Journal of Prevention and Treatment for Stomatological Diseases ›› 2021, Vol. 29 ›› Issue (11): 733-739.doi: 10.12016/j.issn.2096-1456.2021.11.002

• Basic Study • Previous Articles     Next Articles

Preparation and antibacterial properties of a copper-niobium coating on a titanium surface by a microarc oxidation-microwave hydrothermal method

WANG Tianqi1(),DU Qing2,XIE Weili1()   

  1. 1. Department of Prosthodontics, College of Stomatology, Harbin Medical University, Harbin 150001, China
    2. School of Materials Science and Engineering, Harbin Institute of Technology, Harbin 150001, China
  • Received:2021-03-04 Revised:2021-04-28 Online:2021-11-20 Published:2021-07-20
  • Contact: Weili XIE E-mail:349530444@qq.com;xwl811@126.com
  • Supported by:
    Science and Technology Key Projects of Heilongjiang Province(GC12C305-3)

Abstract:

Objective To prepare a copper-nobium antibacterial coating on a titanium surface by a microarc oxidation-microwave hydrothermal two-step method and to study its surface structure and antibacterial properties. Methods Using titanium coated with a microarc oxidation coating (MAO group) as the substrate, copper and niobium were introduced by a microwave hydrothermal method in low (MHL-Cu group), medium (MHM-Cu group) and high (MHH-Cu group) copper chloride solutions and niobium oxalate (MH-Nb group) solutions, respectively. The component with the highest copper content was determined by energy spectrum analysis, and the copper-niobium composite coating (MH-Cu/Nb group) was prepared by microwave hydrothermal mixing with niobium oxalate. The microstructure, element distribution and phase composition of the specimens were characterized by scanning electron microscopy, energy dispersive spectrometry and X-ray diffraction, and the bacteriostatic effect of the coating onEscherichia coliand Staphylococcus aureus was determined by the film method. Results Energy dispersive spectrometry showed that Cu was introduced onto the surface of the MHL-Cu, MHM-Cu, and MHH-Cu groups, and the atomic ratios of copper in each group were (0.68 ± 0.04)%,(1.17 ± 0.06)%, and (1.64 ± 0.03)%. The difference between groups was statistically significant (P< 0.01). Scanning electron microscopy showed a crater-like porous structure on the surface of the MAO group, and the MHL-Cu, MHM-Cu, MHH-Cu, MH-Nb, MH-Cu/Nb groups maintained micropore morphology. The roughness increased with increasing Cu2+ concentration, in which the MH-Nb and MH-Cu/Nb groups showed gully like structures simultaneously. X-ray diffraction showed that the coating of the MAO group was mainly composed of titanium and anatase phase TiO2, and the coatings of the MHL-Cu, MHM-Cu, MHH-Cu, MH-Nb, MH-Cu/Nb groups were mainly composed of anatase and rutile phase TiO2. Compared with the MAO group, Escherichia coli and Staphylococcus aureus in the MHH-Cu, MH-Nb, MH-Cu/Nb groups decreased to varying degrees, with significant differences (P< 0.001); compared with the MH-Cu/Nb group, the colony number difference had statistical significance (P> 0.05).Conclusion The rough, porous coating containing copper and niobium prepared by the microarc oxidation-microwave hydrothermal two-step method can effectively inhibit the growth ofEscherichia coli and Staphylococcus aureus.

Key words: titanium, coating, surface treatment, microarc oxidation, microwave hydrothermal, copper, niobium, antibacterial, Escherichia coli, Staphylococcus aureus

CLC Number: 

  • R78

Table 1

Composition of the microarc oxidation electrolyte"

The name of reagent Content(g/L or mL/L) Purity
EDTA-2Na 15.0 >99%
Ca(CH3COO)2·H2O 8.8 >98%
Ca(H2PO42·H2O 6.3 >98%
Na2SiO3·9H2O 7.1 >98%
NaOH 5.0 >98%
H2O2 6.0 30%

Table 2

Process parameters of the microarc oxidation"

Control mode Voltage(V) Time
(min)
Duty cycle
(%)
Frequency(Hz)
Constant voltage mode 400 5 8 600

Table 3

Grouping and process parameters of microwave hydrothermal treatment of CuCl2 solutions with different concentrations "

