membranes

Article
Preparation of Lateral Flow PVDF Membrane via Combined
Vapor- and Non-Solvent-Induced Phase Separation (V-NIPS)
Xiaoyun Wang 1,2,† , Dejian Chen 1,2,† , Ting He 1,2 , Yue Zhou 1,2,3 , Li Tian 4 , Zhaohui Wang 1,2,3
and Zhaoliang Cui 1,2,3, *

1 State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering,

Nanjing Tech University, Nanjing 210009, China
2 National Engineering Research Center for Special Separation Membrane, Nanjing Tech University,
Nanjing 210009, China
3 Jiangsu National Synergetic Innovation Center for Advanced Materials (SICAM), Nanjing Tech University,
Nanjing 210009, China
4 Nanjing Jiuying Membrane Technologies Co., Ltd., Nanjing 211899, China
* Correspondence: zcui@njtech.edu.cn
† Xiaoyun Wang and Dejian Chen are co-first authors and contributed equally to this article.

Abstract: A large pore size Poly(vinylidene fluoride) (PVDF) membrane was prepared by the V-NIPS
method using PVDF/N, N-dimethylacetamide (DMAc)/Polyvinyl pyrrolidone (PVP)/Polyethylene
glycol (PEG) system. Firstly, the effect of different additive ratios on the membrane morphology and
pore size was studied, and it was found that when the PVP:PEG ratio was 8:2, PVDF membranes with
a relatively large pore size tend to be formed; the pore size is about 7.5 µm. Then, the effects of different
exposure time on the membrane morphology and pore size were investigated, and it was found that
as the vapor temperature increased, the pores on the surface of the membrane first became slightly
smaller and then increased. Finally, the effects of different vapor temperatures on the membrane
properties were discussed. The results showed that the as-prepared membrane exhibited suitable
capillary flow rate and similar performance compared with a commercially available membrane in
colloidal gold tests. The likely cause is that the amount of negative charge is less and the capillary
Citation: Wang, X.; Chen, D.; He, T.; migration rate is too fast. This paper provides a reference for the preparation of PVDF colloidal gold
Zhou, Y.; Tian, L.; Wang, Z.; Cui, Z.
detection membrane.
Preparation of Lateral Flow PVDF
Membrane via Combined Vapor-
Keywords: Poly(vinylidene fluoride); vapor non-solvent-induced phase separation; detection of
and Non-Solvent-Induced Phase
colloidal gold; capillary flow rate
Separation (V-NIPS). Membranes 2023,
13, 91. https://doi.org/10.3390/
membranes13010091

Academic Editors: Chenxiao Jiang, 1. Introduction

Zhe Yang and Ying Mei
Lateral flow assays (LFAs) first emerged in the late 1960s, for monitoring serum
Received: 3 December 2022 proteins. In 1976, LFA was first used to detect human chronic gonadotropin (HCG) in
Revised: 31 December 2022 urine [1]. From that time on, it has been widely used for rapid detection of biomarkers of
Accepted: 2 January 2023 infections and various diseases, such as human immunodeficiency virus (HIV), malaria
Published: 10 January 2023 and dengue virus [2]. As shown in Figure 1, the lateral flow test strip is composed of
several parts: a sample pad, a conjugate pad, a reaction membrane (usually nitrocellulose
membrane) and an absorbent pad, of which nitrocellulose (NC) membrane is the most
critical material.
Copyright: © 2023 by the authors.
NC membranes used for lateral flow testing require the two most relevant parameters:
Licensee MDPI, Basel, Switzerland.
(1) protein-binding capacity, and (2) protein capillary flow rate along the long axis [3].
This article is an open access article
Firstly, the strong dipole of nitrate interacts with the peptide bond of the antibody, which
distributed under the terms and
conditions of the Creative Commons
immobilizes the antibody on the NC membrane through electrostatic interaction; usually,
Attribution (CC BY) license (https://
these peptide bond cannot be fixed directly on NC membrane due to their small molecular
creativecommons.org/licenses/by/
weight. Therefore, small molecules are often chemically coupled to large molecules such
4.0/). as bovine serum albumin (BSA) and then fixed on NC membrane. BSA was used as the

Membranes 2023, 13, 91. https://doi.org/10.3390/membranes13010091 https://www.mdpi.com/journal/membranes

Membranes 2023, 13, x FOR PEER REVIEW 2 of 13

Membranes 2023, 13, 91 2 of 14

used as the basis to evaluate the adsorption capacity of protein. Secondly, the NC mem-
brane itself is a hydrophobic material, but a surfactant is added during its membrane for-
mation, and
basis to the prepared
evaluate membrane
the adsorption hasofa protein.
capacity large pore size, so
Secondly, it NC
the canmembrane
ensure that theissample
itself
a hydrophobic
to be tested moves material,
along but
theaNCsurfactant is added
membrane duringcapillary
through its membrane formation,
action and
[1]. However, NC
the prepared membrane has a large pore size, so it can ensure that the
membrane is a dangerous chemical and is extremely flammable, so special attentionsample to be tested
moves
should bealong
paidthe NC membrane
during through
transportation andcapillary
storage.action [1]. However,
Moreover, with NC
the membrane
development of
is a dangerous chemical and is extremely flammable, so special attention should be paid
LFA, the mechanical strength and protein adsorption capacity of NC membrane can no
during transportation and storage. Moreover, with the development of LFA, the mechanical
longer meet
strength andthe current
protein application
adsorption requirements.
capacity of NC membrane Therefore, it is necessary
can no longer to develop
meet the current
new membrane
application materials for
requirements. LFA. it is necessary to develop new membrane materials
Therefore,
for LFA.

