沉积时间对聚醚醚酮表面类金刚石薄膜的结构和性能的影响

doi:10.11901/1005.3093.2021.315

材料研究学报

2022, Vol. 36

Issue (11): 801-810 DOI: 10.11901/1005.3093.2021.315

研究论文

本期目录 | 过刊浏览

沉积时间对聚醚醚酮表面类金刚石薄膜的结构和性能的影响

崔丽¹, 孙丽丽¹, 郭鹏¹, 马鑫¹^,³, 王舒远¹^,², 汪爱英¹^,²(

)

^1.中国科学院宁波材料技术与工程研究所中国科学院海洋新材料与应用技术重点实验室浙江省海洋材料与防护技术重点实验室宁波 315201
^2.中国科学院大学材料与光电研究中心北京 100049
^3.西安交通大学机械制造系统工程国家重点实验室西安 710049

Effect of Deposition Time on Structure and Performance of Diamond-like Carbon Films on PEEK

CUI Li¹, SUN Lili¹, GUO Peng¹, MA Xin¹^,³, WANG Shuyuan¹^,², WANG Aiying¹^,²(

)

^1.Key Laboratory of Marine Materials and Related Technologies, Zhejiang Key Laboratory of Marine Materials and Protective Technologies, Ningbo Institute of Materials Technology and Engineering, Chinese Academy of Sciences, Ningbo 315201, China
^2.Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China
^3.State Key Laboratory for Manufacturing System Engineering, Xi′an Jiaotong University, Xi′an 710049, China

引用本文:

崔丽, 孙丽丽, 郭鹏, 马鑫, 王舒远, 汪爱英. 沉积时间对聚醚醚酮表面类金刚石薄膜的结构和性能的影响[J]. 材料研究学报, 2022, 36(11): 801-810.
Li CUI, Lili SUN, Peng GUO, Xin MA, Shuyuan WANG, Aiying WANG. Effect of Deposition Time on Structure and Performance of Diamond-like Carbon Films on PEEK[J]. Chinese Journal of Materials Research, 2022, 36(11): 801-810.

全文: PDF(7163 KB) HTML

摘要:

采用直流磁控溅射技术在聚醚醚酮(PEEK)表面制备不同厚度的类金刚石(DLC)薄膜，研究了沉积时间对其表/界面结构、组分、疏水、力学和光透过性能的影响。结果表明，在平均沉积速率为5.71 nm/min的条件下，随着沉积时间的延长DLC薄膜的厚度线性增大、碳原子的致密性提高、界面互锁结构增强，而界面结合强度逐渐降低。沉积时间≤15 min时，基体结构的影响使拟合计算出的I_D/I_G值为0.23~0.25和sp²/sp³比值较小(0.58~0.74)；沉积时间>15 min时基体的影响较小，I_D/I_G值突增大至0.81，sp²/sp³值也比较大(0.96~1.12)。沉积时间的延长使PEEK基体的温度逐渐升高，使膜内的sp²/sp³值逐渐增大。薄膜表面的氧含量先降低然后趋于平缓，部分C=O转化为C-O。随着沉积时间的延长，PEEK/DLC复合薄膜的硬度、弹性模量及防紫外线和阻隔红外线性能都逐渐提高，其表面粗糙度和疏水性的变化趋势是先提高后降低。沉积时间为32 min的薄膜，其表面粗糙度和水接触角达到最大值，分别为495 nm和108.29°。