Experiment
groups
CuCl2concentration(mol/L) Temperature(℃) Holding time(min)
MHL-Cu 0.1 200 60
MHM-Cu 0.5 200 60
MHH-Cu 1.0 200 60

Figure 1

Distribution of elements on the surface of a microwave hydrothermal coating with a high copper content (× 5 000) a: SEM morphology of the MHH-Cu group, 1 mol/LCuCl2 solution microwave hydrothermal treatment coating; b: Na elements uniformly distributed around the micropores; c: Ca elements uniformly distributed around the micropores; d: O elements uniformly distributed around the micropores; e: Ti elements widely distributed and more micropores; f: P elements uniformly distributed around the micropores; g: Si elements uniformly distributed around the micropores; h: Cu elements uniformly distributed around the micropores "

Figure 2

Distribution of the elements on the surface of the microwave hydrothermal coating containing niobium (× 5 000) a: SEM morphology of the MH-Nb group, 1 mol/L C10H5NbO20 solution microwave hydrothermal treatment coating; b: Na elements uniformly distributed around the micropores; c: Ca elements uniformly distributed around the micropores; d: O elements uniformly distributed around the micropores; e: Ti elements widely distributed and more micropores; f: P elements uniformly distributed around the micropores; g: Si elements uniformly distributed around the micropores; h: Nb elements uniformly distributed around the micropores "

Figure 3

Distribution of elements on the surface of the microwave hydrothermal coating of the copper-niobium composite group (× 5 000) a: SEM morphology of the MH-Cu/Nb group, 1 mol/L CuCl2 solution and 1 mol/LC10H5NbO20 solution microwave hydrothermal treatment coating; b: Na elements uniformly distributed around the micropores; c: Si elements uniformly distributed around the micropores; d: O elements uniformly distributed around the micropores; e: Ca elements uniformly distributed around the micropores; f: P elements uniformly distributed around the micropores; g: Ti elements widely distributed and more micropores; h: Nb elements uniformly distributed around the micropores; i: Cu elements uniformly distributed around the micropores "

Figure 4

Surface scanning electron microscope morphology of the coatings on each group of specimens a: MAO group, crater-like morphology, smooth surface; b: MHL-Cu group, porous structure, small grain-like substance with rough surface; c: MHM-Gu group, porous structure, rough surface granular substance; d: MHH-Cu group, porous structure, rough surface with larger particles; e: MH-Nb group, porous and ravine-like structure, rough surface with deposits; f: MH-Cu/Nb group, porous and obvious ravine-like structure, with more rough surface deposits"

Figure 5

X-ray diffraction patters of the different groups (a): MAO group, the coating consists mainly of Ti and Anatase TiO2; (b): MHL-Cu group, the coating consists of Ti、Anatase and Rutile TiO2, and a little Brookite TiO2; (c): MHM-Cu group, the coating consists of Ti、Anatase and Rutile TiO2; (d): MHH-Cu group, the coating consists of Ti、Anatase and Rutile TiO2; (e): MH-Nb group, the coating consists of Ti、Anatase and Rutile TiO2; (f): MH-Cu/Nb group, the coating consists of Ti、Anatase and Rutile TiO2 "

Figure 6

Escherichia coli and Staphylococcus aureus after 24 h surface culture of each group of specimens a: MAO group,Escherichia coligrew in large numbers and densely, with a small amount of fusion; b: MHH-Cu group, the number of Escherichia coli was significantly reduced and isolated; c: MH-Nb group,the number of Escherichia coli was reduced and loose; d: MH-Cu/Nb group, the number of Escherichia coliwas significantly reduced and isolated; e: MAO group, Staphylococcus aureus grew in large numbers and densely; f: MHH-Cu group, the number of Staphylococcus aureuswas significantly reduced and isolated; g: MH-Nb group, reduced number of Staphylococcus aureus and loose growth; h: MH-Cu/Nb group, the number of Staphylococcus aureusdecreased significantly and grew in isolation "

Table 4

Antibacterial effect of each group on Escherichia coliand Staphylococcus aureus n=3, $\bar{x} \pm s$ "

