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Frontiers of Environmental Science & Engineering

ISSN 2095-2201

ISSN 2095-221X(Online)

CN 10-1013/X

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Front. Environ. Sci. Eng.    2016, Vol. 10 Issue (4) : 12    https://doi.org/10.1007/s11783-016-0855-9
RESEARCH ARTICLE
Effect of protein on PVDF ultrafiltration membrane fouling behavior under different pH conditions: interface adhesion force and XDLVO theory analysis
Xudong WANG1,Miao ZHOU1,Xiaorong MENG1,2,Lei WANG1,*(),Danxi HUANG1
1. School of Environmental and Municipal Engineering, Xi’an University of Architecture and Technology, Xi’an 710055, China
2. School of Science, Xi’an University of Architecture and Technology, Xi’an 710055, China
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Abstract

pH values of the BSA solution significantly impact the process of membrane fouling.

Dramatic flux decline is caused by membrane–BSA adhesion force at start of filtration.

XDLVO theory shows the polar or Lewis acid–base interaction plays a major role in membrane fouling.

To further determine the fouling behavior of bovine serum albumin (BSA) on different hydrophilic PVDF ultrafiltration (UF) membranes over a range of pH values, self-made atomic force microscopy (AFM) colloidal probes were used to detect the adhesion forces of membrane–BSA and BSA–BSA, respectively. Results showed that the membrane–BSA adhesion interaction was stronger than the BSA–BSA adhesion interaction, and the adhesion force between BSA–BSA-fouled PVDF/PVA membranes was similar to that between BSA–BSA-fouled PVDF/PVP membranes, which indicated that the fouling was mainly caused by the adhesion interaction between membrane and BSA. At the same pH condition, the PVDF/PVA membrane–BSA adhesion force was smaller than that of PVDF/PVP membrane–BSA, which illustrated that the more hydrophilic the membrane was, the better antifouling ability it had. The extended Derjaguin–Landau–Verwey–Overbeek (XDLVO) theory predicts that the polar or Lewis acid–base (AB) interaction played a dominant role in the interfacial free energy of membrane–BSA and BSA–BSA that can be affected by pH. For the same membrane, the pH values of a BSA solution can have a significant impact on the process of membrane fouling by changing the AB component of free energy.
Keywords PVDF membrane      Membrane fouling      Adhesion force      Protein      Interfacial free energy     
Corresponding Author(s): Lei WANG   
Online First Date: 08 July 2016    Issue Date: 24 August 2016
 Cite this article:   
Xudong WANG,Miao ZHOU,Xiaorong MENG, et al. Effect of protein on PVDF ultrafiltration membrane fouling behavior under different pH conditions: interface adhesion force and XDLVO theory analysis[J]. Front. Environ. Sci. Eng., 2016, 10(4): 12.
 URL:  
https://academic.hep.com.cn/fese/EN/10.1007/s11783-016-0855-9
https://academic.hep.com.cn/fese/EN/Y2016/V10/I4/12
compositions/% PVDF/PVA PVDF/PVP
PVDF 17 17
PVA 3 0
PVP 0 3
PEG 3 0
LiCl 3 3
DMAc 74 77
Tab.1   Compositions of different casting solution
γ l + γ i − γ   L W γ   A B γ   T O T
Ultrapure water 25.5 25.5 21.8 51.0 72.8
Diiodomethane 0.0 0.0 50.8 0.0 50.8
