Facile Fabrication and Application of Superhydrophilic Stainless Steel

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Cite This: ACS Sustainable Chem. Eng. 2017, 5, 10283-10289

Facile Fabrication and Application of Superhydrophilic Stainless Steel Hollow Fiber Microfiltration Membranes Ming Wang, Yue Cao, Zhen-Liang Xu,* Yu-Xuan Li, and Shuang-Mei Xue State Key Laboratory of Chemical Engineering, Membrane Science and Engineering R&D Lab, Chemical Engineering Research Center, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, China S Supporting Information *

ABSTRACT: Superhydrophilic stainless steel hollow fiber microfiltration membranes (SSHF-MFs) were developed through a facile dip-coating method, followed by sintering at a low temperature of 500 °C. A novel mediating additive was explored to mediate the coating suspensions. The additive, which could form hydrogen bonds with TiO2 agglomerations, facilitated the formation of a continuous TiO2 layer on the rough surface of stainless steel hollow fibers (SSHFs). The fabricated SSHF-MFs exhibited superhydrophilic and underwater superoleophobicity wettability, which enabled SSHFMFs to be applied to antifouling fields. The fouling resistance of SSHF-MFs for oil/water emulsion, cake layer foulant (sodium alginate, SA), and adhesive foulant (bovine serum albumin, BSA) were investigated systematically. SSHF-MFs exhibited superior antifouling properties and high rejections of 99% and 90% for oil/water emulsion and SA foulant solution, respectively. For the adhesive BSA solution, SSHF-MFs still showed good antifouling property after washing with a dilute alkaline solution and superior separation performance (90%). Meanwhile, SSHF-MFs exhibited an excellent separation performance for polystyrene microspheres (100 nm) with a rejection of 100%. In conclusion, SSHF-MFs showed great potential, not only in traditional microfiltration fields, such as solid−liquid separation, but also in the antifouling field, such as oil/water separation. The facile fabrication conditions and superior wettability further improved the sustainability of SSHF-MFs in practical applications. KEYWORDS: Hydrogen bond, Superwettability, Microfiltration, Oil/water separation, Antifouling

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membranes suffer from their limited long-term stability.10 Therefore, the exploitation of superhydrophilic inorganic MF membranes still needs significant efforts. In recent years, stainless steel hollow fibers (SSHFs) with different configurations have been developed, because of their typical properties such as high mechanical strength, good thermal shock resistance, and easy integration into modules by welding.11 However, the interests of recent research on SSHFs have mainly been focused on their preparation process;12−16 direct practical application of SSHFs is unavailable, because of their drawbacks of rough surface and large pore size distribution. Since it is a highly energy-consuming task to obtain finer stainless steel powders (SSPs), the composite membranes seem to be a promising alternative to acquire SSHFs with narrow pore size distribution. The composite membranes usually include a functional ceramic layer and stainless steel (SS) substrates. As is well-known, it is easier to handle submicrometer-sized ceramic particles than SSPs with the same size, which enable finer microstructures and well-

INTRODUCTION Crude oil leakage accident and oily wastewater are severely destroying our marine environment, which is one of the top environmental concerns.1 Meanwhile, it is highly desired to reclaim the pure oil from their wastewater. Nevertheless, conventional handling countermeasures, such as skimming, coagulation, in situ burning, and flocculation techniques, are expensive, ineffective, and even not environmentally friendly.2−4 In contrast, membrane processing as a green and low-cost technology has drawn extensive attention for oil/water separation. For the water-in-oil system, various superhydrophobic membranes with superior separation efficiency for water droplet and antifouling property have been developed.5−7 For the oil-in-water system, membrane pores are inclined to be blocked by oil droplets, because of their distortion and high viscosity. However, superhydrophilic microfiltration (MF) membranes could ease the membrane fouling phenomenon, because of the lower oil adhesion to the membrane surface, and exhibit superior separation efficiency for oil droplet, antifouling property, and even antibacterial activity.2,8,9 As we all know, inorganic MF membranes could realize high thermal stability, good chemical stability, and superior cleaning ability through chemistry, high pressure, or backflushing, whereas organic © 2017 American Chemical Society

