Surface modification techniques of membranes to improve their antifouling characteristics: recent advancements and developments
Muhammad Tawalbeh1,2, Haya Aljaghoub2,3, Muhammad Qasim4,5, Amani Al-Othman4()
1. Sustainable and Renewable Energy Engineering Department, University of Sharjah, Sharjah 27272, United Arab Emirates 2. Sustainable Energy & Power Systems Research Centre, RISE, University of Sharjah, Sharjah 27272, United Arab Emirates 3. Industrial Engineering and Engineering Management Department, University of Sharjah, Sharjah 27272, United Arab Emirates 4. Department of Chemical and Biological Engineering, American University of Sharjah, Sharjah 26666, United Arab Emirates 5. Materials Science and Engineering Program, College of Arts and Sciences, American University of Sharjah, Sharjah 26666, United Arab Emirates
Extensive research efforts are currently devoted to developing and improving conventional technologies for water treatment. Membrane-based water treatment technologies are among the most preferred options due to their commercial success, simple operation, low energy and space requirements, and high separation efficiency. Despite the advances made in membrane-based technologies, fouling remains a critical challenge. Fouling occurs upon the accumulation of unwanted impurities on the membrane surface and within the membrane pores which results in a significant decline in the membrane permeate flux. To alleviate the operational challenges from fouling, surface modification to develop antifouling membranes appears to be an effective technique. A comprehensive review of the surface modification techniques for the development of antifouling membranes is provided in this paper. Chemical surface modification techniques (grafting and plasma treatment), physical modification techniques (blending, coating, adsorption, and thermal treatment), and combined physical and chemical modification techniques have been discussed. Moreover, the challenges related to surface modification and the future research directions are addressed.
. [J]. Frontiers of Chemical Science and Engineering, 2023, 17(12): 1837-1865.
Muhammad Tawalbeh, Haya Aljaghoub, Muhammad Qasim, Amani Al-Othman. Surface modification techniques of membranes to improve their antifouling characteristics: recent advancements and developments. Front. Chem. Sci. Eng., 2023, 17(12): 1837-1865.
Upon surface modification, the hydrophilicities of the membranes significantly increased. Moreover, the water fluxes of the membranes significantly improved by 22.45% in comparison to the original membranes. The salt rejection also increased from 95.44% to 98.53%. As a result, grafting enhanced the antifouling properties of the membranes.
[64]
Surface initiated atom transfer radical polymerization
PVDF UF membrane
PSBMA
Porosity: 0.75%, 30 min reaction time
This study discussed the thickness of the brush layer upon grafting the membranes. The results suggested that a thicker brush layer reduces the membrane fouling significantly. On the other hand, the thick layer allowed for a small enhancement in the flux recovery. This drawback was due to internal fouling, which could be inhibited by grafting the surface as well as the internal part of the membrane.
Acrylic acid (AA) and 2-hydroxyethyl methacrylate and PDA and ethylene diamine (EDA) were employed to modify the membrane
WCA: 74°, FRR: 46%, Jw: 231 kg·m–2·h–1, with 6 wt % AA
The UV photo-grafting of hydrophilic monomers to the membranes increased the membrane hydrophilicities, decreased the pure water flux, and somewhat increased the permeability of milk water and the ability to reject protein. As a result, the membrane antifouling abilities and flux recovery were enhanced.
[69]
Surface-initiated radical graft copolymerization
PVDF membrane
PEG methacrylate
WCA: 68° with grafting weight: 0.2 mg·cm–2
Membrane adsorption of protein depends on the hydrophilicity and hydration of the membranes, as well as the grafted layers’ structures on the surface.
