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A special issue of Coatings (ISSN 2079-6412). This special issue belongs to the section "Surface Characterization, Deposition and Modification".

Deadline for manuscript submissions: closed (30 October 2021) | Viewed by 28379

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Prof. Dr. Yanxiang Zhang

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School of Materials Science and Engineering, Harbin Institute of Technology, Harbin, China
Interests: heat treatment and surface engineering
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Dear Colleagues,

We would like to invite you to submit to this Special Issue of “Surface Engineering of C/N/O Functionalized Materials” with a special focus on functionalizing metallic or ceramic materials via surface chemical modifications by C/N/O fast diffusers. Great scientific and technological progress on surface modifications has been achieved in the respective material categories to date, but cross-references across material categories are barely made although common technical mechanisms existing therein. The aim of this Special Issue is to present technical synergies, such as characterization and testing methodology, surface reaction mechanism, diffusion mechanism, process–structure–property relationships, etc., between the surface engineering of metals and ceramics by evaluating the reaction-diffusion of C/N/O, and to accelerate scientific discovery in the area of surface engineering.

The carburizing and nitriding of metallic materials are vital to enhancing the fatigue life of key base components, such as tools and dies. Highly efficient oxygen transport in ceramic oxides is important to accelerate the practical applications of ceramic fuel cells. It appears that metallic materials and ceramic fuel cell materials belong to structural and functional materials, respectively. The thermochemical treatment of metallic materials, such as carburization and nitridation, and oxygen transport in ceramic fuel cells have similarities. For example, they have a similar temperature range (400–1000 °C); the element C/N/O is penetrated into the material bulk; the elemental processes are the same, i.e., reaction first then diffusion. Therefore, the two categories of materials can be integrated as “C/N/O Functionalized Materials”. This Special Issue is dedicated to the up-to-date development of surface engineering of C/N/O functionalized materials. Both experimental and theoretical studies are encouraged. The subtopics to be covered within the issue include but are not limited to:

Heat treatment of steels;
Ceramic fuel cells;
Surface engineering of metals and ceramics;
Carburization and nitridation;
Surface chemical modification;
Process modeling and simulation;
Process–structure–property relationships.

Prof. Dr. Yan Xiang Zhang
Guest Editor

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Keywords

Metallic materials
Ceramic oxides
Heat treatment
Surface engineering
Doping
Carburization
Nitridation
Modeling

Published Papers (12 papers)

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Research

12 pages, 7802 KiB

Open AccessArticle

Influence of Grain Boundary Precipitates on Intergranular Corrosion Behavior of 7050 Al Alloys

by Yuxiao Qiu, Rongying Liu, Linchi Zou, Haitao Chi, Chen Wang, Binshu Wang and Junfeng Chen

Coatings 2022, 12(2), 249; https://doi.org/10.3390/coatings12020249 - 14 Feb 2022

Cited by 5 | Viewed by 2978

Abstract

The effects of the grain boundary precipitation on intergranular corrosion behavior were investigated by exfoliation tests and complementary techniques like scanning electron microscope (SEM), optical profilometry (OP), transmission electron microscope together with energy dispersive spectroscopy (TEM-EDS), and atomic force microscope (AFM). The results reveal the influencing mechanism of intergranular corrosion behavior from grain boundary precipitates (GBPs). The potential discrepancy between GBPs and adjacent areas induces corrosion cavity germination along the grain boundary. Furthermore, the increase of both active Mg and Zn content in GBPs improve the potential difference, which aggravates the intergranular corrosion cavity germination. However, the increment of noble Cu content in GBP is beneficial to reduce the potential difference. On the other side, the distribution of the continuous precipitates in the grain boundary region helps the initial corrosion cavities to connect, which improves the growth of intergranular corrosion cracks. Additionally, discontinuous GBPs and precipitation free zone (PFZ) hinder the spread and connection of intergranular corrosion cavities. Therefore, 7050 aluminum alloy forming different grain boundary precipitation characteristics after different aging treatments shows different resistance to intergranular corrosion: peak-aging < under-aging < over-aging. Full article

