element 131, and the upper wall 1301 is provided with a thermocouple 132.
  • a thermocouple 132 extends into the reaction chamber to measure the temperature within the reaction chamber and control whether heating is required by the control device.
  • the two opposite side walls 1303 are respectively provided with holes (not shown) through which the first rotating shaft 124 and the second rotating shaft 125 protrude into the reaction chamber and are spaced apart by a certain distance.
  • One of the side walls 1303 of the furnace body 130 is provided with a furnace door (not shown).
  • the heating element 131 may be heated by a muffle furnace, infrared heating, microwave heating, or the like.
  • the sintering unit 13 has a temperature range of 0 ° C to 700 ° C.
  • the reaction unit 14 includes a sintered can body 141 and an outer jacket 142 that is fixed within the outer jacket 142.
  • the reaction unit 14 is disposed between the first rotating shaft 124 and the second rotating shaft 125, and is mechanically fixed to the first rotating shaft 124 and the second rotating shaft 125 by welding or bolting. Therefore, as the first rotating shaft 124 rotates, the reaction unit also rotates.
  • the shape of the sintered can body 141 is a regular geometric shape including a column shape, a spherical shape, a square shape, a combined shape, and the like. In the present embodiment, the sintered can body 141 is square.
  • the amount of charge of the sintered can body 141 during heating is 80% or less of the volume of the sintered can body. It will be appreciated that the reaction unit 14 may also be devoid of the outer sheath 142 as described.
  • a second embodiment of the present invention provides a powder sintering apparatus 20 including a supporting unit 11, a driving unit 12, a sintering unit 13, and a reaction unit 24.
  • the driving unit 12 is disposed on the supporting unit 11
  • the reaction unit 24 is disposed inside the sintering unit 13 .
  • the structures of the supporting unit 11, the driving unit 12, and the sintering unit 13 are the same as those of the supporting unit 11, the driving unit 12, and the sintering unit 13 in the first embodiment, and therefore are denoted by the same reference numerals, with the difference that the reaction
  • the structure of the unit 24 is different from that of the reaction unit 14 in the first embodiment.
  • the reaction unit 24 includes a sintered tube 241 and a flange 242 having a closed end and an open end, the closed end being mechanically fixed to the first rotating shaft 124 by welding or bolting or the like.
  • the end portion is mechanically fixed to the flange 242 by bolts or the like, and the flange 242 is mechanically fixed to the end of the second rotating shaft 125 by bolts or the like. That is, the sintered tube 241 is fixed between the first rotating shaft 124 and the second rotating shaft 125. Therefore, as the first rotating shaft 124 rotates, the reaction unit 24 also rotates.
  • the amount of charge of the sintered can body 141 during heating is 80% or less of the volume of the sintered tube 241.
  • the cover on the side of the sintering furnace in the sintering unit 13 can be opened, and the sintered tube 241 can be placed and taken out from the side.
  • the method for preparing a composite material by using the powder sintering device provided by the invention comprises the following steps:
  • a method of preparing a sulfur positive electrode composite using the powder sintering apparatus 10 provided in the first embodiment will be described below in conjunction with a specific embodiment.
  • step (1) 508.5 g of sulfur powder, 169.5 g of polyacrylonitrile, and 25.425 g of diphenyl hydrazine were weighed and taken out in a V-type mixer for 2 hours to form a material to be reacted.
  • the material to be reacted is charged into the sintered can body 141, the volume is one-half of the volume of the sintered can body 141, the sintered can body 141 is sealed, and the sintered can body is sealed.
  • 141 is fixed in the outer sheath 142 to form a reaction unit 14, and then the reaction unit 14 is placed from the furnace door into the reaction chamber, and the reaction unit 14 is fixed to the first rotating shaft 124 and the second rotation. Between the axes 125. Then, it is sintered while rotating, and the sintering temperature is in the range of 200 ° C to 700 ° C, and the sintering time is determined according to the material to be reacted.
  • the material to be reacted provided in this embodiment can be sintered at 200 ° C to 400 ° C for 2 hours to 48 hours.
  • the material to be reacted was sintered at 400 ° C for 3 hours. After sintering, it is naturally cooled with the furnace. Then, the furnace door is opened, the reaction unit 14 is detached from the first rotating shaft 124 and the second rotating shaft 125, and the sintered can body 141 is taken out.
  • the gas in the sintered can body 141 is replaced by a ventilating device or a vacuum device to obtain a composite material.
  • the residual gas inside the sintered can body 141 is evacuated by a vacuum pump in the ventilating kitchen.
  • the composite composite was taken out and the properties of the sintered composite were shown in Figure 3.
  • the powder sintering device provided by the embodiment and the method for preparing the composite material by using the powder sintering device rotate while sintering in the sintering process, and the dynamic sealing effect of the sintered body is good, and the gas leakage can be effectively sealed. Moreover, the problems of material sublimation and liquid phase sedimentation in the sintering process are solved, and the components of the material sintering process are ensured to react according to the designing ratio, thereby improving the purity of the product.

