专

XMR影像引导的脑深部电极植入机器人

1102524196B

发明人

高安柱, 柳江林, 黄少平, 杨广中

受让人

UNIV SHANGHAI JIAOTONG

申请人

GAF Energy LLC

申请号

008601

申请日

1994-11-15

公开(公告)号

1102524196B

公开(公告)日

2017-08-21

IPC分类号

G01R019/25G01R031/327G01R031/04G01R001/04G05B023/02G01R000/00

CPC分类号

优先权号

167931

优先权日

2017-12-07

摘要

NOVELTY - The method (400) involves removably mounting (410) a test fixture to an upper surface of a chamber portion of the processing chamber such that the test fixture includes a first temperature sensor with a field of view including a first area of a first substrate support that is adjacent to a first resistive coil arranged in the first substrate support located in the processing chamber. The temperature measurements of the first area of the first substrate support are obtained (420) with the first temperature sensor and simultaneously calibration resistance measurements of first resistive coil corresponding to temperature measurement are obtained (430). The control of a heating element arranged in the first substrate support is calibrated (450) based on the measured temperature of the first substrate support and the measured calibration resistance of first resistive coil arranged in first substrate support. The test fixture is removed (460).

USE - Method for measuring temperature in processing chamber.

ADVANTAGE - The pyrometer allows measurements of temperature without contact with the substrate support even at low temperatures, to lower any risk of contamination while preserving the accuracy and precision of the measurements. The heating elements of substrate support are calibrated accurately without contact with the surface of substrate and the substrate support. The substrate supports are calibrated to desirable temperature accuracy since the non-contact temperature sensors reliably and accurately measure the temperature over wide range with precision of 2 degrees Celsius. The fittings are coupled to the inlet and outlet of the cooling channel to facilitate easy connection to heat transfer fluid source for circulating heat transfer fluid such as water within the cooling channel to control the temperature of the cover plate.

DETAILED DESCRIPTION - An INDEPENDENT CLAIM is included for a test fixture for measuring temperature in processing chamber.

DESCRIPTION OF DRAWING(S) - The drawing shows a flow diagram illustrating the method for measuring temperature of substrate support in processing chamber without contact with surface of the substrate support.

Method for measuring temperature in processing chamber (400)

Step for removably mounting test fixture (410)

Step for temperature measurements of the first area of the first substrate support (420)

Step for obtaining calibration resistance measurements of the first resistive coil (430)

Step for calibrating control of heating element (450)

Step for test fixture (460)

权利要求

1. An isolated polypeptide, comprising: an amino acid sequence having at least 90%, 95%, 97%, or 99%, sequence identity to the amino acid sequence of SEQ ID NO: 4, wherein said isolated polypeptide comprises laccase activity, oxidizes lignin under conditions of pH greater than or equal to pH 8.0, and retains laccase activity for greater than at least about 5 minutes at greater than or equal to 60° C.

2. The isolated polypeptide of claim 1 , wherein said polypeptide comprises the amino acid sequence of SEQ ID NO: 4.

3. The isolated polypeptide of claim 1 comprising at least one amino acid substitution, wherein the position of the at least one substitution in SEQ ID NO: 4 is selected from the group consisting of amino acid residue: 162, 163, 164, 166, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181, 182, 183, 184, 208, 210, 212, 213, 214, 215, 216, 218, 313, 314, 315, 316, 317, 318, 319, 320, 321, 351, 352, 353, 354, 452, 454, 470, 529, 530, 531,532, 533, 534, 535, 536, 537, 538, 540, 541, 542, 545, 546, 547, 572, 573, 574, 575, 576, 577, 578, 579, 597, 598, 599, 603, 604, 605, 607, 608, 609, 610, 611,612, 613, 614, 615 ,616, 616, 618, 619, and 620, or any combination thereof.

4. The isolated polypeptide of claim 3 , lacking its associated signal peptide.

wherein R 1 , R 2 R 3 , R 4 , R 5 R 6 , R 7 , R 8 , R 9 and R 10 are independently selected from the group consisting of H, CH 3 , CH 2 CH 3 , CH 2 CH 2 CH 3 , CH(CH 3 ) 2 , CH 2 CH 2 (CH 3 ) 2 , C(CH 3 ) 3 , CH 2 CH 2 CH 2 , CH 3 , alkyl, aryl, phenyl, CF 3 , OC(CH 3 ) 3 , OCH(CH 3 ) 2 , CH 2 CH 3 , C(O)OCH 3 , COOH, OCH 3 , OH, OCF 3 , NH 2 , NH(CH 3 ), N(CH 3 ) 2 , CH 2 NH 2 , CH 2 CH 2 NH 2 , Br, and Cl.