关键词 ：材料表面与界面, 聚醚醚酮, 类金刚石薄膜, 表面改性, 沉积时间, 界面结合

Abstract：

Diamond-like carbon (DLC) films with different thickness (11.26~230.93 nm) were prepared on polyether ether ketone (PEEK) via direct current magnetron sputtering in the time ranging from 2 to 40 min. The effect of deposition time on the structure and composition of surface and interface, as well as the surface hydrophobic, the mechanical and optical transmittance properties of composite films PEEK/DLC were systematically studied. Results show that with the increase of deposition time the film thickness will be enhanced linearly with an average deposition rate of 5.71 nm/min. The density of C atoms and the interface interlocking structure gradually increase, while the interface adhesion decreases with time. By fitting peaks of Raman and XPS spectra, it is found that when the time ≤15 min, the I_D/I_Gvalue by data fitting remains at 0.23~0.25 and the ratio of sp²/sp³ is low (0.58~0.74) due to the influence of substrate. When the time >15 min, as the substrate effect becomes weak the I_D/I_G value has a great increase (to 0.81), and the sp²/sp³ value turns to be high (0.96~1.12). Prolonging the time will lead to the rise of substrate temperature inducing the ascending of sp²/sp³ ratio. While O content at the surface presents a low-flat trend and part of C=O bonds transformed into C-O bonds. The hardness, elastic modulus, the anti-ultraviolet and infrared barrier properties of PEEK/DLC composite films will rise over time, while the surface roughness and hydrophobicity both have a trend from high to low, reaching a maximum surface roughness and water contact angle of 495 nm and 108.29° at 32 min, respectively.

Key words： surface and interface in the materials polyether ether ketone diamond-like carbon films surface modification deposition time interface adhesion

收稿日期: 2021-05-19

ZTFLH:

O484

基金资助:王宽诚率先人才计划卢嘉锡国际团队项目(GJTD-2019-13);浙江省自然科学基金(LQ20E020004);宁波市科技创新2025重大专项(2020Z023);宁波市科技创新2025重大专项(2018B10012)

作者简介: 崔丽，女，1989年生，硕士

	服务

	把本文推荐给朋友
	加入引用管理器
	E-mail Alert
	RSS
	作者相关文章
	崔丽
	孙丽丽
	郭鹏
	马鑫
	王舒远
	汪爱英
44.8K

链接本文:

https://www.cjmr.org/CN/10.11901/1005.3093.2021.315 或 https://www.cjmr.org/CN/Y2022/V36/I11/801

图1 DLC薄膜沉积系统的示意图

图2 不同沉积时间PEEK/DLC复合薄膜表面的SEM照片

图3 不同沉积时间PEEK/DLC复合薄膜横截面的HRTEM照片

图4 PEEK表面DLC薄膜的厚度和平均沉积速率与沉积时间的关系

图5 不同沉积时间PEEK/DLC复合薄膜的粘结力

图6 不同沉积时间PEEK/DLC复合薄膜的Raman谱、ID/IG值、腔体温度以及PEEK的分子结构式

图7 不同沉积时间PEEK/DLC复合薄膜表面的O 1s谱图、C 1s谱图、C元素、O元素、C-O键和C=O键的相对浓度以及C/O比、sp2和sp3含量和sp2/sp3值