Received: July 9, 2017 Revised: September 7, 2017 Published: September 18, 2017 10283

DOI: 10.1021/acssuschemeng.7b02300 ACS Sustainable Chem. Eng. 2017, 5, 10283−10289

Research Article

ACS Sustainable Chemistry & Engineering defined pore size.17 The combination of both advantages of ceramic and SS membranes overcomes the insufficiency of individual SS membranes efficiently. Commonly preferred ceramic particles are metallic oxide such as ZrO2, Al2O3, and TiO2, among which TiO2 grains have drawn considerable attention, because of their numerous characteristics including hydrophilicity, catalysis, semiconductivity, low melting temperature (compared with ZrO2, Al2O3), and good adhesive ability with metal substrates.10 Until now, dip coating,18,19 wet powder spraying,10,17 slip casting,20,21 and electrophoretic deposition22,23 techniques have been commonly used to functionalize these materials. Among these methods, dip coating is a conventional and facile technique to form a ceramic layer. Although sometimes the fine particles would penetrate into the support pores resulting in the sacrifice of original permeability of supports, the particles penetration could improve the binding strength and thermal stability between the ceramic layer and metal substrates. Asymmetric TiO2 microfiltration membranes supported on SS tubes or flat sheets have been commercialized for years by corporations such as GKN, Mott, Graver Technologies, Pall, Hyflux, and so on. However, since Forschungszentrum Juelich developed graded TiO2 microfiltration membranes with a mean pore size of 0.11 μm on planar SS substrates using a wet powder spraying technique,10,17 the reports on stainless steel microfiltration (SS-MF) membranes are limited, especially on their application fields. Therefore, the preparation and application of SS-MF still show great potential to be optimized and explored. In the present study, superhydrophilic SSHF-MFs are fabricated by dip-coating TiO2 suspensions on SS substrates, followed by sintering at a low temperature (500 °C). A novel additive that could form hydrogen bonds with TiO 2 agglomerations facilitated the formation of a continuous TiO2 layer. Corresponding experiments and characterization have verified the positive effect of hydrogen bonds. It is well-known that the more hydrophilic the surface, the better the antifouling property it presents.3,24 According to the intrinsic superhydrophilic property of TiO2 layer, a series of antifouling and separation experiments have been conducted. Bovine serum albumin (BSA), sodium alginate (SA), and oil/water emulsion are used to evaluate the antifouling properties of SSHF-MFs. In addition, the morphology, wettability, and pore size distribution of SSHF-MFs are characterized systematically.

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for 30 min. Subsequently, the suspension was pressed out through the spinneret under a pressure of 0.1 MPa. The precursors then were immersed in DI water for 24 h to remove the residual solvent. Lastly, the precursors were dried naturally and sintered in an atmosphere furnace. The temperature was increased to 350 °C, using a heating rate of 1 °C/min, and held at that temperature for 1 h to burn out the polymer. The fibers then were sintered at 1100 °C for 2 h, using a heating rate of 5 °C/min to acquire the mechanical strength. SSHF-MF Supports. A TiO2 coating suspension with a particle content of 10 wt % was obtained by dispersing TiO2 nanoparticles in DI water. Three types of monomers (PIP, PEI, and ethylenediamine), which were used as additives, were added to mediate the coating suspension. SSHFs with both ends wrapped by Teflon tape were pulled up from the suspension at a speed of 50 cm/min after being dipped for 30 s, and then were dried in ambient temperature for 24 h. Lastly, SSHF-MFs were obtained after calcining at 500 °C for 2 h to ensure the coalescence of TiO2 particles. SSHF-MFs prepared from four different TiO2 suspensions (without additive, with PIP, with PEI, and with ethylenediamine) were abbreviated as SSHF-MF0, SSHFMF1, SSHF-MF2, and SSHF-MF3, respectively. Characterization. The morphology of SSHF-MFs was examined via scanning electron microscopy (SEM) (Model JSM-6380 LV, JEOL, Japan). SSHF-MFs were affixed to a copper holder and sputter-coated with gold under vacuum. Attenuated total reflectance Fourier transform infrared spectra (ATR-FTIR) of different coating solutions were measured by the spectrometer (Model 6700, Nicolet, USA) to analyze the existence of hydrogen bonds in coating solutions. The pore size distribution of pristine SSHFs and SSHF-MFs were measured by the capillary flow porosimetry (Model 3H-2000PB, Beishide Instruments, China). The effective pore size was evaluated by the rejection of PS microspheres. The particle sizes of PS microspheres were measured by dynamic light scattering (DLS) (Model Nano ZS, Zetasizer, U.K.). Water and oil contact angles were measured using equipment made by Shanghai Zhongcheng Digital Equipment Co., Ltd. (China) (Model JC2000A) to investigate the surface wettability. Antifouling Properties of SSHF-MFs. The mass-transfer property of SSHF-MFs was characterized based on pure water flux (Jw1). The filtration test module was referenced in our previous work.11 The value of Jw1 was obtained after stable operation at 0.1 MPa for 30 min. The calculation method is described by eq 1:

Jw1 =

Q A × t × ΔP

(1)

Herein, Q represents the volume of permeate (given in liters), A represents the effective outer surface area (in units of m2), t represents the collecting time (given in seconds), and ΔP represents the transmembrane pressure (ΔP = 0.1 MPa). Antifouling properties of SSHF-MFs were evaluated through the separation and recovery experiments of three types of common model foulant: pump oil, SA, and BSA. The concentration of SA and BSA feed solutions were both 300 ppm. For a pump oil system, a high concentration (5000 ppm) of oil-in-water emulsion was prepared as follows. 2.5 g of pump oil and 0.1 g of SDS were added into 500 mL of distilled water. The mixture was blended through a high-speed stirrer (Gong Yi Yu Hua Instrument Co., Ltd., China) for 4 h to form a stable oil-in-water emulsion. The resultant emulsion was used within 24 h. The droplet sizes of emulsion were measured using equipment made by Malvern Instruments (U.K.) (Mastersizer 3000). To be specific, the permeate flux of SA and BSA solutions were measured every 10 min under a pressure of 0.1 MPa and the stable permeate flux (Jp) was obtained after 1 h of filtration testing. The membranes were subsequently washed with DI water and 5‰ NaOH solution for SA- and BSA-polluted membranes for 30 min, respectively. The pure water flux (Jw2) of the cleaned membranes were obtained after a stable operation at 0.1 MPa for 30 min. Similarly, the Jp value of the oil-inwater emulsion was measured every 10 min, not under a pressure of 0.1 MPa but at 0.05 MPa in case of oil droplet transformation. The membranes were washed with DI water for 30 min after the emulsion filtration test. The Jw2 value of the cleaned membrane was obtained after stable operation at 0.05 MPa for 30 min. Thre flux recovery ratio

EXPERIMENTAL SECTION

Materials. BSA, SA, and vacuum pump oil were supplied by Shanghai Lianguan Biochemical Engineering Co., Ltd., Sinopharm Chemical Reagent Co., Ltd. and Shanghai VACDO Vacuum Equipment Co., Ltd., respectively. TiO2 particles (nominal particle size: 25 nm) were provided by Xuan Cheng Jing Rui New Material Co., Ltd. Polystyrene microspheres (PS, nominal particle size: 100 nm) were provided by Suzhou SmartyNano Technology Co., Ltd. Surfactant sodium dodecyl sulfate (SDS), piperazine (PIP), ethylenediamine, and dichloromethane (CH2Cl2, DCM) were provided by Sinopharm Chemical Reagent Co., Ltd. Polyethylenimine (PEI) was provided by Aladdin. Deionized (DI) water was made in our own laboratory. Preparation of SSHFs and SSHF-MFs. SSHF Supports. The preparation technique for SSHFs was referenced in our previous work.25 In brief, polyacrylonitrile (PAN) and polyvinylpyrrolidone (PVP) first mixed in N,N-dimethylacetamide (DMAc) and then SSP were added to form the uniform casting solution with an SSP:PAN:DMAc:PVP mass ratio of 80:3.2:16.6:0.2. Then, the suspension was poured into a tubular vessel and vacuum-degassed 10284

DOI: 10.1021/acssuschemeng.7b02300 ACS Sustainable Chem. Eng. 2017, 5, 10283−10289

Research Article

ACS Sustainable Chemistry & Engineering (FRR) and decay ratio (DR) were used to evaluate the antifouling properties of SSHF-MFs. The calculation methods of FRR and DR are shown in eqs 2 and 3, respectively.