7. The method of claim 6 , further comprising contacting the phenolic or aromatic substrate with a mediator selected from the group consisting of violuric acid; 2,2,6,6-tetramethylpiperidine 1-oxy_(TEMPO); 1-hydroxybenzotriazole (HBT); 2,2′-azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) (ABTS); syringaldazine; N-benzoyl-N-phenyl hydroxylamine (BPHA); N-hydroxyphthalimide, 3-Hydroxy-1,2,3-benzotriazin-4-one; promazine; 1,8-Dihydroxy-4,5-dinitroanthraquinone; phenoxazine; anthraquinone; 2-hydroxy-1,4-naphthoquinone; phenothiazine; anthrone; anthracene, anthrarufin, anthrarobin, ; dimethoxyphenol (DMP); ferulic acid; catechin; epicatechin; homovanillic acid (HMV); and 2,3-dihydroxybenzoic acid (2,3-DHB); or any combination thereof.

8. The method of claim 7 , further comprising contacting said phenolic or aromatic substrate with a laccase.

9. The method of claim 8 , wherein said laccase is the polypeptide of claim 1 .

10. A method of delignifying a composition comprising lignin, comprising contacting a phenolic substrate with the polypeptide of claim 1 .

11. The method of claim 10 , further comprising contacting the composition with a mediator.

14. The method of claim 11 , wherein the mediator is selected from the group consisting of: violuric acid; 2,2,6,6-tetramethylpiperidine 1-oxy (TEMPO); 1-hydroxybenzotriazole (HBT); 2,2′-azino-bis (3-ethylbenzthiazoline-6- sulfonic acid) (ABTS); syringaldazine; N-benzoyl-N-phenyl hydroxylamine (BPHA); N-hydroxyphthalimide, 3-Hydroxy-1,2,3-benzotriazin-4-one; promazine; 1,8-Dihydroxy-4,5-dinitroanthraquinone; phenoxazine; anthraquinone; 2-hydroxy-1,4-naphthoquinone; phenothiazine; anthrone; anthracene, anthrarufin, anthrarobin, ; dimethoxyphenol (DMP); ferulic acid; catechin; epicatechin; homovanillic acid (HMV); and 2,3-dihydroxybenzoic acid (2,3-DHB); or any combination thereof.

15. The method of claim 10 , wherein said delignification reaction proceeds under conditions of between pH 8 and pH 11.

16. The method of claim 10 , wherein said delignification reaction proceeds at a temperature of at least 50° C.

17. A method of oxidizing a composition comprising a fiber, comprising: contacting said composition with the polypeptide of claim 1

18. The method of claim 17 , further comprising contacting the composition with a mediator.

19. The method of claim 18 , wherein said mediator is a compound represented by Formula I or Formula II.

21. The method of claim 18 , wherein the mediator is selected from the group consisting of: violuric acid; 2,2,6,6-tetramethylpiperidine 1-oxy (TEMPO); 1-hydroxybenzotriazole (HBT); 2,2′-azino-bis (3-ethylbenzthiazoline-6-sulfonic acid) (ABTS); syringaldazine; N-benzoyl-N-phenyl hydroxylamine (BPHA); N-hydroxyphthalimide, 3-Hydroxy-1,2,3-benzotriazin-4-one; promazine; 1,8-Dihydroxy-4,5-dinitroanthraquinone; phenoxazine; anthraquinone; 2-hydroxy-1,4-naphthoquinone; phenothiazine; anthrone; anthracene, anthrarufin, anthrarobin, ; dimethoxyphenol (DMP); ferulic acid; catechin; epicatechin; homovanillic acid (HMV); and 2,3-dihydroxybenzoic acid (2,3-DHB); or any combination thereof.