[103]
Ugi four-component reaction
PA RO membrane
MPEG aldehyde (MPEG-CHO), and an amino-terminated antibacterial component, tris(2-aminoethyl)amine or sulfamethoxazole
WCA: 41.5°, R: > 99%, Jw: 40 L·m–2·h–1
Followed by the membrane grafting, the membrane surface roughness reduced, while the hydrophilicity increased. Additionally, upon fouling, the modified membranes attained high flux recovery and low flux attenuation ratios. Thus, the surface modified membranes exhibited improved antifouling and antibacterial properties.
[71]
Graft polymerization
PES hollow fiber membrane
Acrylamide and Ag nanoparticles
WCA: ~0°, Jw: ~220 L·m–2·h–1·atm–1 at 1 mg·cm?2 grafting at contact angle less than 40° with grafting at contact angle less with grafting weight: 10 mg·cm–2
Membrane grafting could increase hydrophilicity, which ultimately enhances membrane antifouling properties. The incorporated Ag nanoparticles enhanced the antibacterial properties of the membranes.
[90]
Self-polymerization
PA RO membrane
Epoxy group in 2,3-epoxypropyl trimethyl ammonium chloride
Jw: 55.6 L·m–2·h–1, R: 99.25% with tris(dimethylaminomethyl)-phenol content 0.5% (wt/v), 2,3-epoxypropyl trimethyl ammonium chloride content: 5% (wt/v), preserving time = 5 d
Surface modification achieves the dual goal of reducing the pore size with polymerization and improving the antifouling properties through the phenomena of electric repulsion.
[77]
SI-ATRP
NF membrane
PDA and SBMA monomers
WCA: 18.4°, Jw: 7.6 L·m–2·h–1·bar–1
The modified membranes in this study exhibited improved hydrophilicity, reduced negative electric charge, and deflated pore sizes. The modified membranes retained about 99.1% and 80.7% of the filtered salts. Moreover, the modified membranes achieved a reduction in the permeability of about 10%. Additionally, the membranes reached a 92.1% flux recovery during filtration and enhanced anti-biofouling with a reduction of 86.1% of the bacteria stuck on the membrane surface.
[78]
Acylation reaction
Fluorinated polyacrylonitrile (PAN) membrane
Perfluoroalkyl groups
WCA: 83.1°, FRR: 60%, Jw: 140 L·m–2·h–1 with hydrolysis time: 2 h, animation time: 3 h, fluorination time: 2 h
Grafting perfluoroalkyl on the membrane surfaces enhances the antifouling properties of the membranes, increases the flux recovery ratio to about 99%, and decreases the flux decline ratio to 13% (the lowest percentage).
Grafting the membranes increased the hydrophilicities of the membranes, which in return enhanced the antifouling properties of the membranes and increased their water flux.
[68]
Silanization process
Alumina membrane
Organosilane
FRR: 82% with organosilane with methyl group
The modified membranes presented in this study showed a small reduction in pore size, enhanced flux recovery, and reduced flux decline, while simultaneously achieving lower membrane fouling.
[104]
Photo-induced graft polymerization method
PES membrane
PEG-amide binary monomer
–
Incorporating mixed monomers to graft membranes further lowers fouling than incorporating individual monomers. Additionally, grafting the membranes decreases the membrane pore sizes and increases the water permeability.
[79]
In situ chemical reactions
Polyimide membrane
Ag particle
WCA: 97.7°
This study investigated the addition of Ag particles to impart antifouling behavior.
[70]
Chemical grafting method
Hollow fiber membrane
PVP-GO nanocomposite
Porosity: 62.5%, WCA: 72°, Jw: ~250 L·m–2·h–1
After chemically grafting the membrane with PVP-GO nanocomposites, the hydrophilicity of the membrane was enhanced. The contact angle of the modified membrane was reduced by 35°. Moreover, the water permeability and flux recovery rate of the membrane improved by 1.7 times and 96%, respectively, after the surface modification. The grafting technique enhanced the removal of contaminants by more than 97.8%, NH4-N+ by more than 93.1%, and NO3-N by more than 68.7% in comparison to the unmodified membrane.