(This article belongs to the Special Issue Surface Engineering of C/N/O Functionalized Materials)

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21 pages, 12659 KiB

Open AccessArticle

Enhancement Research on Piezoelectric Performance of Electrospun PVDF Fiber Membranes with Inorganic Reinforced Materials

by Chong Li, Haoyu Wang, Xiao Yan, Hanxige Chen, Yudong Fu and Qinhua Meng

Coatings 2021, 11(12), 1495; https://doi.org/10.3390/coatings11121495 - 05 Dec 2021

Cited by 8 | Viewed by 2635

Abstract

The electrospun PVDF fiber membranes with the characteristics of light weight, strong signal and measurability, have been widely applied in the fields of environment, energy sensors and biomedical treatment. Due to the weakness of the piezoelectric and service properties, the conventional PVDF fiber membranes cannot meet the operating requirements. Based on the obtained optimal technological parameter of electrospun pure PVDF fiber membranes (P-PVDF) in the previous experiment (unpublished), three inorganic reinforced substances (AgNO₃, FeCl₃·6H₂O, nanographene) were respectively used to dope and modify PVDF to prepare composite fiber membranes with the better piezoelectric performance. The morphology and crystal structure of the hybrid fiber membranes were observed and detected by scanning electron microscopy and X-ray diffraction, respectively. The results showed that the dopant could effectively promote the formation of β-phase, which can enhance the piezoelectric performance. The mechanical properties test and piezoelectric performance test exhibited that the static flexural strength, the elastic modulus, and the piezoelectric performance were improved with the addition of dopant. In addition, the influence on the addition of dopant and the doping modification mechanism were discussed. Finally, the conclusions showed that the minimum average diameter was obtained with the 0.3 wt% addition of AgNO₃; the piezoelectric performance reached the strongest with the 0.8 wt% addition of FeCl₃·6H₂O; the mechanical properties were best with the 1.0 wt% addition of nanographene. Full article

(This article belongs to the Special Issue Surface Engineering of C/N/O Functionalized Materials)

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12 pages, 9882 KiB

Open AccessArticle

Acceleration of Plasma Nitriding at 550 °C with Rare Earth on the Surface of 38CrMoAl Steel

by Dongjing Liu, Yuan You, Mufu Yan, Hongtao Chen, Rui Li, Lin Hong and Tingjie Han

Coatings 2021, 11(9), 1122; https://doi.org/10.3390/coatings11091122 - 16 Sep 2021

Cited by 5 | Viewed by 2164

Abstract

In order to explore the effect of the addition of rare earth (RE) to a steel microstructure and the consequent performance of a nitrided layer, plasma nitriding was carried out on 38CrMoAl steel in an atmosphere of NH₃ at 550 °C for 4, 8, and 12 h. The modified layers were characterized using an optical microscope (OM), a microhardness tester, X-ray diffraction (XRD), a scanning electron microscope (SEM), a transmission electron microscope (TEM), and an electrochemical workstation. After 12 h of nitriding without RE, the modified layer thickness was 355.90 μm, the weight gain was 3.75 mg/cm², and the surface hardness was 882.5 HV_0.05. After 12 h of RE nitriding, the thickness of the modified layer was 390.8 μm, the weight gain was 3.87 mg/cm², and the surface hardness was 1027 HV_0.05. Compared with nitriding without RE, the ε-Fe_2-3N diffraction peak was enhanced in the RE nitriding layer. After 12 h of RE nitriding, La, LaFeO₃, and a trace amount of Fe₂O₃ appeared. The corrosion rate of the modified layer was at its lowest (15.089 × 10⁻² mm/a), as was the current density (1.282 × 10⁻⁵ A/cm²); therefore, the corrosion resistance improved. Full article

(This article belongs to the Special Issue Surface Engineering of C/N/O Functionalized Materials)