22. The method of claim 17 , wherein said oxidation reaction proceeds under conditions of between pH 8 and pH 11.

23. The method of claim 17 , wherein said oxidation reaction proceeds at a temperature of at least 50° C.

24. A method of bleaching a composition comprising pulp or paper, comprising contacting said composition with the polypeptide of claim 1 .

25. The method of claim 24 , further comprising contacting the composition with a mediator.

26. The method of claim 25 , wherein said mediator is a compound represented by Formula I or Formula II.

28. The method of claim 25 , wherein the mediator is selected from the group consisting of: violuric acid; 2,2,6,6-tetramethylpiperidine 1-oxy (TEMPO); 1-hydroxybenzotriazole (HBT); 2,2′-azino-bis (3-ethylbenzthiazoline-6- sulfonic acid) (ABTS); syringaldazine; N-benzoyl-N-phenyl hydroxylamine (BPHA); N-hydroxyphthalimide, 3-Hydroxy-1,2,3-benzotriazin-4-one; promazine; 1,8-Dihydroxy-4,5-dinitroanthraquinone; phenoxazine; anthraquinone; 2-hydroxy-1,4-naphthoquinone; phenothiazine; anthrone; anthracene; anthrarufin; anthrarobin; dimethoxyphenol (DMP); ferulic acid; catechin; epicatechin; homovanillic acid (HMV); and 2,3-dihydroxybenzoic acid (2,3-DHB); or any combination thereof.

29. The method of claim 24 , wherein said bleaching reaction proceeds under conditions of between pH 8 and pH 11.

30. The method of claim 24 , wherein said bleaching reaction proceeds at a temperature of at least 50° C.

说明书

[0001]技术领域

[0002]本发明涉及一种陶瓷材料及其制备方法，尤其涉及一种纳米MAX相的制备方法。

[0003]背景技术

[0004]三元层状化合物MAX相是一种新型可加工陶瓷材料，其通式为M n+1 AX n ，其中M是过渡金属，A主要为主族元素，X是碳和/或氮，n通常为1-3。MAX相由于其层状结构、优异的抗氧化性、耐腐蚀性、金属导电性、高强度和弹性模量，作为功能材料具有巨大的应用潜力。传统方法制备的MAX相多为微米以上大块颗粒，这阻碍其功能应用。

[0005]以MAX相在锂离子电池中的应用为例，2017年，Gogotsi等人首次报道了通过减小颗粒尺寸，Ti 2 SC MAX相在1000次循环后提升至180mAh g -1 ；2021年，许建光等人采用超声剥离技术，研制出的Ti 3 Si 0.75 Al 0.25 C 2 超薄纳米片作为锂离子电池的负极，具有约350mAh g -1 的容量(200mA g -1 )。诸多研究表明，MAX相储锂容量对其颗粒尺寸具有大的依赖性，而目前得到较小尺寸的MAX相主要依靠球磨、超声等自上而下的手段，很难获得尺寸均匀的MAX相颗粒。

[0006]2020年，黄庆等人发明一种熔盐法制备小尺寸锂离子电池阳极MAX相的方法，获得的Ti 2 SnC能够提供390mAhg -1 (0.1Ag -1 )的锂离子存储容量，由此可见，自下而上制备纳米MAX相的方法开发对提高其储锂性能具有重大意义。

[0007]发明内容

[0008]发明目的：本发明的目的是提供一种尺寸均匀的纳米MAX相的制备方法。

[0009]技术方案：本发明所述的纳米MAX相的制备方法，包括以下步骤：

[0010](1)将M离子源材料、A离子源材料混合，加入碳源材料兼络合剂、水，获得前驱体纺丝溶液；

[0011](2)将所述前驱体纺丝溶液进行静电纺丝，得到前驱体纳米纤维；

[0012](3)将所述前驱体纳米纤维干燥后煅烧，得到所述纳米MAX相。

[0013]其中，所述纳米MAX相的化学式表示为M n+1 AX n ，其中M包括Ti、V、Mn、Cr和Zr中的任意一种或者两种以上的组合，A为Ga、Al、In、Sn和Zn中的任意一种或者两种以上的组合，X为C元素，n为1、2或3。

