CN109628818A - 一种VCrNbMoW难熔高熵合金材料及其制备方法 - Google Patents
一种VCrNbMoW难熔高熵合金材料及其制备方法 Download PDFInfo
- Publication number
- CN109628818A CN109628818A CN201811613687.0A CN201811613687A CN109628818A CN 109628818 A CN109628818 A CN 109628818A CN 201811613687 A CN201811613687 A CN 201811613687A CN 109628818 A CN109628818 A CN 109628818A
- Authority
- CN
- China
- Prior art keywords
- entropy alloy
- vcrnbmow
- preparation
- infusibility
- powder
- 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.)
- Pending
Links
- 239000000956 alloy Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 43
- 239000000843 powder Substances 0.000 claims abstract description 32
- 238000005245 sintering Methods 0.000 claims abstract description 21
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 13
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 13
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 13
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 12
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 4
- 239000010439 graphite Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract 2
- 238000000498 ball milling Methods 0.000 claims description 18
- 238000005275 alloying Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 238000000713 high-energy ball milling Methods 0.000 claims description 3
- 238000004886 process control Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 2
- 238000000875 high-speed ball milling Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000003466 welding Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 7
- 238000005551 mechanical alloying Methods 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000001816 cooling Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- 239000000470 constituent Substances 0.000 description 5
- 239000006104 solid solution Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004033 diameter control Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
-
- 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
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
-
- 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
- B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
- B22F2003/1051—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding by electric discharge
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
-
- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
-
- 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
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Manufacturing & Machinery (AREA)
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
本发明公开了一种VCrNbMoW难熔高熵合金材料的配方及其制备方法,其高熵合金的材料配方由V、Cr、Nb、Mo、W各单质粉末以近等摩尔比混合组成,制备方法为:按等摩尔比称取纯度不低于99.9%(wt)的V、Cr、Nb、Mo、W单质粉末并混合,将混合后的金属粉末至于高速摆阵式球磨罐中经机械合金化,此时制得高熵合金粉末,将适量高熵合金粉末装入石墨模具中并置于放电等离子烧结腔中抽真空,烧结温度1200℃,烧结过程保持恒压30MPa,烧结完毕后随炉冷却。本发明中配方的高熵合金具有单一体心立方结构,表现出高强度和高硬度,具有优异的室温及高温力学性能,制备过程无污染,低能耗,机械合金化后的高熵合金粉末可近净成型应用前景广阔。