Groups Escherichia coli Staphylococcus aureus
Colony
count(CFU)
Antibacterial
rate(%)
Colony
count(CFU)
Antibacterial rate(%)
MAO 590.3±23.0 - 488.0±21.0 -
MHH-Cu 46.0±5.71) 92.2 34.7±3.51) 92.9
MH-Nb 273.0±9.21)2) 53.8 213.0±7.01)2) 56.4
MH-Cu/Nb 39.0±2.61)3) 94.4 28.3±2.11)3) 94.2
F 1 237.560 1 102.054
P < 0.001 < 0.001
[1] Ottria L, Lauritano D, Andreasi Bassi M, et al. Mechanical, chemical and biological aspects of titanium and titanium alloys in implant dentistry[J]. J Biol Regul Homeost Agents, 2018, 32(2 Suppl. 1):81-90.
[2] Chouirfa H, Bouloussa H, Migonney V, et al. Review of titanium surface modification techniques and coatings for antibacterial applications[J]. Acta Biomater, 2019, 83:37-54. doi: 10.1016/j.actbio.2018.10.036.
doi: S1742-7061(18)30635-4 pmid: 30541702
[3] Zhao QM, Yang HL, Liu ZT, et al. Fabrication of hydroxyapatite on pure titanium by micro-arc oxidation coupled with microwave-hydrothermal treatment[J]. J Mater Sci Mater Med, 2015, 26(2):88. doi: 10.1007/s10856-015-5429-z.
doi: 10.1007/s10856-015-5429-z
[4] Zhuang Y, Ren L, Zhang S, et al. Antibacterial effect of a copper-containing titanium alloy against implant-associated infection induced by methicillin-resistantStaphylococcus aureus[J]. Acta Biomater, 2021, 119:472-484. doi: 10.1016/j.actbio.2020.10.026.
doi: 10.1016/j.actbio.2020.10.026
[5] Tamai M, Isama K, Nakaoka R, et al. Synjournal of a novel beta-tricalcium phosphate/hydroxyapatite biphasic calcium phosphate containing niobium ions and evaluation of its osteogenic properties[J]. J Artif Organs, 2007, 10(1):22-28. doi: 10.1007/s10047-006-0363-y.
doi: 10.1007/s10047-006-0363-y
[6] Zhao YC, Cao HL, Qin H, et al. Balancing the osteogenic and antibacterial properties of titanium by codoping of Mg and Ag: anin vitro andin vivo study[J]. Acs Applied Materials & Interfaces, 2015, 7(32):17862-17836. doi: 10.1021/acsami.5b04168.
[7] 周雯, 彭显, 程磊. 口腔种植体表面影响细菌黏附因素的研究进展[J]. 口腔疾病防治, 2020, 28(2):102-106. doi: 10.12016/j.issn.2096-1456.2020.02.008.
Zhou W, Peng X, Cheng L. Research progress on factors affecting bacterial adhesion on the oral implant surface[J]. J Prev Treat Stomatol Dis, 2020, 28(2):102-106. doi: 10.12016/j.issn.2096-1456.2020.02.008.
[8] Scarano A, Valbonetti L, Degidi M, et al. Implant-abutment contact surfaces and microgap measurements of different implant connections under 3-Dimensional X-Ray microtomography[J]. Implant Dent, 2016, 25(5):656-662. doi: 10.1097/id.0000000000000465.
doi: 10.1097/ID.0000000000000465
[9] Pan X, Li Y, Abdullah AO, et al. Micro/nano-hierarchical structured TiO2 coating on titanium by micro-arc oxidation enhances osteoblast adhesion and differentiation[J]. Royal Society Open Science, 2019, 6(4):182031. doi: 10.1098/rsos.182031.
doi: 10.1098/rsos.182031
[10] Insua A, Monje A, Wang HL, et al. Basis of bone metabolism around dental implants during osseointegration and peri-implant bone loss[J]. J Biomed Mater Res A, 2017, 105(7):2075-2089. doi: 10.1002/jbm.a.36060.
doi: 10.1002/jbm.a.v105.7
[11] Yu W, Sun TW, Ding Z, et al. Copper-doped mesoporous hydroxyapatite microspheres synthesized by a microwave-hydrothermal method using creatine phosphate as an organic phosphorus source: application in drug delivery and enhanced bone regeneration[J]. J Mater Chem B, 2017, 5(5):1039-1052. doi: 10.1039/c6tb02747d.
doi: 10.1039/C6TB02747D
[12] Kulkarni Aranya A, Pushalkar S, Zhao M, et al. Antibacterial and bioactive coatings on titanium implant surfaces[J]. J Biomed Mater Res A, 2017, 105(8):2218-2227. doi: 10.1002/jbm.a.36081.
doi: 10.1002/jbm.a.36081 pmid: 28380669
[13] Ran W, Tian ZH, Guo B, et al. Superior biocompatibility and osteogenic efficacy of micro-arc oxidation-treated titanium implants in the canine mandible[J]. Biomed Mater, 2009, 4(5):055003. doi: 10.1088/1748-6041/4/5/055003.
doi: 10.1088/1748-6041/4/5/055003
[14] Ghosh R, Swart O, Westgate S, et al. Antibacterial copper-hydroxyapatite composite coatings via electrochemical synjournal[J]. Langmuir, 2019, 35(17):5957-5966. doi: 10.1021/acs.langmuir.9b00919.
doi: 10.1021/acs.langmuir.9b00919
[15] Li Y, Munir KS, Lin J, et al. Titanium-niobium pentoxide composites for biomedical applications[J]. Bioact Mater, 2016, 1(2):127-131. doi: 10.1016/j.bioactmat.2016.10.001.