FRR =

DR =

Jw2 Jw1

(2)

Jw1 − Jp Jw1

(3)

The concentrations of pump oil, SA, and BSA were determined using ultraviolet−visible light (UV-vis) absorbance (Model UV-1800, Shimadzu, Japan) at wavelengths of 290, 220, and 280 nm, respectively. The rejection (R) was obtained using eq 4:

R=

Figure 2. SEM images of SSHFs and SSHF-MF1: (A) surface of SSHF, (B) cross section of SSHF, (C) pore size distribution of SSHF, (D) surface of SSHF-MF1, (E) cross section of SSHF-MF1, and (F) pore size distribution of SSHF-MF1.

CF − Cp CF

(4)

Herein, CF and CP were the concentrations of the feed and the permeate, respectively.

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to a high Jw1 value of pristine HF. The surface of SSHF-MF1 was continuous and the thickness of TiO2 layer was ∼3 μm. Some fundamental properties of SSHFs and SSHF-MF1 are summarized in Table 1. In particular, the tensile strength of SSHF-MF1 was more than two times larger than that of SSHFs. To verify the effect of PIP, a comparative experiment was performed. Figure 3 shows SEM images of SSHFs and SSHF-MF1 with different coating suspensions. Figures 3A and 3B are magnified images of the pristine SSHFs. The surfaces of metal crystals were smooth, and the crystal boundary was well-defined. Figures 3C and 3D are magnified images of the SSHF-MF0, whose coating suspension was missing PIP. It can be seen that TiO2 particles stuck to the crystal surfaces, rather than forming a continuous layer. The crystal boundary was still distinct. Figures 3E and 3F are magnified images of the SSHF-MF1, whose coating suspension consists of PIP. It can be found that most of the surface area was continuous and some large particles were still visible, and there were no obvious defects on the surface. A photograph of SSHF, SSHF-MF0, and SSHFMF1 is provided as Figure S1 in the Supporting Information. The appearances of the SSHF and SSHF-MF0 were similar. However, SSHF-MF1 showed a distinguished appearance. In short, both figures demonstrated the positive effect of PIP. Figure 4 shows the ATR-FTIR spectrum of PIP solution (spectrum A) and a TiO2 suspension containing PIP (spectrum B). The peak of spectrum A at 3414 cm−1 corresponded to OH stretching vibrations in water. After the addition TiO2 into the PIP solution, the OH vibration band broadened inhomogeneously and the peak offset to 3421 cm−1 in spectrum B was due to the hydrogen bonds between PIP molecules and TiO2 agglomerations, which affected the transition frequency of the individual OH stretching vibrations.26 The peak of spectrum A at 1560 cm−1 corresponded to N−H deformation vibrations, which were usually weak.28,29 In spectrum B, the weak N−H deformation vibrations were covered by the strong peak at 1642 cm−1, which was due to the offset of the vibration band. The change of O−H and N−H vibrations demonstrated the hypothesis presented in Figure 1. To further confirm the universal effect of hydrogen bonds, different additives (PEI and ethylenediamine) that could form hydrogen bonds with surface hydroxyl groups were investigated. Figure 5 shows SEM images of SSHF-MF2 and SSHFMF3, whose coating suspensions contained different additives. It can be seen that most of the surface areas of the two

RESULTS AND DISCUSSION Characterization of SSHF-MFs. It is well-known that nanoparticles in suspension have a tendency to agglomerate, because of their large surface energy. The agglomeration segments were always isolated with others. These segments were unable to form a continuous layer on the rough surface directly via a dip-coating process. Accidentally, we found that the addition of PIP in suspension had a beneficial effect on the formation of a continuous layer. The possible function mechanism is illustrated in Figure 1.