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10 pages, 6768 KiB

Open AccessArticle

Low-Temperature Plasma Nitriding of 3Cr13 Steel Accelerated by Rare-Earth Block

by Yuan You, Rui Li, Mufu Yan, Jihong Yan, Hongtao Chen, Chaohui Wang, Dongjing Liu, Lin Hong and Tingjie Han

Coatings 2021, 11(9), 1050; https://doi.org/10.3390/coatings11091050 - 31 Aug 2021

Cited by 3 | Viewed by 1809

Abstract

The plasma nitriding of 3Cr13 steel occurred at 450 °C for 4, 8 and 12 h in NH₃ with and without rare earth (RE). The nitrided layers were characterized using an OM, SEM, TEM, XRD, XPS, microhardness tester and electrochemical workstation. The modified layer, with and without La, are composed of a compound layer and diffusion layer from surface to core. After the addition of La during nitriding, the maximum increase of layer thickness, mass gain and average microhardness was 15.6%, 35.8% and 212.50HV_0.05, respectively. With the increase of the proportion of ε-Fe_2-₃N, the passivation zone of the corrosion resistance curve increases from 2.436 to 3.969 V, the corrosion current density decreases, the corrosion potential and pitting potential both increase, and, consequently, the corrosion resistance is significantly improved. Most of the surface microstructures of the nitrided layer was refined by the addition of La. The presence of La reduces the N content in the modified layer, which accelerates the diffusion of N atoms and, thus, accelerates the nitriding process. Full article

(This article belongs to the Special Issue Surface Engineering of C/N/O Functionalized Materials)

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14 pages, 6531 KiB

Open AccessArticle

Effect of Deformation on the Microstructure of Cold-Rolled TA2 Alloy after Low-Temperature Nitriding

by Guotan Liu, Huanzheng Sun, Enhong Wang, Keqiang Sun, Xiaoshuo Zhu and Yudong Fu

Coatings 2021, 11(8), 1011; https://doi.org/10.3390/coatings11081011 - 23 Aug 2021

Cited by 6 | Viewed by 1899

Abstract

In order to improve the low hardness and poor wear resistance of TA2, this paper proposes a composite process of cold-rolling and low-temperature plasma nitriding with recrystallization. This composite modification process can effectively achieve the dual goals of modifying the matrix structure and surface of TA2 alloy simultaneously. The cold-rolling experimental results indicate that when the deformation rate increases, the small-sized grains in the sample increase significantly, and the grain orientation changes from TD (transverse direction) to RD (rolling direction) and then to TD. The nitriding experimental results indicate that the {0001} basal surface texture deflected from the TD direction to the RD direction, {10-10} cylindrical texture components gradually increased, and the special orientation phenomenon of cylindrical and conical texture disappeared, it can be seen that an increase in the deformation rate promotes recrystallization. The XRD test results indicate that after low-temperature nitriding, metastable nitriding phase TiN0.26 is formed on the surface of TA2. The SEM morphology of the cross-section shows that a relatively special nitrided zone is formed, and mechanical performance test results indicate the wear resistance and hardness of the alloy increased. Full article

(This article belongs to the Special Issue Surface Engineering of C/N/O Functionalized Materials)

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11 pages, 2668 KiB

Open AccessArticle

Fabrication and Properties of Electrospun and Electrosprayed Polyethylene Glycol/Polylactic Acid (PEG/PLA) Films

by Weichang Ke, Xiang Li, Mengyu Miao, Bing Liu, Xiaoyu Zhang and Tong Liu

Coatings 2021, 11(7), 790; https://doi.org/10.3390/coatings11070790 - 30 Jun 2021