Glycerol 3.9 57.4 34.0 30.0 64.0
Tab.2  Surface tension properties (mJ·m-2) of probe liquids at 20℃
Fig.1  FTIR spectra of PVDF/PVA and PVDF/PVP membranes
types PVDF/PVA PVDF/PVP
BSA rejection/% 89.2 78.5
porosity/% 62.9 78.5
mean pore size/nm 46.8 43.6
contact angle/(º) 62.7 69.8
flux/LMH 258.6 308.8
Tab.3   PVDF UF membrane structure parameters
Fig.2  Effect of BSA solution pH on zeta potential and particle size
Fig.3  Flux decline in BSA ultrafiltration at different pHs (a) is for PVDF/PVA, (b) is for PVDF/PVP)
Fig.4  Adhesion forces of PVDF/PVA membrane-BSA (a) and BSA-BSA (b)
Fig.5  Adhesion forces of PVDF/PVP membrane-BSA (a) and BSA-BSA (b)
Fig.6  The surface SEM images of membranes fouled by BSA solutions (Experimental conditions: test temperature, room temperature; Filtration time: 2 h)
Fig.7  The 3-dimensional AFM images of BSA fouled membranes (Experimental conditions: test temperature, room temperature; Filtration time: 2 h)
Types pH qW/(°) qD/(°) qG/(°) γ l + γ i − γ   A B γ   L W γ   T O T
PVDF/PVA 3 67.21 (±0.15) 42.05 (±0.11) 50.76 (±0.31) 0.23 25.70 4.86 34.16 39.02
4.7 67.70 (±0.37) 46.30(±0.52) 57.93(±0.55) 0.69 13.91 6.20 36.70 42.90
9 62.72 (±0.29) 43.54 (±0.17) 51.75 (±0.16) 1.31 11.63 7.81 39.79 47.60
PVDF/PVP 3 84.40 (±0.35) 47.80 (±0.24) 59.10 (±0.18) 0.65 7.84 4.51 30.51 35.02
4.7 80.77 (±0.51) 60.91 (±0.67) 69.42 (±0.12) 0.91 6.81 4.98 28.58 33.56
9 73.91 (±0.27) 52.82 (±0.26) 63.00 (±0.57) 0.96 10.50 6.35 33.74 40.09
BSA 3 76.59 (±0.29) 37.16 (±0.31) 66.95 (±0.15) 0.07 7.09 1.41 40.96 42.37
4.7 77.16 (±0.24) 37.56 (±0.18) 67.41 (±0.28) 0.06 7.08 1.30 42.20 43.50
9 72.43 (±0.13) 34.17 (±0.25) 65.64 (±0.34) 0.02 10.60 0.92 40.83 41.75
Tab.4  The contact angles, surface tension components and parameters (mJ·m–2) of membrane and BSA
membranes pH Δ G m l f L W Δ G m l f A B Δ G m l f A D Δ G f l f L W Δ G f l f A B Δ G f l f c o
PVDF/PVA 3 –5.09 –32.90 –37.99 –4.16 –20.91 –25.07
4.7 –5.29 –37.91 –43.20 –4.91 –22.81 –27.72
9 –4.24 –28.27 –32.51 –1.69 –19.64 –21.33
PVDF/PVP 3 –2.49 –43.13 –45. 62 –2.67 –23.21 –25.88
4.7 –4.43 –53.40 –57.83 –3.44 –23.13 –26.57
9 –2.92 –36.19 –39.11 –2.68 –20.23 –22.91
Tab.5  PVDF UF membranes-BSA interfacial free energies of adhesion and BSA-BSA interfacial free energies of adhesion (mJ·m–2)
J water flux (L·m-2·h -1)
J0 pure water flux (L·m-2·h -1)
q contact angle (deg)
qw contact angle measured by ultrapure water (deg)
qD contact angle measured by diiodomethane (deg)
qG contact angle measured by glycerol (deg)
LW Lifshitz–van der Waals interactions
AB polar or Lewis acid–base interactions
EL electrostatic double layer interactions
ΔG  LW LW component of free energy (mJ·m-2)
ΔG  AB AB component of free energy (mJ·m-2)
ΔG  EL EL component of free energy (mJ·m-2)
γ  LW LW component of surface tension (mJ·m-2)
γl+ electron acceptor component of surface tension (mJ·m-2)
γi− electron donor component of surface tension (mJ·m-2)
γ  TOT total component of surface tension (mJ·m-2)
ΔGmlfAD membrane–BSA interfacial free energy of adhesion (mJ·m-2)
ΔGflfCO BSA–BSA interfacial free energy of adhesion (mJ·m-2)
Tab.1  
m membrane
l liquid environment
f foulant
Tab.1  
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