Abstract

一种粉体烧结装置（10）以及利用该装置（10）制备复合材料的方法，其包括：支撑单元（11）、驱动单元（12）、烧结单元（13）以及反应单元（14）,所述驱动单元（12）设置于所述支撑单元（11）；所述反应单元（14）设置于所述烧结单元（13）的内部并可以由该烧结单元（13）加热，且该反应单元（14）固定在所述驱动单元（12），在该驱动单元（12）的驱动下可以旋转。

Description

粉体烧结装置 技术领域
本发明涉及一种粉体烧结装置，尤其涉及一种能够旋转的粉体烧结装置。
背景技术
对于无机材料的制备过程，烧结过程是重要的环节之一。从烧结状态式来看，主要分为静态烧结和动态烧结方式。动态烧结可以实现多种材料的边混合边烧结，更容易实现材料局部的化学计量比准确，避免杂相的生成。从动态烧结设备来看，工业炉主要以回转炉为主，在烧结过程边烧结边旋转。但其缺点是，回转炉的动态密封效果差，不能有效密封住气体外泄。对于硫、磷等在烧结过程中产生部分有毒气体，需要发展新型烧结设备。
发明内容
有鉴于此，确有必要提供一种密封性好的粉体烧结装置。
一种粉体烧结装置，其包括：支撑单元、驱动单元、烧结单元以及反应单元。所述驱动单元设置于所述支撑单元；所述反应单元设置于所述烧结单元的内部并可以由该烧结单元加热，且该反应单元固定在所述驱动单元，在该驱动单元的驱动下可以旋转。
一种利用上述的粉体烧结装置制备复合材料的方法，包括以下步骤：
提供待反应物料并混合；将该待反应物料装入所述反应单元中，并将该反应单元固定在所述烧结单元的内部，边旋转反应单元边烧结；卸下所述反应单元，置换反应单元内的气体，得到复合材料。
与现有技术相比较，本发明提供的粉体烧结装置和利用该粉体烧结装置制备复合材料的方法在烧结过程边烧结边旋转，所述烧结体的动态密封效果好，能有效密封住气体外泄。
 附图说明
图1是本发明第一实施例提供的粉体烧结装置的剖视结构示意图。
图2是本发明第二实施例提供的粉体烧结装置的剖视结构示意图。
图3是利用本发明第一实施例提供的粉体烧结装置制备的硫正极复合材料的性能。
主要元件符号说明
粉体烧结装置 10、20
支撑单元 11
驱动单元 12
烧结单元 13
反应单元 14、24
第一横梁 110
第二横梁 111
第一竖梁 112
第二竖梁 113
第三竖梁 114
第一轴承 115
第二轴承 116
轴承座 117
电机 120
减速机 121
传送带 122
链轮 123
第一旋转轴 124
第二旋转轴 125
炉体 130
加热元件 131
热电偶 132
上壁 1301
下壁 1302
侧壁 1303
烧结罐体 141
外护套 142
烧结管 241
法兰盘 242
如下具体实施方式将结合上述附图进一步说明本发明。
具体实施方式
下面将结合附图及具体实施例，对本发明提供的粉体烧结装置作进一步的详细说明。
请参见图1，本发明第一实施例提供一种粉体烧结装置10，该粉体烧结装置10包括支撑单元11、驱动单元12、烧结单元13、反应单元14。所述驱动单元12设置于所述支撑单元11，所述反应单元14设置于所述烧结单元13的内部。
所述支撑单元11包括第一横梁110、第二横梁111、第一竖梁112、第二竖梁113、第三竖梁114、第一轴承115以及第二轴承116。所述第一横梁110由第一竖梁112和第二竖梁113支撑，所述第二横梁111由第一竖梁112和第三竖梁114支撑。所述第一轴承115通过轴承座117设置于所述第一竖梁112的顶端，所述第二轴承116通过轴承座117设置于所述第二竖梁113的顶端。
所述驱动单元12包括电机120、减速机121、传送带122、链轮123、第一旋转轴124以及第二旋转轴125。所述电机120和所述减速机121设置在所述第二横梁111，该减速机121与所述电机120连接。所述第一旋转轴124和第二旋转轴125相对且间隔设置。所述链轮123设置于所述第一旋转轴124，所述传送带122的一端设置于所述减速机121，另一端设置于所述链轮123。因此，所述减速机121可以将所述电机120主轴的旋转减速，而且所述传送带122可以带动所述链轮123旋转，故，该链轮123可以带动所述第一旋转轴124旋转，而且该转速低于所述电机120的转速。所述第一旋转轴124的转速优选为大于0r/min且小于等于10r/min。所述第一旋转轴124和第二旋转轴125分别设置在所述第一轴承115和所述第二轴承116，该第一轴承115和所述第二轴承116起支撑所述第一旋转轴124和第二旋转轴125的作用。