Cited by 13 | Viewed by 2319

Abstract

Polylactic acid (PLA) film is an alternative filter material for heat-not-burn (HNB) tobacco, but its controllability in cooling performance is limited. In this work, polyethylene glycol (PEG) was introduced to form a polyethylene glycol/polylactic acid (PEG/PLA) film by electrospinning or electrospraying techniques to enhance the cooling performance, due to its lower glass transition and melting temperatures. The PEG/PLA films with typical electrospun or electrosprayed morphologies were successfully fabricated. One typical endothermic peak at approximately 65 °C was clearly observed for the melting PEG phase in the heating process, and the re-crystallization temperature represented by an exothermic peak was effectively lowered to 90–110 °C during the cooling process, indicating that the cooling performance is greatly enhanced by the introduction of the PEG phase. Additionally, the wetting properties and adsorption properties were also intensively studied by characterizing the contact angles, and the as-prepared PEG/PLA films all showed good affinity to water, 1,2-propandiol and triglyceride. Furthermore, the PEG/PLA film with a PLA content of 35 wt.% revealed the largest elasticity modulus of 378.3 ± 68.5 MPa and tensile strength of 10.5 ± 1.1 MPa. The results achieved in this study can guide the development of other filter materials for HNB tobacco application. Full article

(This article belongs to the Special Issue Surface Engineering of C/N/O Functionalized Materials)

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19 pages, 5642 KiB

Open AccessArticle

Investigation of Mechanical Properties for Basalt Fiber/Epoxy Resin Composites Modified with La

by Chong Li, Haoyu Wang, Xiaolei Zhao, Yudong Fu, Xiaodong He and Yiguo Song

Coatings 2021, 11(6), 666; https://doi.org/10.3390/coatings11060666 - 31 May 2021

Cited by 15 | Viewed by 2524

Abstract

As an efficient reinforcing material in resin matric composites, the application of basalt fibers (BFs) in composites is limited by the poor interfacial adhesion between BFs and the resin matrix. In this study, to obtain the basalt fibers/epoxy resin composites with enhanced mechanical properties, the modification solution containing different concentrations of Lanthanum ions (La³⁺) was synthesized to modify the BFs surfaces to enhance the poor interfacial adhesion between BFs and the matrix. The morphology, the chemical structure and the chemical composition of the modified BFs surface were observed and detected by scanning electron microscopy, Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy, respectively. The results show that, after BFs were soaked in the modification solution, the more active groups (C=O, –OH, C–O, etc.) were introduced to the BFs surfaces and effectively enhanced the bond strength between BFs and the resin matrix. The obtained mechanical performances of prepared basalt fibers/epoxy resin composites showed that the tensile strength, bending strength and interlaminar shear strength (ILSS) were improved with the modified BFs, and reached to 458.7, 556.7 and 16.77 Mpa with the 0.5 wt.% La. Finally, the enhancement mechanism of the modification solution containing La element is analyzed. Full article

(This article belongs to the Special Issue Surface Engineering of C/N/O Functionalized Materials)

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11 pages, 4077 KiB

Open AccessArticle

Exploring the Effect of NiO Addition to La_0.99Ca_0.01NbO₄ Proton-Conducting Ceramic Oxides

by Kaili Yuan, Xuehua Liu and Lei Bi

Coatings 2021, 11(5), 562; https://doi.org/10.3390/coatings11050562 - 11 May 2021

Cited by 1 | Viewed by 1690

Abstract

To improve the performance and overcome the processing difficulties of La_0.99Ca_0.01NbO₄ proton-conducting ceramic oxide, external and internal strategies were used, respectively, to modify La_0.99Ca_0.01NbO₄ with NiO. The external strategy refers to the use of the NiO as a sintering aid. The NiO was added to the synthesized La_0.99Ca_0.01NbO₄ powder as a secondary phase, which is the traditional way of using the NiO sintering aid. The internal strategy refers to the use of NiO as a dopant for the La_0.99Ca_0.01NbO₄. Both strategies improve the sinterability and conductivity, but the effect of internal doping is more significant in enhancing both grain growth and conductivity, making it more desirable for practical applications. Subsequently, the influences of different concentrations of NiO were compared to explore the optimal ratio of the NiO as the dopant. It was found that the sample with 1 or 2 wt.% NiO had similar performance, while with 5 wt.%, NiO doping content hampered the grain growth. In addition, the inhomogeneous distribution of the element in the high-NiO content sample was found to be detrimental to the electrochemical performance, suggesting that the moderate doping strategy is suitable for La_0.99Ca_0.01NbO₄ proton-conducting electrolyte with improved performance. Furthermore, first-principle calculations indicate the origin of the enhanced performance of the internally modified sample, as it lowers both oxygen formation energy and hydration energy compared with the un-modified one, facilitating proton migration. Full article