Zwitterionic hyperbranched PEI moieties were grafted onto the membrane. It was noticed that the membrane attained greater hydrophilicity. Moreover, the modifiers improved the membrane’s water permeability by 11.6% in comparison to the original membrane. Furthermore, the modified membrane attained better ion rejection selectivity. The grafted zwitterionic hyperbranched PEI moieties increased the flux recovery and lowered the flux decline. These properties improved the antifouling behavior of the membrane.
[105]
LbL-IP method
PA TFC membranes
Sulfonamide monomers 4-aminobenzene sulfonamide (4-ABSA) and 2-aminoethanesulfo-namide (2-AESA)
WCA: 42.5°, Jw: 3.85 L·m–2·h–1·atm–1, R: 99.4%
Two membranes were chemically modified and compared them to a pristine membrane. It was reported that the modified membranes were associated with higher water fluxes than the pristine membrane by 50.8% and 59.1%. In addition to that, the membranes acquired an NaCl rejection rate of more than 99.25%. Most importantly, the surface modification of the membranes enhanced their hydrophilicities and lowered their surface roughness. Consequently, the membranes attained better antifouling properties. These properties enabled the modified membranes to attain high chlorine resistance.
[106]
One-step graft copolymerization and surface functionalization
Grafting the membrane with zwitterions enhanced its hydrophilicity, rejection rate of BSA, and antimicrobial properties. The permeability of water was positively influenced by the thickness of the zwitterionic microgel layer, solution temperature, and pressure. The water permeability of the modified membrane was enhanced due to the enhancements induced in its flux recovery rate, gating ratio, and antifouling performance.
PVDF-HFP membrane was chemically grafted a to enhance the antifouling performance. The water flux and the salt rejection of the grafted membrane increased by 36% and 99.99%, respectively. Hence, the grafted membrane was deemed suitable for desalinating saline water.
Hydrophilic and hydrophobic substrate layers were compared. The hydrophilic substrate reduced the resistance to moisture transfer. On the other hand, the hydrophobic layer lowered the surface energy and enhanced the surface roughness. As a result, it increased the pressure upon entering the membrane and resisted the entrance of water into the pores. The hydrophobic layer repelled water from entering and created a disparity between the membrane surface and water, which mitigated the accumulation of foulants.
[108]
In situ grafting
PSf
GO/Pt nanoparticle
WCA: 56°
Increased hydrophilicity and biofouling resistance. Membrane with 0.75 wt % GO/Pt GO particles had the best performance in terms of nitrate rejection and water flux.
[91]
Two-step grafting method
TFC RO membrane
PEI grafting followed by zwitterionic modification
Increased hydrophilicity, good performance against both charged and electroneutral foulants
[92]
Grafting polymerization
PEI NF membrane
Quaternized bipyridine monomer
WCA: 72.7°, Jw: 96.6 L·m–2·h–1, R: 92% MgCl2
Water flux increased by 2.8 times higher water flux compared to the pristine membrane. Antifouling properties were enhanced, and antibacterial properties were imparted with long-term operational stability
The usage of covalent bonding to reduce membrane fouling. The modified membranes acquired a pure water flux of 764?L·m–2·h–1, and a flux recovery ratio of 83%. Additionally, the fouling resistance of the membranes significantly improved.
[95]
Covalent bonding
PA-TFC RO membrane
Polypeptide, ε-poly-l-lysine (PL)
Jw: 48.7 L·m–2·h–1, R: 98.7% with 0.1% PL
The surface modification led to an increase in the membrane hydrophilicity. This in return lowered membrane fouling and achieved a salt rejection more than 99.5%.
[96]
Covalent bonding
PDA composite membrane
GO
Jw: 100 L·m–2·h–1·MPa–1, R: 90% for chromotropic acid disodium
Upon modifying the membrane surface, the reduction in the flux decreased from 36% to 19%, followed by fouling. Moreover, the water permeation improved from (56.3 ± 18.2) to (103.7 ± 12.0) L·m–2·h–1·MPa–1. Hence, the membranes attained enhanced antifouling properties, with a fouling reversibility of 18%. While the original membranes acquired a fouling reversibility of less than 1%.