[16] Wojcieszak D, Kaczmarek D, Adamiak B, et al. Influence of Cu and Nb additives on specific surface properties and biological activity of transparent TiO2 thin-film coatings[J]. Polim Med, 2013, 43(3):141-146.
pmid: 24377179
[1] CHEN Jing,CHEN Wenchuan. Research progress on tetrabutylammonium dihydrogen trifluoride as a substitute for hydrofluoric acid used for porcelain surface treatment [J]. Journal of Prevention and Treatment for Stomatological Diseases, 2021, 29(9): 629-633.
[2] ZHOU Zeying,ZHANG Jingyue,NIU Ju,LIU Dandan,ZHAO Wendi,LIU Xiaoqiu. Research progress on the antibacterial properties of dental resin materials [J]. Journal of Prevention and Treatment for Stomatological Diseases, 2021, 29(9): 638-643.
[3] ZHANG Ying,HU Dandan,HUANG Haoning,LUO Xiaoping. Effect of different treatments of highly translucent zirconia on the bonding strength between zirconia and veneering porcelain [J]. Journal of Prevention and Treatment for Stomatological Diseases, 2021, 29(7): 456-461.
[4] WANG Ke,PENG Guoguang,HE Shanzhi,TAN Yulian. Retrospective analysis of the treatment of mandibular condylar sagittal fracture with Kirschner wire in 13 cases [J]. Journal of Prevention and Treatment for Stomatological Diseases, 2021, 29(7): 474-478.
[5] QI Xia,KONG Lingxue,LI Shujuan,MA Siting,QI Yali,ZHAO Lei. Inhibitory effects of epigallocatechin-3-gallate on the pathogenic properties of P. gingivalis in vitro [J]. Journal of Prevention and Treatment for Stomatological Diseases, 2021, 29(5): 314-321.
[6] WANG Min,JIANG Nan,ZHU Songsong. A novel biomimetic micro/nano hierarchical interface of titanium enhances adhesion, proliferation and osteogenic differentiation of bone marrow mesenchymal cells [J]. Journal of Prevention and Treatment for Stomatological Diseases, 2021, 29(4): 226-233.
[7] FAN Dongyang,WANG Qiang,ZHOU Yijun,LI Siwen,FENG Xu,LIU Chunran,CUI Jiasen,SUN Hongchen. Research progress on the application of antibacterial titanium alloys in stomatology [J]. Journal of Prevention and Treatment for Stomatological Diseases, 2021, 29(4): 284-288.
[8] WANG Chenwei,SUN Fangfang,YANG Chuncheng,DING Ling,CHEN Xi,ZHANG Jiaqi,WU Guofeng. Effects of concentrated sulfuric acid etching durations on the shear bond strength between polyether-ketone-ketone and dentin [J]. Journal of Prevention and Treatment for Stomatological Diseases, 2021, 29(3): 151-156.
[9] CHEN Shuang,XUE Xin,JIN Xing′ai,LIU Yingqun. Effect of dentin surface treatments on the bond strength of resin-modified glass ionomer cement [J]. Journal of Prevention and Treatment for Stomatological Diseases, 2021, 29(2): 130-134.
[10] XU Tengfei,CHEN Bin,AO Huizhi,SUN Weibin,WU WenLei. Effect of the antimicrobial photodynamic therapy in the treatment of periodontitis in type 2 diabetes mellitus: a systematic review and meta-analysis [J]. Journal of Prevention and Treatment for Stomatological Diseases, 2021, 29(11): 752-760.
[11] XIE Lin,FENG Xiaoli,DENG Zi,MA Rui,HU Chen,SHAO Longquan. Neurotoxicity and mechanism of dental nanomaterials [J]. Journal of Prevention and Treatment for Stomatological Diseases, 2020, 28(9): 594-598.
[12] KONG Jingjing,LI Chunnian,YIN Liangliang,DAI Xinpeng. Experimental study on central location ability and clearance rate of three nickel-titanium instruments for root canal retreatment [J]. Journal of Prevention and Treatment for Stomatological Diseases, 2020, 28(8): 494-498.
[13] CAO Li,ZHANG Ning,BAI Yuxing. Mechanical strength and inhibition of plaque biofilm activity of a novel antibacterial Hawley retainer [J]. Journal of Prevention and Treatment for Stomatological Diseases, 2020, 28(8): 499-505.
[14] ZHU Shaojun,RENA· Maimaiti,ZHANG Bei,WANG Zhiheng,GE Jinlian,LIU Yishan. Serum levels of iron, zinc, copper and vitamin D in severe early childhood caries [J]. Journal of Prevention and Treatment for Stomatological Diseases, 2020, 28(8): 506-509.
[15] WANG Wanrong,GU Junting,GAO Peng,LI Jing,WAN Meichen,JIAO Kai,NIU Lina. Progress in the application of metal and metal oxide nanoparticles in the antibacterial modification of dental materials [J]. Journal of Prevention and Treatment for Stomatological Diseases, 2020, 28(8): 540-544.
Viewed
Full text