所述烧结单元13包括炉体130、设置在炉体130内的加热元件131和热电偶132。所述炉体130由上壁1301、下壁1302以及四个侧壁1303组成，并形成一个反应腔（图未标示）。所述下壁1302设置在所述支撑单元11中的第一横梁110，其中，所述上壁1301和下壁1302内分别设置有加热元件131，且上壁1301内设置有热电偶132，该热电偶132伸入所述反应腔，可以测量该反应腔内的温度，并通过控制装置控制是否需要继续加热。所述相对设置的两个侧壁1303分别设置有孔（图未示），所述第一旋转轴124和第二旋转轴125通过所述孔伸入所述反应腔，并间隔一定距离。所述炉体130的其中一个侧壁1303设置有炉门（图未示）。
所述加热元件131的加热方式可以为马弗炉加热、红外加热、微波加热等，所述烧结单元13的使用温度区间为0℃~700℃。
所述反应单元14包括烧结罐体141和外护套142，该烧结罐体141固定在外护套142内。该反应单元14设置在所述第一旋转轴124和第二旋转轴125之间，并通过焊接的方式或螺栓等机械方式固定在所述第一旋转轴124和第二旋转轴125。因此，随着所述第一旋转轴124的旋转，所述反应单元也随之旋转。所述烧结罐体141的形状为规则几何图形，包括柱型、球形、方形和组合形体等。在本实施例中，所述烧结罐体141为方形。在加热过程中烧结罐体141的装料量是烧结罐体容积的80%以下。可以理解，所述反应单元14也可以没有所述的外护套142。
另外，请参见图2，本发明第二实施例提供一种粉体烧结装置20，该粉体烧结装置20包括支撑单元11、驱动单元12、烧结单元13、反应单元24。所述驱动单元12设置于所述支撑单元11，所述反应单元24设置于所述烧结单元13的内部。所述支撑单元11、驱动单元12、烧结单元13的结构与第一实施例中支撑单元11、驱动单元12、烧结单元13的结构相同，所以用相同的标号来表示，其区别在于所述反应单元24的结构与第一实施例中反应单元14的结构不同。
所述反应单元24包括烧结管241和法兰盘242，该烧结管241具有一封闭端和一开口端，所述封闭端通过焊接的方式或螺栓等机械方式固定在所述第一旋转轴124的端部，所述开口端通过螺栓等机械方式固定在所述法兰盘242，该法兰盘242通过螺栓等机械方式固定在所述第二旋转轴125的端部。也就是说，所述烧结管241固定在所述第一旋转轴124和第二旋转轴125之间。因此，随着所述第一旋转轴124的旋转，所述反应单元24也随之旋转。在加热过程中烧结罐体141的装料量是烧结管241的容积的80%以下。当然，所述烧结单元13中烧结炉一侧的盖子是可以打开的，所述烧结管241可以从该侧放入和取出。
利用本发明提供的粉体烧结装置制备复合材料的方法，包括以下步骤：
（1）提供待反应物料并混合；（2）将该待反应物料装入所述反应单元中，并将该反应单元固定在所述烧结单元的内部，边旋转反应单元边烧结；（3）卸下所述反应单元，置换反应单元内的气体，得到复合材料。
下面将结合一个具体实施例来说明利用第一实施例提供的粉体烧结装置10制备硫正极复合材料的方法。
在步骤（1）中，称取硫粉508.5g、聚丙烯腈169.5g、二苯胍25.425g，在V型混料机内混合2小时取出，形成待反应物料。
在步骤（2）中，将所述待反应物料装入所述烧结罐体141，装入体积占烧结罐体141容积的二分之一，密闭好烧结罐体141，并将该烧结罐体141固定在所述外护套142内形成反应单元14，然后将该反应单元14从炉门放入所述反应腔，并将该反应单元14固定在所述第一旋转轴124和第二旋转轴125之间。然后边旋转边烧结，烧结温度在200℃~700℃，烧结时间根据待反应物料确定。本实施例提供的待反应物料可以在200℃～400℃烧结2小时至48小时。本实施例中，将待反应物料在400℃烧结3小时。烧结完毕后随炉子一起自然冷却。然后打开炉门，将所述反应单元14从第一旋转轴124和第二旋转轴125卸下，并取出所述烧结罐体141。
在步骤（3）中，通过通风装置或真空装置置换烧结罐体141内的气体，得到复合材料。本实施例中，在通风厨内，用真空泵将烧结罐体141内部的剩余气体抽走。取出合成的复合材料，通过烧结的复合材料的性能图3所示。
本实施例提供的粉体烧结装置和利用该粉体烧结装置制备复合材料的方法在烧结过程边烧结边旋转，所述烧结体的动态密封效果好，能有效密封住气体外泄。并且，解决了烧结过程物质升华、液相沉降等问题，确保材料烧结过程各组分按照设计计量比进行反应，提升了产物的纯度。
另外，本领域技术人员还可以在本发明精神内做其它变化，这些依据本发明精神所做的变化，都应包含在本发明所要求保护的范围内。