图8 PEEK/DLC复合薄膜表面的粗糙度(Ra)和水接触角与沉积时间的关系

图9 不同沉积时间PEEK/DLC表面的三维高度图

图10 PEEK/DLC复合薄膜硬度和弹性模量与沉积时间的关系

图11 不同沉积时间PEEK/DLC复合薄膜的光透过率曲线

1	Zheng Y Y, Xiong C D, Wang Z C, et al. A combination of CO₂ laser and plasma surface modification of poly(etheretherketone) to enhance osteoblast response [J]. Appl. Surf. Sci., 2015, 344: 79 doi: 10.1016/j.apsusc.2015.03.113
2	Tsuka H, Morita K, Kato K, et al. Effect of laser groove treatment on shear bond strength of resin-based luting agent to polyetheretherketone (PEEK) [J]. J. Prosthodont. Res., 2019, 63: 52 doi: S1883-1958(18)30213-5 pmid: 30220621
3	Li X W, Zhang D, Lee K R, et al. Effect of metal doping on structural characteristics of amorphous carbon system: a first-principles study [J]. Thin Solid Films, 2016, 607: 67 doi: 10.1016/j.tsf.2016.04.004
4	Wang A Y, Lee K R, Ahn J P, et al. Structure and mechanical properties of W incorporated diamond-like carbon films prepared by a hybrid ion beam deposition technique [J]. Carbon, 2006, 44: 1826 doi: 10.1016/j.carbon.2005.12.045
5	Takikawa H, Miyakawa N, Minamisawa S, et al. Fabrication of diamond-like carbon film on rubber by T-shape filtered-arc-deposition under the influence of various ambient gases [J]. Thin Solid Films, 2004, 457: 143 doi: 10.1016/j.tsf.2003.12.029
6	Ma X, Zhang Q, Guo P, et al. Residual compressive stress enabled 2D-to-3D junction transformation in amorphous carbon films for stretchable strain sensors [J]. ACS Appl. Mater. Interfaces, 2020, 12: 45549 doi: 10.1021/acsami.0c12073
7	Smietana M, Bock W J, Szmidt J. Evolution of optical properties with deposition time of silicon nitride and diamond-like carbon films deposited by radio-frequency plasma-enhanced chemical vapor deposition method [J]. Thin Solid Films, 2011, 519: 6339 doi: 10.1016/j.tsf.2011.04.032
8	Shirakura A, Nakaya M, Koga Y, et al. Diamond-like carbon films for PET bottles and medical applications [J]. Thin Solid Films, 2006, 494: 84 doi: 10.1016/j.tsf.2005.08.366
9	Martinez-Martinez D, De Hosson J T M. On the deposition and properties of DLC protective coatings on elastomers: a critical review [J]. Surf. Coat. Technol., 2014, 258: 677 doi: 10.1016/j.surfcoat.2014.08.016
10	Qiang L, Bai C N, Gong Z B, et al. Microstructure, adhesion and tribological behaviors of Si interlayer/Si doping diamond-like carbon film developed on nitrile butadiene rubber [J]. Diamond Relat. Mater., 2019, 92: 208 doi: 10.1016/j.diamond.2019.01.005
11	Xu W, Lin S S, Dai M J, et al. Effects of bias voltage on the microstructure and properties of Al-doped hydrogenated amorphous carbon films synthesized by a hybrid deposition technique [J]. Vacuum, 2018, 154: 159 doi: 10.1016/j.vacuum.2018.05.008
12	Ferrari A C, Robertson J. Resonant Raman spectroscopy of disordered, amorphous, and diamondlike carbon [J]. Phys. Rev., 2001, 64B: 075414
13	Park S J, Ko T J, Yoon J, et al. Highly adhesive and high fatigue-resistant copper/PET flexible electronic substrates [J]. Appl. Surf. Sci., 2018, 427: 1
14	Martinez-Martinez D, Schenkel M, Pei Y T, et al. Microstructural and frictional control of diamond-like carbon films deposited on acrylic rubber by plasma assisted chemical vapor deposition [J]. Thin Solid Films, 2011, 519: 2213 doi: 10.1016/j.tsf.2010.11.006
15	Hatada R, Flege S, Ensinger W, et al. Deposition of diamond-like carbon films on insulating substrates by plasma source ion implantation [J]. Surf. Coat. Technol., 2020, 385: 125426 doi: 10.1016/j.surfcoat.2020.125426
16	Zhang X Q, Huang M D, Ke P L, et al. Impact of bias on the graphite-like carbon films grown by high power impulse magnetron sputtering [J]. Chin. J. Vac. Sci. Technol., 2013, 33: 969
16	张学谦, 黄美东, 柯培玲等. 基体偏压对高功率脉冲磁控溅射制备类石墨碳膜的影响研究 [J]. 真空科学与技术学报, 2013, 33: 969
17	Schenkel M, Martinez-Martinez D, Pei Y T, et al. Tribological performance of DLC films deposited on ACM rubber by PACVD [J]. Surf. Coat. Technol., 2011, 205: 4838 doi: 10.1016/j.surfcoat.2011.04.072