Figure 1. Schematic diagram of function mechanism of hydrogen bondsbetween PIP and TiO2 particles.

The secondary diamines of PIP formed hydrogen bonds (blue dotted line) with the surface hydroxyl groups of TiO2. These hydrogen bonds connected the isolated segments, forming a random and fluctuating three-dimensional network in suspension, which were analogous to the network in water.26 The mutual connecting segments were easily coated on the rough surface of pristine SSHF. In our previous report, the positive effect of PIP has been demonstrated in the zeolite seeds dispersion aspect.27 Therefore, with the assistance of PIP, a continuous TiO2 layer could be formed only through a dipcoating method. The following experiments demonstrated the function mechanism of hydrogen bonds. The morphology and pore size of SSHFs and SSHF-MF1 are shown in Figure 2. It could be seen that the pristine HF exhibited a rough surface and a large pore size. Large areas of fingerlike regions gave rise 10285

DOI: 10.1021/acssuschemeng.7b02300 ACS Sustainable Chem. Eng. 2017, 5, 10283−10289

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ACS Sustainable Chemistry & Engineering Table 1. Summary of the Fundamental Properties of SSHFs and SSHF-MF1 membrane

mean pore size (μm)

contact angle (deg)

tensile strength (MPa)

pure water flux (L/(m2 h bar))

N2 permeance (× 10−5 mol/(m2 s Pa))

SSHF SSHF-MF1

1.43 ± 0.27 0.24 ± 0.05

18 ± 2

20 ± 3 53 ± 4

1900 ± 300 680 ± 97

32.0 ± 3.8 6.1 ± 1.1

Figure 5. (A, C) SEM images of SSHF-MF2 (panel (A) shows the surface, panel (C) shows the cross section) and (B, D) SSHF-MF3 (panel (B) shows the surface, panel (D) shows the cross section).

Figure 3. SEM images of SSHFs, SSHF-MF0, and SSHF-MF1: (A and B) surfaces of SSHFs, (C and D) surfaces of SSHF-MF0, and (E and F) surfaces of SSHF-MF1.

Figure 6. Photographs of the entire process of underwater−oil contact angle measurement.

Oil/Water Emulsion Antifouling Property and Separation Performance of SSHF-MFs. In the oil/water separation process, a water film that forms on the membrane surface prevented direct contact between the oil droplet and the membrane surface. Generally, membranes with superhydrophilic and underwater superoleophobicity characteristics are propitious to mitigate the membrane fouling phenomenon and maintain a high oil/water emulsion separation efficiency.4 Therefore, SSFH-MF1 could be applied to oil/water separation, because of its aforementioned superior wettability. Figure 7 shows the pore size distribution of a pump-oil-in-water emulsion and a photograph of the emulsion and permeate. The oil-in-water emulsion belonged to the microemulsion system. The permeate became transparent after the separation test, which was indicative of a good separation efficiency for the oil-in-water emulsion.

Figure 4. ATR-FTIR spectra of PIP solution (spectrum A) and TiO2 suspension with PIP (spectrum B).

membranes were continuous, proving that the hydrogen bonds were in favor of the formation of continuous layers. The water contact angle and underwater−oil contact process are shown in Figure S2 in the Supporting Information and Figure 6. Figure S2 shows that the initial water contact angle was 18° and the water droplet disappeared within 5 s. Figure 6 shows the low oil adhesion of SSHF-MF1. The oil (DCM) droplet approached the surface and was compressed to skew the needle. When the needle gradually lifted up, the oil droplet detached from the surface without oil adhesion. Both results revealed the properties of superhydrophilic and underwater superoleophobicity, which enabled the antifouling property of SSHF-MF1. 10286

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ACS Sustainable Chemistry & Engineering