[97]
Covalent bonding
PVDF UF membrane
COF-PAA modifier
Jw: 95 L·m–2·h–1, FRR: 95%, WCA: 55°
After modification, the water flux of the membrane increased to around 95?L·m–2·h–1. Additionally, the rejection rates of BSA and sodium alginate increased. Moreover, the contact angle of the modified membrane decreased by 55°. As a result, the modifiers enabled the membrane to acquire superior fouling resistance and stability. These enhancements are attributed to the pore size reduction after the surface modification.
The relation between the pure water flux and the time to plasma treat the membranes were investigated. The findings indicated that upon increasing the treatment time, the water flux increased, however, the enhancement stopped when the time reached 120 s. It was also observed throughout this study that the flux recovery of the treated membranes was higher than the untreated membranes.
[118]
AA
PA layer of thin film nanocomposite membrane
The treated membranes demonstrated higher salt rejection while simultaneously keeping consistent pure water flux. Moreover, the results showed that the modified membrane enhanced its fouling resistance by attaining a flux recovery rate of more than 95%, while the original membranes only attained a flux recovery rate of about 85.8%. The high flux recovery rate is due to the improved hydrophilicity of the membranes and a decrease in surface roughness.
[113]
Ar
Polypropylene hollow fiber microporous membrane
The plasma treated membranes with Ar in comparison to the non-modified membranes achieved a higher flux recovery of 20%, higher flux ratio followed by fouling of 143%, and a lower flux reduction of 28.6%.
[111]
H2O
Polypropylene hollow fiber macroporous membrane
The relationship between the time of plasma treatment and the water flux is linear. Moreover, upon the H2O plasma treatment, the flux reduction further declined by 1.1%, the water flux recovery increased by 2%, and the flux ratio followed by fouling declined by 22%, in comparison to the non-modified membranes.
[117]
O2
Polypropylene hollow fiber microporous membrane
There is a linear relationship between the pure water flux and the time to plasma treat the membranes. However, this is only restricted to any time below 60 s. Similarly, the flux recovery and flux ratio were higher for the treated membranes.
[116]
N2
Polypropylene hollow fiber microporous membrane
The time for plasma treatment increases, the pure water flux increases accordingly. The flux recovery for the N2 treated membranes was higher by 62.9% after water cleaning and 67.8% after NaOH cleaning. The results also showed that upon plasma treatment, the antifouling behavior was weakened.
[119]
Zwitterionic nanoparticles
TFC membrane
This study discusses the enhancement of thin-film membrane’s biofouling and organic-fouling resistances after adding zwitterionic nanoparticles. Moreover, the nanoparticles increased the water permeability of the membrane and the salt rejection.
[114]
O2
TFC membrane
Hydrophilic groups were added on a polyethylene film via O2 plasma treatment to form the TFC membrane. The pure water flux of the plasma treated polyethylene TFC membrane improved by about 42%. Moreover, the membrane was able to reject Na2SO4 by 90.28%, MgSO4 by 81.77%, MgCl2 by 74.79%, and NaCl by 70.94%. Moreover, the treated membrane exhibited higher fouling resistance than the other membranes.
[115]
Ar
PVDF membrane
After treating the PVDF membrane, its contact angle decreased from 95.63° to 62.19°. Moreover, the water flux of the treated membrane increased to 151.98 L·m–2·h–1, the rejection rate was obtained as 90% and the fouling rate as 34.7%.
[120]
Tab.2
Blending materials/particles
Type of membrane
Inferences
Ref.
Ag and nanogel
Polymeric membrane
The usage of nanogels and Ag nanoparticles were proposed to improve the antifouling and hydrophilic properties of the membranes. Moreover, this resulted in enhancing the membrane’s water flux.