[0014]其中，步骤(1)中，为了制备得到不同种类的MAX相，所述M离子源材料、A离子源材料的摩尔比为(1-4):1。

[0015]其中，步骤(1)中，为更好地控制纺丝液粘度，所述前驱体纺丝溶液中络合剂的浓度为5-30％。

[0016]其中，步骤(1)中，所述M离子源材料为钛酸四丁酯、乙酰丙酮氧钒、硝酸锰、硝酸铬、硝酸锆中的至少一种。

[0017]其中，步骤(1)中，所述A离子源材料为硝酸镓、硝酸铝、硝酸锌、硝酸铟、氯化锡中的至少一种。

[0018]其中，步骤(1)中，所述碳源材料兼络合剂为聚乙烯吡咯烷酮和/或聚乙烯醇。

[0019]其中，步骤(2)中，为更好地匹配纺丝液粘度，静电纺丝过程中的针头内径为0.1-3mm，更优选为0.1-2.99mm。

[0020]其中，步骤(2)中，静电纺丝过程中的针头与集丝辊之间的电压为10-30kV，有助于获得连续、直径均匀且表面光滑的前驱体纳米纤维。

[0021]其中，步骤(2)中，为了有效收集前驱体纳米纤维，静电纺丝过程中的针头到集丝辊的距离为10-30cm。

[0022]其中，步骤(2)中，静电纺丝过程中的注射器推进速率为0.5-4mL h -1 ，有助于获得稳定的针尖纳米纤维射流并调节纺丝速度。

[0023]有益效果：本发明与现有技术相比，取得如下显著效果：(1)本发明首次利用溶胶凝胶法结合静电纺丝技术实现了自下而上制备纳米MAX相，产物纯度较高，且MAX相限域在碳纳米线中，尺寸均匀可控；纳米Cr 2 GaC在5A g -1 的倍率下可以提供高达168.2mAh g -1 的锂存储容量，是MAX相微米颗粒的近10倍。(2)合成方法简单，在电化学储能中具有巨大的应用潜力。

[0024]附图说明

[0025]图1是实施例1中制得的纳米MAX相Cr 2 GaC的XRD衍射图；

[0026]图2是实施例1中制得的纳米MAX相Cr 2 GaC的SEM图像；

[0027]图3是实施例1中制得的纳米MAX相Cr 2 GaC的TEM和EDS图像；

[0028]图4是对比例1中制得的微米MAX相Cr 2 GaC的SEM图像；

[0029]图5是实施例1中制得的纳米MAX相Cr 2 GaC与对比例1中制得的微米Cr 2 GaC分别应用于锂离子电池负极，在不同电流密度下的容量对比；

[0030]图6是实施例1中制得的纳米MAX相Cr 2 GaC在5Ag -1 电流密度下的容量和库仑效率图。

[0031]具体实施方式

[0032]下面对本发明作进一步详细描述。

[0033]实施例1

[0034]本实施例的纳米MAX相材料为纳米Cr 2 GaC，其制备方法如下：

[0035](1)将1.7mmol Cr(NO 3 ) 3 和1mmol Ga(NO 3 ) 3 混合均匀，加入1.5g聚乙烯吡咯烷酮和去离子水，充分搅拌混合均匀，获得络合剂浓度为15％的前驱体纺丝溶液。

[0036](2)利用静电纺丝设备，将前驱体纺丝溶液进行静电纺丝，针头内径0.4mm，在针头与集丝辊之间加25kV电压，针头到集丝辊的距离为15cm，注射器推进速率2.4mL h -1 ，得到前驱体纳米纤维。

[0037](3)将前驱体纳米纤维在80℃干燥12h，并在1000℃下煅烧2h，得到纳米MAX相。

[0038]图1为本实施例中制得的纳米MAX相Cr 2 GaC的XRD衍射图，从图中可以看出，得到的产物中出现了Cr 2 GaC典型的特征峰，纯度高达95.42wt.％，说明得到了纯度较高的MAX相Cr 2 GaC。

[0039]图2为本实施例中制备的纳米MAX相Cr 2 GaC的SEM图，图中可以看出得到的纳米Cr 2 GaC限域于碳纳米线中，且尺寸均匀。

[0040]图3为本实施例中制备的纳米MAX相Cr 2 GaC的TEM和EDS图，图中可以看出Cr 2 GaC在C纳米线上均匀分布，Cr,Ga,C元素均匀分布。

[0041]图5是本实施例中制得的纳米MAX相在不同电流密度下的容量与对比例1中微米Cr 2 GaC在不同电流密度下的容量对比。通过对比可以看出，相比微米Cr 2 GaC，纳米Cr 2 GaC在不同电流密度下的性能都有明显提升。