Description
技术领域
本发明涉及合金材料及其制备领域,具体为一种VCrNbMoW难熔高熵合金材料及其制备方法。
技术背景
当前,传统合金体系的发展应用已几近饱和,已传统的合金设计理念很难再开发出新的材料体系。高熵合金在材料领域被认为是合金化理论的创新。高熵合金以其结构简单,性能优越以及较大的应用潜力在材料工程方面备受人们关注。高熵合金指组元数不少于5种,各组元的含量为等摩尔比或近等摩尔比,且形成高熵固溶的一类合金。
高熵合金块体材料的传统制备方法为中高频感应炉加热和熔铸法等,此类方法对组元具有选择性,对于部分组元通过熔炼法难以或不能使合金元素形成合金化。
本发明采用了机械合金化和放电等离子烧结相结合。通过高能摆振式球磨罐对难熔金属粉末的球磨,粉末颗粒发生极大的塑性变形,引起晶格强烈畸变,这种畸变将使难熔金属粉末间的固溶度大幅度扩展,甚至合成亚稳态的过饱和固溶体。通过放电等离子烧结,将制备的高熵合金粉末快速烧结成型,从而形成高致密度的高熵合金材料。
发明内容
本发明的目的是开发一种兼具高熔点与优异力学性能的合金材料,此高熵合金结构为单一体心立方,熔点高,压缩强度大,硬度高。
本发明的技术方案是:
一种VCrNbMoW难熔高熵合金材料,组元由纯度均为99.9%以上的V、Cr、 Nb、Mo、W各单质粉末以等摩尔比或近等摩尔比混合组成。
所述的VCrNbMoW难熔高熵合金的制作方法包括以下步骤:
步骤一:将V、Cr、Nb、Mo、W各单质粉末以等摩尔比或近等摩尔比混合;
步骤二:采用高速摆振式球磨罐对混合后的原料进行高能球磨20小时;
步骤三:对已合金化的高熵合金粉末取适量于石墨模具中,然后置于放电等离子烧结腔中烧结得VCrNbMoW难熔高熵合金。
所述的VCrNbMoW难熔高熵合金,制备此合金时,机械合金化前应先将含称取好的V、Cr、Nb、Mo、W单质粉末置于混粉机上充分混合以至均匀。
所述的VCrNbMoW难熔高熵合金的制备方法,为防止粉末之间、粉末与球磨罐之间发生冷焊,向球磨罐中加入工艺过程控制剂乙醇,且用量为粉末总量的 3%(wt)。
所述的VCrNbMoW难熔高熵合金的制备方法,为防止因高速球磨而使磨球附着在球磨罐上一起转动降低球磨效果,从而采用摆振式球磨。
所述的VCrNbMoW难熔高熵合金的制备方法,为保证合金化,所述球磨罐转速控制在1200r/min。
所述的VCrNbMoW难熔高熵合金的制备方法,烧结温度1200℃,烧结腔抽真空,烧结过程保持恒压30MPa。
本发明的优点及有益效果如下:
1、本发明中配方的VCrNbMoW高熵合金具有单一体心立方结构,表现出高强度和高硬度,具有优异的室温及高温力学性能。
2、本发明的VCrNbMoW高熵合金制备方法将机械合金化与放电等离子烧结技术相结合,制备过程无污染,低能耗,可近净成型。
3、本发明的VCrNbMoW高熵合金制备方法使得在固相下较难互溶的金属在室温状态下就能生成高熵固溶体,可以突破合金平衡固溶度的极限。
附图说明
图1为本发明实施例中VCrNbMoW高熵合金球磨20h后的XRD图谱。
图2为V、Cr、Nb、Mo、W粉末经球磨前后的XRD对比图。
其中1#为球磨前的V、Cr、Nb、Mo、W粉末;2#为球磨5h;3#为球磨10h; 4#为球磨20h。V、Cr、Nb、Mo、W粉末经球磨处理后,峰形逐渐宽化,强度降低,点阵常数逐渐靠拢,球磨20h后,各强峰合并,固溶体形成。
具体实施方式
以下通过具体实施例和附图更为详细的说明本发明,但下面具体描述内容仅为示例性而非限制性,不应限制本发明的保护范围。
实施例
1、制备VCrNbMoW高熵合金的关键步骤如下:
1)配方设计:本发明选用V、Cr、Nb、Mo、W高纯(≥99.9%)单质粉末,按等摩尔比称量后置于混粉机上充分混合以至均匀。
2)粉末合金化:采用摆振式球磨罐对混合好的粉末进行高能球磨,球磨罐为不锈钢材料,球磨介质选用不同直径的氧化锆珠,向球磨罐中加入工艺过程控制剂乙醇,且用量为粉末总量的3%(wt),球磨罐转速控制在1200r/min,球磨时间20h。
3)放电等离子烧结:对已合金化的高熵合金粉末取适量于石墨模具中,然后置于放电等离子烧结腔中烧结,烧结温度1200℃,烧结腔抽真空,烧结过程保持恒压30MPa。
2、合金的结构分析及性能表征;
1)X射线衍射测试及分析
XRD分析采用D8ADVANCE型衍射仪对不同球磨时间的粉末进行物相分析,扫描步长2θ=0.02deg,扫描速度为2°/min,扫描范围10~80°。由图2对比图可以分析出,机械合金化前,V、Cr、Nb、Mo、W混合粉末中各元素的衍射峰尖锐而分散,随球磨时间延长,部分衍射峰强度降低甚至消失,峰形逐渐宽化,晶格点阵常数逐渐靠拢,球磨20h后,各强峰合并,固溶体形成。
2)合金显微硬度分析
首先将烧结的样品依次在240目、400目、1500目、3000目的金刚石磨盘预磨抛光。然后采用MH-5L型维氏显微硬度计测试样品硬度,实验加载载荷为 1000g,保持10s。样品随机测试9个点,去除最大值和最小值,剩余7个点求平均值作为最后的硬度值,最终合金硬度测试结果为3536.7Hv。
不局限于此,任何不经过创造性劳动想到的变化或替换,都应涵盖在本发明的保护范围之内。因此,本发明的保护范围应该以权利要求书所限定的保护范围为准。
Claims (7)
1.一种VCrNbMoW难熔高熵合金材料,其特征在于:此高熵合金材料由等摩尔比的V、Cr、Nb、Mo、W各单质粉末混合组成,高熵合金结构为单一体心立方。
2.根据权利要求1中所述VCrNbMoW难熔高熵合金的制备方法,其特征在于,包括以下步骤:
步骤一:将V、Cr、Nb、Mo、W各单质粉末以等摩尔比混合;
步骤二:采用高速摆振式球磨罐对混合后的原料进行高能球磨20小时;
步骤三:对已合金化的高熵合金粉末取适量于石墨模具中,然后置于放电等离子烧结腔中烧结得VCrNbMoW难熔高熵合金。
3.根据权利要求2所述VCrNbMoW难熔高熵合金的制备方法,其特征在于,步骤一混合过程将含称取好的V、Cr、Nb、Mo、W单质粉末置于混粉机上充分混合以至均匀。
4.根据权利要求2所述VCrNbMoW难熔高熵合金的制备方法,其特征在于,为防止粉末之间、粉末与球磨罐之间发生冷焊,向球磨罐中加入工艺过程控制剂乙醇,且用量为粉末总量的3%(wt)。
5.根据权利要求2所述VCrNbMoW难熔高熵合金的制备方法,其特征在于,为防止因高速球磨而使磨球附着在球磨罐上一起转动降低球磨效果,采用摆振式球磨。
6.根据权利要求2所述VCrNbMoW难熔高熵合金的制备方法,其特征在于,为保证合金化,所述球磨罐转速控制在1200r/min。