[122]
TiO2 nanoparticles
PVDF/sulfonated PES membrane
After adding the TiO2 nanoparticles, the membrane pore sizes were deflated, the hydrophilicities were improved, and the antifouling properties were enhanced.
Followed by blending, the contact angles and accumulated proteins were reduced. On the other hand, the antifouling properties and the water flux of the membranes were enhanced. Moreover, the hydrophilicities of the membranes significantly increased.
[121]
Sulfonic groups
Sulfonated PES membrane
After modifying the membranes, the water contact angles were significantly reduced, however, the water flux experienced a drastic enhancement. Moreover, the modified membranes attained increased hydrophilicities.
[127]
TiO2 nanoparticles
Hollow fiber PES membrane
After modification, the membranes’ pure water flux and pores sizes increased. However, flux recovery remained the same.
[128]
Mg(OH)2 nanoparticles
PVDF microfiltration (MF) membrane
Upon adding Mg(OH)2 nanoparticles onto the membrane surface, the OH improved the hydrophilicity of the membranes. Additionally, the modified membranes exhibited enhanced antifouling properties and lower flux reductions.
[125]
Hydrous manganese dioxide nanoparticles
PES UF membrane
After adding the nanoparticles, the membranes exhibited lower contact angles and higher porosities. On the other hand, the pore size deflated on the membrane’s surface. The nanoparticles led to an enhancement of the antifouling properties due to an increase in the flux recovery and hydrophilicity.
[129]
GO nanoplates
PES mixed matrix NF membrane
After blending the nanoparticles, the hydrophilicities of the membranes increased and led to an increase in the water flux. The results of this study indicated that a 0.5 wt % GO membrane achieved optimal anti-biofouling and antifouling properties. This was due to the increase in the pore size, water flux and porosity.
[130]
ZnO-DMF: nano-ZnO and PVP
PES UF membrane
Blending ZnO onto the membranes, produced bigger pore sizes, porosity, and density, in addition to an increase in the hydrophilicity and water flux of the membrane. The enhancement of the water flux was about 210% in comparison to the original membranes. Additionally, the addition of the ZnO particles enhanced the antifouling properties of the membranes and imparted thermal stability to the membranes.
[124]
Functionalized silica particles
PES UF membrane
Membrane modification achieved optimal antifouling properties and stabilized the water permeability.
[131]
Zwitterionic glycosyl
PES UF membrane
Upon membrane modification the membranes acquired improved antifouling properties and higher flux recovery ratios (about 100%).
[132]
Tannic acid coated boehmite
Nanocomposite membrane
Tannic acid coated boehmite blended membranes presented enhanced performance for the removal of Direct Red 16 and licorice dye. The removal level of Direct Red 16 and licorice dye surpassed 96% compared to the unmodified membrane. Furthermore, the modified membranes exhibited better antifouling properties than the unmodified membrane. Hence, tannic acid coated boehmite presented significant benefits for the membranes.
[133]
Polystyrene sulfonic acid (PSSA) functionalized ZWP ion exchanger and sulfonated PVDF (SPVDF)
Composite membrane
The PSSA and SPVDF were blended with the membrane to enhance the water permeability by 26%, methanol permeability by 22%, and mechanical and chemical stability. Furthermore, the blended membrane presented high-performance ion selectivity.
Sericin macromolecule
Cellulose acetate membrane
The main objective was to investigate the rejection levels of protein. The rejection levels of BSA increased to 96% after blending sericin onto the membrane surface.
[134]
Acrylamide grafted bentonite
PVC membrane
Flux and hydrophilicity were enhanced, and antifouling properties were observed. The best performance was reported with incorporation of 8 wt % acrylamide grafted bentonite. Flux recovery of 82.12% was reported.
[126]
Tab.3
Fig.4
Coating layer
Type of membrane
Inferences
Ref.