Abstract

Cited

  Shared   
  Discussed   
[1] . [J]. journal1, 2016, 24(1): 58 -60 .
[2] Juan LI,Ting HUANG,Wen XUE,Hai-yan LI. Clinical efficacy of basic periodontal therapy combined with local medication for erosive oral lichen planus[J]. Journal of Prevention and Treatment for Stomatological Diseases, 2016, 24(3): 162 -165 .
[3] Ming CHEN,Xi CHEN,Zhen-ting ZHANG. The precision comparison of the denture occlusal plane preparation by the occlusal plane plate between experienced and newly-graduated dentists[J]. Journal of Prevention and Treatment for Stomatological Diseases, 2016, 24(3): 173 -176 .
[4] Zhong-juan TAN,Yue-ping ZHAO,Yuan-yuan LUO. The research progress of dental pulp regeneration[J]. Journal of Prevention and Treatment for Stomatological Diseases, 2016, 24(6): 374 -377 .
[5] Lan LIAO, Lijun ZENG. Updated research on digitalization in aesthetic restoration[J]. Journal of Prevention and Treatment for Stomatological Diseases, 2018, 26(7): 409 -414 .
[6] Yan-mei DONG. Causes and management of post-treatment apical periodontitis[J]. Journal of Prevention and Treatment for Stomatological Diseases, 2016, 24(10): 561 -566 .
[7] LI Chun,LI Yan-hong,LIU Juan. Application of probiotics for dental caries prevention in children[J]. Journal of Prevention and Treatment for Stomatological Diseases, 2016, 24(9): 558 -560 .
[8] Mingyu SUN, Hanjiang WU. Research progresses in occult lymph node metastasis of oral squamous cancer[J]. Journal of Prevention and Treatment for Stomatological Diseases, 2018, 26(1): 61 -65 .
[9] Qian-qian HAN,Zhao LIU,Li JIANG,Hui-yi TANG,Xiao-na LI. Effects of LMK-235 on osteoblast/odontoblast differentiation in hPDLCs[J]. Journal of Prevention and Treatment for Stomatological Diseases, 2016, 24(7): 390 -394 .
[10] Nu MI,Ying GUO,Xiao-yu YANG. Clinical evaluation of anterior teeth aesthetic restoration with thin porcelain laminate veneer[J]. Journal of Prevention and Treatment for Stomatological Diseases, 2016, 24(10): 589 -593 .
This work is licensed under a Creative Commons Attribution 3.0 License.