18	Konkhunthot N, Photongkam P, Wongpanya P. Improvement of thermal stability, adhesion strength and corrosion performance of diamond-like carbon films with titanium doping [J]. Appl. Surf. Sci., 2019, 469: 471 doi: 10.1016/j.apsusc.2018.11.028
19	Ferrari A C, Robertson J. Interpretation of Raman spectra of disordered and amorphous carbon [J]. Phys. Rev., 2000, 61B: 14095
20	Zhang S, Zeng X T, Xie H, et al. A phenomenological approach for the I_d/I_g ratio and sp³ fraction of magnetron sputtered a-C films [J]. Surf. Coat. Technol., 2000, 123: 256 doi: 10.1016/S0257-8972(99)00523-X
21	Zeng Y L, Jiang L, Cai X Y, et al. Identification of the characteristic vibrations for 16 PAHs based on Raman spectrum [J]. Spectrosc. Spect. Anal., 2014, 34: 2999
21	曾娅玲, 姜龙, 蔡啸宇等. 拉曼光谱的16种多环芳烃(PAHs)特征振动光谱辨识 [J]. 光谱学与光谱分析, 2014, 34: 2999
22	Kim S, Lee K J, Seo Y. Polyetheretherketone (PEEK) surface functionalization by low-energy ion-beam irradiation under a reactive O₂ environment and its effect on the PEEK/Copper adhesives [J]. Langmuir, 2004, 20: 157 doi: 10.1021/la035396h
23	Roy M, Kubacki J, Psiuk B, et al. Photofunctionalization effect and biological ageing of PEEK, TiO₂ and ZrO₂ abutments material [J]. Mater. Sci. Eng., 2021, 121C: 111823
24	Robertson J. Diamond-like amorphous carbon [J]. Mater. Sci. Eng., 2002, 37R: 129
25	Liu F X, Yao K L, Liu Z L. Substrate tilting effect on structure of tetrahedral amorphous carbon films by Raman spectroscopy [J]. Surf. Coat. Technol., 2007, 201: 7235 doi: 10.1016/j.surfcoat.2007.01.030
26	Soin N, Roy S S, Ray S C, et al. Thickness dependent electronic structure of ultra-thin tetrahedral amorphous carbon (ta-C) films [J]. Thin Solid Films, 2012, 520: 2909 doi: 10.1016/j.tsf.2011.12.039
27	Sattel S, Robertson J, Ehrhardt H. Effects of deposition temperature on the properties of hydrogenated tetrahedral amorphous carbon [J]. J. Appl. Phys., 1997, 82: 4566 doi: 10.1063/1.366193
28	Huang J X, Wan S H, Liu B, et al. Improved adaptability of PEEK by Nb doped graphite-like carbon composite coatings for bio-tribological applications [J]. Surf. Coat. Technol., 2014, 247: 20 doi: 10.1016/j.surfcoat.2014.03.016
29	Du J Y, Zhang G F, Li G Q, et al. Diamond-like-carbon film prepared on stainless steel substrates by liquid phase electrochemical deposition [J]. Electrochemistry, 2007, 13: 58
29	杜景永, 张贵锋, 李国卿等. 不锈钢上液相电沉积类金刚石薄膜 [J]. 电化学, 2007, 13: 58
30	Ko T J, Her E K, Shin B, et al. Water condensation behavior on the surface of a network of superhydrophobic carbon fibers with high-aspect-ratio nanostructures [J]. Carbon, 2012, 50: 5085 doi: 10.1016/j.carbon.2012.06.048
31	Shin B, Lee K R, Moon M W, et al. Extreme water repellency of nanostructured low-surface-energy non-woven fabrics [J]. Soft Matter, 2012, 8: 1817 doi: 10.1039/C1SM06867A
32	Ko T J, Her E K, Shin B, et al. Water condensation behavior on the surface of a network of superhydrophobic carbon fibers with high-aspect-ratio nanostructures [J]. Carbon, 2012, 50: 5085 doi: 10.1016/j.carbon.2012.06.048
33	Asl A M, Kameli P, Ranjbar M, et al. Correlations between microstructure and hydrophobicity properties of pulsed laser deposited diamond-like carbon films [J]. Superlattices Microst., 2015, 81: 64 doi: 10.1016/j.spmi.2014.11.041
34	Cassie A B D, Baxter S. Wettability of porous surfaces [J]. Trans. Faraday Soc., 1944, 40: 546
35	Cha T G, Yi J W, Moon M W, et al. Nanoscale patterning of microtextured surfaces to control superhydrophobic robustness [J]. Langmuir, 2010, 26: 8319 doi: 10.1021/la9047402
36	Yang S, Zhang Y W, Zeng K Y. Analysis of nanoindentation creep for polymeric materials [J]. J. Appl. Phys., 2004, 95: 3655 doi: 10.1063/1.1651341
37	Liu C K, Lee S, Sung L P, et al. Load-displacement relations for nanoindentation of viscoelastic materials [J]. J. Appl. Phys., 2006, 100: 033503
38	Briscoe B J, Fiori L, Pelillo E. Nano-indentation of polymeric surfaces [J]. J. Phys., 1998, 31D: 2395
39	Xu Z Y, Zheng Y J, Jiang F, et al. The microstructure and mechanical properties of multilayer diamond-like carbon films with different modulation ratios [J]. Appl. Surf. Sci., 2013, 264: 207 doi: 10.1016/j.apsusc.2012.10.003