Thin chitosan film
PES NF membrane
The coated membranes are more hydrophilic and have higher surface roughness. Additionally, it showed that the membranes achieved higher water flux and reached an efficiency of 86% for removing manganese from the water. Additionally, the membranes attained better antibacterial and antifouling properties.
[141]
Nano Ag particles
RO membrane
The Ag-coating the membrane and the spacer results in better antifouling properties, leading to better biofouling control.
[152]
GO nanosheets
MF membrane
The coated membranes exhibit superior antifouling properties than uncoated membranes, and substantially decreased the energy utilization. Moreover, coated membranes are associated with high removal efficiency and water flux, and lower transmembrane pressure due to the newly attained antifouling properties.
[58]
GO and PDA
Anion exchange membrane
Surface modification of the membranes increased the membrane hydrophilicity and negative charge and decreased the surface roughness. Moreover, the modified membranes attained better antifouling properties and stability.
[142]
Sulfonated PVA
PA RO membrane
The coated membranes in this study achieved lower water fluxes and higher salt rejection of around 99.18%. Moreover, the modified membranes exhibited enhanced antifouling properties.
[150]
SiO2 sol-gel
Alumina membrane
The addition of the SiO2 to the membrane surface reduced the pore size and the water permeation. This addition eventually improved the fouling resistance.
[138]
Perfluorooctyl trichlorosilane containing SiO2 nanoparticles (for the hydrophobic membrane)-PVA hydrogel (for the hydrophilic membrane)
PVDF membrane
A comparative study between hydrophobic and hydrophilic membranes was carried out. Hydrophobic membranes demonstrated self-cleaning properties and antiwetting when faced with various foulants. Moreover, hydrophobic membranes presented fouling and wetting resistance. On the other hand, adding a hydrophilic layer onto the membrane surface showed resistance to fouling and wetting when faced with limited number of foulants.
[147]
GO coating
PAN fiber hierarchical-structured membrane
The added coating layer added hydrophilicity to the membranes, increased the water flux, and presented enhanced antifouling properties to the membranes. The high porosity of the membrane caused substantial increase in the water flux.
[143]
Trimethylaluminium
TFC PA membrane
The hydrophilicity of the membrane specifies the number of adhered bacteria on the membrane surface. Hence, the membrane with the highest hydrophilicity, attained the minimum number of adhered bacteria.
[146]
PDA coating
Polyester filter membrane
Surface modified membranes that attained high water fluxes, enhanced fouling resistance, and improved stability were displayed.
[149]
Bifunctional hydrogel coatings
PSF UF membrane
The hydrogel coated membranes acquired enhanced antifouling properties.
[153]
Polymeric coating
PES membrane
The addition of polymers onto the membrane surface added antifouling and antibacterial properties to the membranes and enhanced the membrane hydrophilicity.
[11]
Iron acetylacetonate
NF membrane
The coated layers on the NF membranes increased the hydrophilicity and the water permeability of the membranes. Furthermore, the surface modification enhanced the dye rejection by 99.6%.
[154]
Cellulose nanocrystals and tannic acid/PEI/V
PVDF membrane
The coated layer of cellulose nanocrystals enhanced the hydrophilicity and antifouling performance of the membranes. The coated layer inhibited the accumulation of oil and protein on the membrane surface. Moreover, the coated layer increased the water flux to more than 6000 L·m–2·h–1·bar–1 and flux recovery to 100%.
[155]
MOFs
?
The coated layer resulted in a more hydrophilic membrane with antifouling properties. Due to these enhancements, the coated membrane facilitated oil and water separation with high efficiency, more than 99.35%, and high flux, more than 12308 L·m–2·h–1. The coated membrane was able to remove oil in water emulsion efficiently. The coated layer presented the membrane with significant thermal and chemical stability. As a result, these benefits make MOFs coated membranes suitable for desalinating wastewater.