(This article belongs to the Special Issue Surface Engineering of C/N/O Functionalized Materials)

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10 pages, 4814 KiB

Open AccessArticle

A Novel Decarburizing-Nitriding Treatment of Carburized/through-Hardened Bearing Steel towards Enhanced Nitriding Kinetics and Microstructure Refinement

by Fuyao Yan, Jiawei Yao, Baofeng Chen, Ying Yang, Yueming Xu, Mufu Yan and Yanxiang Zhang

Coatings 2021, 11(2), 112; https://doi.org/10.3390/coatings11020112 - 20 Jan 2021

Cited by 1 | Viewed by 2478

Abstract

Decarburization is generally avoided as it is reckoned to be a process detrimental to material surface properties. Based on the idea of duplex surface engineering, i.e., nitriding the case-hardened or through-hardened bearing steels for enhanced surface performance, this work deliberately applied decarburization prior to plasma nitriding to cancel the softening effect of decarburizing with nitriding and at the same time to significantly promote the nitriding kinetics. To manifest the applicability of this innovative duplex process, low-carbon M50NiL and high-carbon M50 bearing steels were adopted in this work. The influence of decarburization on microstructures and growth kinetics of the nitrided layer over the decarburized layer is investigated. The metallographic analysis of the nitrided layer thickness indicates that high carbon content can hinder the growth of the nitrided layer, but if a short decarburization is applied prior to nitriding, the thickness of the nitrided layer can be significantly promoted. The analysis of nitriding kinetics shows that decarburization reduces the activation energy for nitrogen diffusion and enhances nitrogen diffusivity. Moreover, the effect of decarburization in air can promote surface microstructure refinement via spinodal decomposition during plasma nitriding. Full article

(This article belongs to the Special Issue Surface Engineering of C/N/O Functionalized Materials)

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10 pages, 4329 KiB

Open AccessArticle

Insights in to the Electrochemical Activity of Fe-Based Perovskite Cathodes toward Oxygen Reduction Reaction for Solid Oxide Fuel Cells

by Dan Ma, Juntao Gao, Tian Xia, Qiang Li, Liping Sun, Lihua Huo and Hui Zhao

Coatings 2020, 10(12), 1260; https://doi.org/10.3390/coatings10121260 - 19 Dec 2020

Cited by 2 | Viewed by 2212

Abstract

The development of novel oxygen reduction electrodes with superior electrocatalytic activity and CO₂ durability is a major challenge for solid oxide fuel cells (SOFCs). Here, novel cobalt-free perovskite oxides, BaFe_1−xY_xO_3−δ (x = 0.05, 0.10, and 0.15) denoted as BFY05, BFY10, and BFY15, are intensively evaluated as oxygen reduction electrode candidate for solid oxide fuel cells. These materials have been synthesized and the electrocatalytic activity for oxygen reduction reaction (ORR) has been investigated systematically. The BFY10 cathode exhibits the best electrocatalytic performance with a lowest polarization resistance of 0.057 Ω cm² at 700 °C. Meanwhile, the single cells with the BFY05, BFY10 and BFY15 cathodes deliver the peak power densities of 0.73, 1.1, and 0.89 W cm⁻² at 700 °C, respectively. Furthermore, electrochemical impedance spectra (EIS) are analyzed by means of distribution of relaxation time (DRT). The results indicate that the oxygen adsorption-dissociation process is determined to be the rate-limiting step at the electrode interface. In addition, the single cell with the BFY10 cathode exhibits a good long-term stability at 700 °C under an output voltage of 0.5 V for 120 h. Full article