[1]	王乾, 蒲磊, 贾彩霞, 李志歆, 李俊. 碳纤维/环氧复合材料界面改性的不均匀性[J]. 材料研究学报, 2023, 37(9): 668-674.
[2]	陆益敏, 马丽芳, 王海, 奚琳, 徐曼曼, 杨春来. 脉冲激光沉积技术生长铜材碳基保护膜[J]. 材料研究学报, 2023, 37(9): 706-712.
[3]	冯叶, 陈志勇, 姜肃猛, 宫骏, 单以银, 刘建荣, 王清江. 一种NiCrAlSiY涂层对Ti65钛合金板材循环氧化和室温力学性能的影响[J]. 材料研究学报, 2023, 37(7): 523-534.
[4]	王刚, 杜雷雷, 缪自强, 钱凯成, 杜向博文, 邓泽婷, 李仁宏. 聚多巴胺改性碳纤维增强尼龙6复合材料的界面性能[J]. 材料研究学报, 2023, 37(3): 203-210.
[5]	闫春良, 郭鹏, 周靖远, 汪爱英. Cu掺杂非晶碳薄膜的电学性能及其载流子输运行为[J]. 材料研究学报, 2023, 37(10): 747-758.
[6]	陈开旺, 张鹏林, 李树旺, 牛显明, 胡春莲. 莫来石粉末化学镀镍和涂层的高温摩擦学性能[J]. 材料研究学报, 2023, 37(1): 39-46.
[7]	单位摇, 王永利, 李静, 熊良银, 杜晓明, 刘实. 锆合金表面Cr基涂层的耐高温氧化性能[J]. 材料研究学报, 2022, 36(9): 699-705.
[8]	程红杰, 刘黄娟, 姜婷, 王法军, 李文. 近红外反射超疏水黄色涂层的制备和性能[J]. 材料研究学报, 2022, 36(9): 687-698.
[9]	张红亮, 赵国庆, 欧军飞, Amirfazli Alidad. 基于聚多巴胺的超疏水棉织物的一锅法制备及其油水分离性能[J]. 材料研究学报, 2022, 36(2): 114-122.
[10]	李建中, 朱博轩, 王振宇, 赵静, 范连慧, 杨柯. 输尿管支架表面化学接枝镀铜涂层及其性能[J]. 材料研究学报, 2022, 36(10): 721-729.
[11]	李蕊, 王浩, 张天刚, 牛伟. Ti811合金表面激光熔覆Ti₂Ni+TiC+Al₂O₃+Cr_xS_y复合涂层的组织和性能[J]. 材料研究学报, 2022, 36(1): 62-72.
[12]	李修贤, 邱万奇, 焦东玲, 钟喜春, 刘仲武. α籽晶促进低温反应溅射沉积α-Al₂O₃薄膜[J]. 材料研究学报, 2022, 36(1): 8-12.
[13]	陈怿咨, 张承双, 陈平. 用常压空气等离子体对PBO纤维表面接枝改性[J]. 材料研究学报, 2021, 35(9): 641-650.
[14]	范金辉, 李鹏飞, 梁晓军, 梁建平, 徐长征, 蒋力, 叶祥熙, 李志军. 镍-不锈钢复合板轧制过程中界面的结合机制[J]. 材料研究学报, 2021, 35(7): 493-500.
[15]	卢壹梁, 杜瑶, 王成, 辛丽, 朱圣龙, 王福会. 纳米Al₂O₃和TiO₂改性有机硅涂层对304不锈钢高温氧化行为的影响[J]. 材料研究学报, 2021, 35(6): 458-466.

Viewed

Full text

Abstract

Cited

Shared

Discussed