[145]
Epoxied SiO2 nanoparticles and PEI
PVDF membrane
The PVDF membrane was coated to enhance the fouling resistance, separation performance, and ion removal abilities. The coated layer enhanced the hydrophilicity of the membrane, improved the oil–water separation after retaining 98% of the oil, and increased the membrane’s flux recovery rate to 96.3%. Finally, the coated layer improved the filtering and rejecting performance of the membrane to heavy metal ions and organic dyes.
[144]
PDA
UF membrane
Membrane was more hydrophilic and retained 87% of the normal organic matter. Furthermore, pore size was enhanced resulting in higher permeability
[151]
Tab.4
Compounds for adsorption
Type of membrane
Inferences
Ref.
PVA
PES UF membrane
Strong correlation between the surface modification applied to the membranes and to the enhancement in the antifouling properties of the membranes. Similarly, as the fouling decreased, the flux recoveries of the membranes increased.
[158]
Zwitterionic copolymer
Polymer membrane
The modified membranes showed enhanced organic fouling and biofouling resistance. This enhancement was caused by more hydrophilic and less negatively charged surface.
[157]
Polyampholytic copolymer
UF membrane
The adsorption technique was utilized for modifying the membrane surface. Polyampholytic copolymers were adsorbed onto the membrane surface to present higher water flux, enhanced fouling resistance, and better stability than the unmodified and coated membranes.
[159]
Hydrophobic styrene
PVDF membrane
Membrane adsorption was facilitated in this study to reduce the water contact angle by 105.1° and the accumulation of protein on the membrane surface by 108.3 μg·cm–2. Moreover, the modified membrane achieved protein rejection more than 90%.
[160]
Tab.5
Fig.5
Type of membrane
Inferences
Ref.
Thin PAN membrane
The membrane was developed and modified via thermal treatment. The modified membrane’s water flux improved more than 30% in comparison to the non-modified membrane. Moreover, the membranes attained enhanced bacterial and fouling resistance. These advantages show that the modified membrane can be utilized for efficiently treating wastewater.
[163]
PES nanohybrid membrane
The thermal treatment enhances the hydrophilicities of the membranes and reduces their water contact angle by 13.84°. Furthermore, the modified membranes exhibited an enhancement in the water flux by 200%. Moreover, the modified membranes possessed better antifouling properties, such as higher water permeability and rejection rate. Due to these enhancements, the modified membrane can be employed for efficiently purifying biodiesel.
[164]
UF PSf membrane
The membrane was initially coated to enhance its antifouling properties. Subsequently, it was thermally treated for one week at 80 °C. The thermal treatment did not negatively influence the antifouling efficiency of the previously modified membrane. This indicates that the membrane can withstand high temperatures for extended periods of time without compromising its antifouling performance.
[165]
Tab.6
Surface modification method
Advantages
Disadvantages
Chemical methods
Grafting
? Control over structure and properties of the membrane
? Grafting efficiency can be low
? Grafting is classified as easy and simple
? Nanoparticles can be added
Plasma treatment
? Short reaction time
? High cost
? High reproducibility
? Vacuum is required
? Low environmental impact.
? Monitoring and control of the treatment time is necessary
Physical methods
Blending
? Low cost
? Low effectiveness
? Simple method
Coating
? Easy and simple
? Addition of resistive layer, which can affect permeability
Adsorption
? Easy and simple
? Leaching is possible
Tab.7
Antifouling techniques
Type of membrane
Inferences
Ref.
Grafting and blending
PVC membrane
The modified membranes acquired higher surface hydrophilicity than the original membranes, as well as enhanced permeation and fouling resistance. The optimal blending ratio was found to be 7 to 3.
[202]
Coating and thermal treatment
PA TFC RO membrane
The higher the coating solution is utilized, the higher the salt rejection and the lower the water flux become. The membranes acquired enhanced antifouling properties. In addition to that, the membrane loses reduced and flux recoveries increased after modification.