[0042]图6是本实施例中制得的纳米MAX相Cr 2 GaC应用于锂离子电池负极，在5A g -1 电流密度下的容量和库仑效率图。图中可以看出，在5A g -1 的大电流密度下，碳纤维限域的纳米Cr 2 GaC仍有205mAh g -1 的质量比容量，循环近3000圈后容量保持率高达96.33％，库伦效率近100％。

[0043]实施例2

[0044]本实施例的纳米MAX相材料为纳米Cr 2 GaC，其制备方法如下：

[0045](1)将1.7mmol Cr(NO 3 ) 3 和1mmol Ga(NO 3 ) 3 混合均匀，加入0.7g聚乙烯吡咯烷酮和去离子水，充分搅拌混合均匀，获得络合剂浓度为15％的前驱体纺丝溶液。

[0046](2)利用静电纺丝设备，将前驱体纺丝溶液进行静电纺丝，针头内径0.4mm，在针头与集丝辊之间加25kV电压，针头到集丝辊的距离为15cm，注射器推进速率2.4mL h -1 ，得到前驱体纳米纤维。

[0047](3)将前驱体纳米纤维在80℃干燥12h，并在1000℃下煅烧2h，得到纳米MAX相。

[0048]实施例3

[0049]本实施例的纳米MAX相材料为Cr 2 GaC，其制备方法如下：

[0050](1)将1.0mmol Cr(NO 3 ) 3 和1mmol Ga(NO 3 ) 3 混合均匀，加入1.0g聚乙烯醇和去离子水，充分搅拌混合均匀，获得络合剂浓度为5％的前驱体纺丝溶液。

[0051](2)利用静电纺丝设备，将前驱体纺丝溶液进行静电纺丝，针头内径0.1mm，在针头与集丝辊之间加10kV电压，针头到集丝辊的距离为10cm，注射器推进速率0.5mL h -1 ，得到前驱体纳米纤维。

[0052](3)将前驱体纳米纤维在80℃干燥12h，并在1000℃下煅烧2h，到得到纳米MAX相。

[0053]实施例4

[0054]本实施例的纳米MAX相材料为Cr 2.7 Mn 1.3 GaC 3 ，其制备方法如下：

[0055](1)将2.7mmol Cr(NO 3 ) 3 ，1.3mmol Mn(NO 3 ) 3 和1mmol Ga(NO 3 ) 3 混合均匀，加入3.0g聚乙烯吡咯烷酮(PVP)和去离子水，充分搅拌混合均匀，获得络合剂浓度为30％的前驱体纺丝溶液。

[0056](2)利用静电纺丝设备，将前驱体纺丝溶液进行静电纺丝，针头内径2.85mm，在针头与集丝辊之间加30kV电压，针头到集丝辊的距离为30cm，注射器推进速率4mL h -1 ，得到前驱体纳米纤维。

[0057](3)将前驱体纳米纤维在80℃干燥12h，并在1000℃下煅烧2h，到得到纳米MAX相。

[0058]对比例1

[0059]本对比例中的MAX相材料为微米Cr 2 GaC，其制备方法如下：

[0060](1)将1.7mmol Cr(NO 3 ) 3 和1mmol Ga(NO 3 ) 3 混合均匀，加入1.5g聚乙烯吡咯烷酮和去离子水，充分搅拌混合均匀，获得络合剂浓度为15％的溶胶凝胶液。

[0061](2)将溶胶凝胶液在80℃干燥12h，并在1000℃下煅烧2h，到得到微米MAX相。

[0062]图3为本对比例中制备的微米MAX相Cr 2 GaC的SEM图，图中可以看出得到的微米Cr 2 GaC为较大块状。

[0063]图5是实施例1中制得的纳米MAX相在不同电流密度下的容量与本对比例中微米Cr 2 GaC在不同电流密度下的容量对比。通过对比可以看出，相比微米Cr 2 GaC，纳米Cr 2 GaC在不同电流密度下的性能都有明显提升。

同族专利

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