(This article belongs to the Special Issue Surface Engineering of C/N/O Functionalized Materials)

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13 pages, 2806 KiB

Open AccessArticle

The Effects of Transition Metal Oxides (Me = Ti, Zr, Nb, and Ta) on the Mechanical Properties and Interfaces of B₄C Ceramics Fabricated via Pressureless Sintering

by Guanqi Liu, Shixing Chen, Yanwei Zhao, Yudong Fu and Yujin Wang

Coatings 2020, 10(12), 1253; https://doi.org/10.3390/coatings10121253 - 18 Dec 2020

Cited by 5 | Viewed by 1741

Abstract

There is little available research on how different transition metal oxides influence the behavior of B₄C-based ceramics, especially for Ta₂O₅ and Nb₂O₅. B₄C-MeB₂ (Me = Ti, Zr, Nb, and Ta) multiphase ceramic samples were prepared via in situ pressureless sintering at 2250 °C, involving the mixing of B₄C and MeO_x powders, namely TiO₂, ZrO₂, Nb₂O₅, and Ta₂O₅. The phase constituents, microstructures, and mechanical properties of the samples were tested. The results indicated that different transition metal elements had different effects on the ceramic matrix, as verified through a comparative analysis. Additionally, the doped WC impurity during the ball milling process led to the production of (Me, W)B₂ and W₂B₅, which brought about changes in morphology and performance. In this study, the Ta₂O₅-added sample exhibited the best performance, with elastic modulus, flexural strength, Vickers hardness, and fracture toughness values of 312.0 GPa, 16.3 GPa, 313.0 MPa, and 6.08 MPa·m^1/2, respectively. The comprehensive mechanical properties were better than the reported values when the mass fraction of the second phase was around five percent. Full article

(This article belongs to the Special Issue Surface Engineering of C/N/O Functionalized Materials)

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11 pages, 2479 KiB

Open AccessEditor’s ChoiceArticle

Distribution of Characteristic Times: A High-Resolution Spectrum Approach for Visualizing Chemical Relaxation and Resolving Kinetic Parameters of Ionic-Electronic Conducting Ceramic Oxides

by Fuyao Yan, Yiheng Wang, Ying Yang, Lei Zhu, Hui Hu, Zhuofu Tang, Yanxiang Zhang, Mufu Yan, Changrong Xia and Yueming Xu

Coatings 2020, 10(12), 1240; https://doi.org/10.3390/coatings10121240 - 17 Dec 2020

Cited by 5 | Viewed by 2504

Abstract

Surface exchange coefficient (k) and bulk diffusion coefficient (D) are important properties to evaluate the performance of mixed ionic-electronic conducting (MIEC) ceramic oxides for use in energy conversion devices, such as solid oxide fuel cells. The values of k and D are usually estimated by a non-linear curve fitting procedure based on electrical conductivity relaxation (ECR) measurement. However, the rate-limiting mechanism (or the availability of k and D) and the experimental imperfections (such as flush delay for gaseous composition change, τ_f) are not reflected explicitly in the time–domain ECR data, and the accuracy of k and D demands a careful sensitivity analysis of the fitting error. Here, the distribution of characteristic times (DCT) converted from time–domain ECR data is proposed to overcome the above challenges. It is demonstrated that, from the DCT spectrum, the rate-limiting mechanism and the effect of τ_f are easily recognized, and the values of k, D and τ_f can be determined conjunctly. A strong robustness of determination of k and D is verified using noise-containing ECR data. The DCT spectrum opens up a way towards visible and credible determination of kinetic parameters of MIEC ceramic oxides. Full article

(This article belongs to the Special Issue Surface Engineering of C/N/O Functionalized Materials)

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