[206]
Coating and UV-LED polymerization
Commercial PES UF membrane
This study presented modified membranes with excellent antifouling properties that were acquired by testing the permeation of water with the addition of the foulant, humic acid.
[17]
Plasma treatment and coating
PSf composite UF membrane
The O2 treated membrane acquired higher hydrophilicity, foulant rejection rates (about 83%), and pure water flux (about 350.7 m2·h–1). Upon the addition of the metallic glass, further enhancements in the rejection rates occurred (98.6%–99.9%). On the other hand, the tungsten coating also led to high pure water flux and rejection rates, with excellent antifouling properties. These advantages were due to the enhancement in the hydrophilicity of the membranes and the strong electric negative charges.
[199]
Plasma treatment and grafting
Polymeric nanofiber membrane
It is suggested combining two techniques to modify the membranes’ surfaces. By applying grafting and plasma treatment, the membranes attained higher water permeation and better fouling resistance.
[203]
Grafting and blending
PES UF hybrid membrane
The addition of the N-halamine@HNTs led to an increase in the hydrophilicities of the modified membranes. If the addition mounted up to 1 wt %, then the water flux achieved was about 248.3 L·m–2·h–1. The addition of the N-halamine@HNTs also enabled the membranes to attain better antibacterial properties.
[207]
Grafting and blending
UF membrane
The modified membranes showed great permeability, increased flux, and enhanced rejection efficiency. While the original membranes presented stabilized the flux for long periods of time and achieved excellent fouling resistance.
[208]
Plasma treatment and surface-initiated atom transfer radical polymerization
MF membrane
The modified membranes attained excellent wetting properties and a significant reduction in the contact angle (121.6°–29°). Additionally, the modified membranes presented improved anti-protein fouling with 86% recovery ratio.
[209]
Initiated CVD and coating
RO membrane
The modified membranes experienced a maximum decrease in the permeability of 43%, with far enhanced fouling resistance.
[210]
Initiated CVD and coating
RO membrane
It is suggested that the foulant absorption to the membrane surface significantly decreased.
[211]
Initiated CVD and coating
PVDF hollow fiber membrane
The membrane hydrophilicity improved, the flux rejection
[212]
Surface adsorption and coating
Polymer membrane
The enhancement in the hydrophilicity and the reduction in the negative charges led to excellent biofouling and organic fouling resistances.
[157]
Coating and UV irradiation
RO membrane
The formation of TiO2 coat resulted in increased hydrophilicity of the membrane. Upon applying UV irradiation to the coated membranes, a noticeable increase in the water flux occurred. Moreover, the membranes acquired self-cleaning properties.
[201]
PDA coating and PD-g-PEG
PES UF membrane
Grafted membranes to fully coat the membranes were compared. The results suggested that the modified membranes acquired mechanical stability. However, the grafted membranes acquired better chemical stability. Both modified membranes possessed lower flux reductions and adsorption. As a result, the grafted membranes enhanced the membrane stability and adsorption.
[213]
Coating and grafting
PVDF membrane
The studied grafted membranes showed better anti-protein and antibacterial properties, especially against Staphylococcus aureus. Additionally, the membranes exhibited higher pure water flux.
[200]
UV irradiation and blending
PVDF UF membrane
The modified membrane produced high water flux ratios. This is due to the enhancement in the membrane’s hydrophilicity caused by the addition of the TiO2. As a result, the membrane showed enhanced antifouling properties and self-cleaning abilities.
[204]
UV irradiation and blending
PVDF membrane
The modified membrane attained super antifouling properties and significantly enhanced self-cleaning behaviors. These advantages are due to addition of TiO2 to the membrane surface.
[162]
Coating, grafting, and zwitterionization
PVDF membrane
High resistance to fouling by BSA and oil. Superhydrophilic and underwater superoleophobic properties were imparted.
[205]
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