Claims (10)

  1. 一种粉体烧结装置，其包括：
    一支撑单元；
    一驱动单元，该驱动单元设置于所述支撑单元；
    一烧结单元；
    一反应单元，该反应单元设置于所述烧结单元的内部并可以由该烧结单元加热，且该反应单元固定在所述驱动单元，在该驱动单元的驱动下可以旋转。
  2. 如权利要求1所述的粉体烧结装置，其特征在于：所述驱动单元包括电机、减速机、传送带、链轮、第一旋转轴以及第二旋转轴，所述电机和所述减速机设置在所述支撑单元，该减速机与所述电机连接，所述第一旋转轴和第二旋转轴相对间隔设置，所述链轮设置于所述第一旋转轴，所述传送带的一端设置于所述减速机，另一端设置于所述链轮。
  3. 如权利要求2所述的粉体烧结装置，其特征在于：所述反应单元包括烧结罐体和外护套，该烧结罐体固定在所述外护套内。
  4. 如权利要求2所述的粉体烧结装置，其特征在于：所述反应单元包括烧结管和法兰盘，该烧结管具有一封闭端和一开口端，所述开口端固定在所述法兰盘。
  5. 如权利要求3所述的粉体烧结装置，其特征在于：所述烧结罐体和外护套固定在所述第一旋转轴和第二旋转轴之间。
  6. 如权利要求4所述的粉体烧结装置，其特征在于：所述烧结管和法兰盘固定在所述第一旋转轴和第二旋转轴之间，所述烧结管的封闭端固定在所述第一旋转轴的端部，所述法兰盘固定在所述第二旋转轴的端部。
  7. 如权利要求2所述的粉体烧结装置，其特征在于：所述第一旋转轴的转速为大于0r/min且小于等于10r/min。
  8. 如权利要求1所述的粉体烧结装置，其特征在于：所述烧结单元包括炉体、设置在炉体内的加热元件和热电偶。
  9. 一种利用如权利要求1～8任意一项所述的粉体烧结装置制备复合材料的方法，包括以下步骤：
    提供待反应物料并混合；
    将该待反应物料装入所述反应单元中，并将该反应单元固定在所述烧结单元的内部，边旋转反应单元边烧结；
    卸下所述反应单元，置换反应单元内的气体，得到复合材料。
  10. 如权利要求9所述的利用如权利要求1～8任意一项所述的粉体烧结装置制备复合材料的方法，其特征在于：在卸下所述反应单元，置换反应单元内的气体，得到复合材料的步骤中，通过通风装置或真空装置置换反应单元内的气体。
PCT/CN2014/095750 2014-11-24 2014-12-31 粉体烧结装置 WO2016082288A1 (zh)

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