7.根据权利要求2所述VCrNbMoW难熔高熵合金的制备方法,其特征在于,烧结温度1200℃,烧结腔抽真空,烧结过程保持恒压30MPa。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811613687.0A CN109628818A (zh) | 2018-12-27 | 2018-12-27 | 一种VCrNbMoW难熔高熵合金材料及其制备方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201811613687.0A CN109628818A (zh) | 2018-12-27 | 2018-12-27 | 一种VCrNbMoW难熔高熵合金材料及其制备方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
CN109628818A true CN109628818A (zh) | 2019-04-16 |
Family
ID=66078402
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201811613687.0A Pending CN109628818A (zh) | 2018-12-27 | 2018-12-27 | 一种VCrNbMoW难熔高熵合金材料及其制备方法 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN109628818A (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111304479A (zh) * | 2020-03-18 | 2020-06-19 | 南昌航空大学 | 一种VCrNbMoW难熔高熵合金制备方法 |
CN115213406A (zh) * | 2022-06-24 | 2022-10-21 | 中北大学 | 一种爆炸加载制备难熔高熵合金的方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105950945A (zh) * | 2016-06-29 | 2016-09-21 | 华南理工大学 | 一种高强度高熵合金NbMoTaWVCr及其制备方法 |
-
2018
- 2018-12-27 CN CN201811613687.0A patent/CN109628818A/zh active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105950945A (zh) * | 2016-06-29 | 2016-09-21 | 华南理工大学 | 一种高强度高熵合金NbMoTaWVCr及其制备方法 |
Non-Patent Citations (1)
Title |
---|
于镇洋: ""原位生长陶瓷晶须增强铝基复合材料的制备与性能"", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111304479A (zh) * | 2020-03-18 | 2020-06-19 | 南昌航空大学 | 一种VCrNbMoW难熔高熵合金制备方法 |
CN115213406A (zh) * | 2022-06-24 | 2022-10-21 | 中北大学 | 一种爆炸加载制备难熔高熵合金的方法 |
CN115213406B (zh) * | 2022-06-24 | 2024-02-27 | 中北大学 | 一种爆炸加载制备难熔高熵合金的方法 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN106435323B (zh) | 一种氧化物弥散强化ods高熵合金及其制备方法 | |
CN104372230B (zh) | 一种高强韧超细晶高熵合金及其制备方法 | |
CN103639408B (zh) | 一种以氢化钛铝合金粉末短流程制备钛铝金属间化合物的方法 | |
CN102717086B (zh) | 一种短流程制备高铌钛铝合金球形微粉的方法 | |
CN108421985B (zh) | 一种制备氧化物弥散强化中熵合金的方法 | |
CN105441765B (zh) | 弹用高比重钨合金及其制备方法 | |
CN105950944A (zh) | 一种高熔点高熵合金NbMoTaWVTi及其制备方法 | |
CN104911379A (zh) | 一种高性能金属基复合材料的制备方法 | |
CN108504916B (zh) | 精密仪器用高耐磨钨合金粉末冶金材料及其制备方法 | |
CN102825259B (zh) | 一种用氢化钛粉制备TiAl金属间化合物粉末的方法 | |
CN108342635A (zh) | 一种高强度难熔六元高熵合金CoCrFeNiVAlx及其制备方法 | |
CN109628818A (zh) | 一种VCrNbMoW难熔高熵合金材料及其制备方法 | |
CN110004349A (zh) | 一种碳纳米管增强高熵合金复合材料及其制备方法 | |
CN110004348A (zh) | 一种石墨烯增强高熵合金复合材料及其制备方法 | |
CN109023004B (zh) | 一种面向等离子体含钨的单相难熔高熵合金及其制备方法 | |
JP2885098B2 (ja) | スポンジチタン粉の処理方法 | |
CN101397617B (zh) | 一种纳米稀土氧化物掺杂钼-硅-硼合金的制备方法 | |
CN105154703B (zh) | 一种纯净单相三元碳化物Co6W6C的制备方法 | |
CN104232961B (zh) | 一种高强高硬Cu-Cr复合材料及其制备方法和应用 | |
CN109295399A (zh) | 一种高阻尼高熵合金材料及其制备方法 | |
CN106868372B (zh) | 一种MoFeB基金属陶瓷涂层的制备方法 | |
CN109811236B (zh) | 一种高性能硬质合金材料的制备方法 | |
CN104525935A (zh) | 一种高韧性立方氮化硼烧结材料及其制备方法 | |
CN103710576B (zh) | 一种钪、钽增强的高强度镍铌合金材料 | |
JP2005307226A (ja) | Mo系ターゲット材 |
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 | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190416 |
|
WD01 | Invention patent application deemed withdrawn after publication |