80% in three cycles. Two possible reasons could account for the high flux decay in filtration process: (i) the absorption of BSA enhanced the concentration polarization, and (ii) small BSA molecules were stuck in some

were conducted to verify its antifouling property for the separation high concentration of oil in water emulsion. SSHFMF1 exhibited a significant rejection (99%) for oil in the entire test process. FRR was >90% in the first cycle, indicating a good flux recovery property. In the following two cycles, FRR reached values up to 99%, meaning an almost full recovery of flux. The oil droplets deposited on the membrane surface were washed away easily, resulting in the high FRR. The DR values in three cycles were 90% for three cycles. For the SA solution, SSHF-MFs showed a high flux of 305 L/(m2 h) and a good rejection of 90% after three cycles. The flux recovery ratio reached up to 95% after three cycles. For the BSA solution, SSHF-MFs showed a flux of 73 L/ (m2 h) and a rejection of 91% after three cycles. In summary, SSHF-MFs displayed excellent antifouling properties and separation performance for nonadsorption solutions. Moreover, SSHF-MFs also displayed superior separation performance and good antifouling property for adsorption solutions (BSA) on the premise of washing with dilute alkaline solution.

Figure 10. (Left) Time-dependent flux and rejection of SSHF-MF1 in the BSA filtration process. Each cycle contains four steps: pure water flux of fresh membrane, BSA solution separation, 5‰ NaOH solution cleaning for 30 min (not shown), and pure water flux of refreshed membrane. (Operating pressure = 0.1 MPa, concentration of the BSA solution = 300 ppm.) (Right) Graph showing the changes in the DR and FRR values for different cycles.

pores and blocked some channels. To further determine the effect of BSA adsorption, long-term running operation for BSA solution was conducted, as shown in Figure 11. After three days

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.7b02300. Photograph of SSHF, SSHF-MF0, and SSHF-MF1; photographs of the entire process of water contact angle measurement; particle size distribution of PS microspheres (PDF)

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AUTHOR INFORMATION

Corresponding Author

Figure 11. Time-dependent flux and rejection of SSHF-MF1 in a BSA long-term filtration process. Inset image represents the variation of flux and rejection in the first 6 h.

*Tel.: 86-21-64253670. Fax: 86-21-64252989. E-mail: [email protected]. ORCID

of operation, SSHF-MF1 reached a steady state with the flux and rejection (60 L/(m2 h) and 75%, respectively). In the first 6 h, the rejection of BSA was ∼90% and the flux decreased gradually. In this period, the adsorption of BSA was the key factor to affect its separation performance. After 18 h of operation, the rejection had an obvious decline, which may be induced by the diffusion of BSA molecules across the channel under the pressure. Meanwhile, the adsorption of BSA was also close to the saturation state. After another 12 h, the adsorption process eventually reached the saturation state with a flux fluctuation of ∼60 L/(m2 h) in the following time. However, the diffusion of BSA molecules reached a steady state after 66 h of operation. After that period, the rejection also maintained a value of 75%. In other words, for the BSA separation process, the adsorption and diffusion of BSA molecules determined the ultimate separation performance. In terms of the performance in the first 6 h, SSHF-MFs were qualified for the separation of BSA, with a flux and rejection of 93 L/(m2 h) and 88%, respectively. However, with the prolonged operation time, the separation performance degraded. Fortunately, the separation performance could recover to a great extent with dilute alkaline solution washing.

Zhen-Liang Xu: 0000-0002-1436-4927 Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS The authors are thankful for the financial support received from the National Natural Science Foundation of China (Nos. 20076009, 21176067, 21276075, and 21406060), Project of National Energy Administration of China (Nos. 2011-1635 and 2013-117), and the Open Project of State Key Laboratory of Chemical Engineering (No. SKL-ChE-14C03).

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CONCLUSION Novel superhydrophilic and underwater superoleophobic stainless steel hollow fiber microfiltration membranes (SSHFMFs) were prepared successfully via a facile dip-coating method, followed by sintering at a low temperature (500 10288

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Research Article

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DOI: 10.1021/acssuschemeng.7b02300 ACS Sustainable Chem. Eng. 2017, 5, 10283−10289