Figure 1. Schematic diagram of immunochromatographic diagnostic strip.

Figure 1. Schematic diagram of immunochromatographic diagnostic strip.
Poly(vinylidene fluoride) (PVDF) is a semi-crystalline polymer with -(CH2 -CF2 )n -
Poly(vinylidene
repeating fluoride)high
units. It presents (PVDF)
thermal,is a chemical
semi-crystalline
and aging polymer with
resistance -(CH
[4,5]. 2-CF2)n- re-
PVDF
peating units. have
membranes It presents
been used highinthermal, chemical fields,
many application and aging resistance
including [4,5]. PVDF
ultrafiltration (UF), mem-
microfiltration
branes have been(MF), usedmembrane bioreactor (MBR),
in many application fields,membrane
including distillation
ultrafiltration(MD)(UF),and microfil-
so
on [4]. In addition, PVDF membranes also have some
tration (MF), membrane bioreactor (MBR), membrane distillation (MD) and so on applications in biology. Ideris et al. [4]. In
reported the effect of solvent dissolution temperature in the casting solution on PVDF
addition, PVDF membranes also have some applications in biology. Ideris et al. reported
membrane protein binding. When the dissolution temperature was below 40 ◦ C, the crystal
thestructure
effect ofofsolvent dissolution temperature in the casting solution on PVDF membrane
PVDF had a greater influence on its protein-binding ability, and the lower the α
protein
form,binding.
the stronger When the dissolutionability.
the protein-binding temperature
However,was abovebelow 40protein
40 ◦ C, °C, thebinding
crystalwas structure
of PVDF had a greater influence on its protein-binding ability,
more affected by porosity, with more protein retained at higher porosity [6]. Furthermore, and the lower the α form,
theadditives
strongerare thealso
protein-binding
important factors ability. However,
affecting membraneabove 40 °C, protein
structure binding The
and properties. was more
most common
affected by porosity,polymer with additives are hydrophilic
more protein retained polymers,
at higher such as polyvinylpyrrolidone
porosity [6]. Furthermore, ad-
(PVP)are
ditives and polyethylene
also importantglycol factors(PEG). In the membrane
affecting film-formingstructure
process, hydrophilic additives
and properties. The most
can promote the formation of pores, improve the connectivity of pores, increase the water
common polymer additives are hydrophilic polymers, such as polyvinylpyrrolidone
flux of the membrane, and improve the hydrophilicity and pollution resistance of the
(PVP) and polyethylene glycol (PEG). In the film-forming process, hydrophilic additives can
membrane. Li et al. studied the effect of PVP as an additive on the structure and properties
promote
of PVDF the formation
hollow of pores, improve
fiber membranes, and found the
thatconnectivity
when using lower of pores, increase
molecular the PVP,
weight water flux
of the membrane, and improve the hydrophilicity and pollution
the permeability and retention performance of the membrane were improved, whereas the resistance of the membrane.
Li et al. studied
higher molecular theweight
effectPVPof PVP
wouldasmake an additive
the membraneon the structure
structure and
dense, properties
thereby reducing of PVDF
its permeability
hollow fiber membranes,[7]. Lin et andal. found
found thatthatwhen
whenpolyethylene
using lowerglycol (PEG) weight
molecular was used as an
PVP, the per-
additive to make PVDF membrane, the surface pore size of
meability and retention performance of the membrane were improved, whereas the higher the membrane increased with
the increase in PEG molecular weight, and the flux and retention rate were the opposite,
molecular weight PVP would make the membrane structure dense, thereby reducing its
but increased with the increase in PEG content [8]. In this paper, PVP and PEG were
permeability [7]. Lin etand
selected as additives, al. found that when
their molecular polyethylene
weight, concentration glycol
and(PEG) wasparameters
proportion used as an addi-
tivewere
to make
adjusted PVDF membrane,
to improve the surface
the flatness, poreuniformity
pore size size of the andmembrane increasedrate
capillary migration with the
increase in PEG molecular weight, and the flux and retention
of the film. However, there is no literature on the preparation of large-pore-size PVDF rate were the opposite, but
increased
membranes withandthe their
increase in PEGin
application content [8]. In thisthis
LFA. Therefore, paper,
paperPVP and PEG
discusses were selected as
the conditions
for the preparation of large-pore-size PVDF membranes,
additives, and their molecular weight, concentration and proportion parameters such as the ratio of additives, were ad-
exposure time and temperature, etc. In addition, this paper used the
justed to improve the flatness, pore size uniformity and capillary migration rate of the film. prepared membrane
in LFA.
However, there is no literature on the preparation of large-pore-size PVDF membranes and
Non-solvent-induced phase separation (NIPS) is a common method for preparing
their application
PVDF membranes. in LFA. Therefore,
It involves this paper
pouring a polymerdiscusses
solution theonto
conditions
a suitableforcarrier
the preparation
and
of large-pore-size
then immersing PVDF membranes,bath
it in a coagulation such as the ratio
containing of additives,
a non-solvent. exposure
The exchange time and tem-
of the
perature, etc. In addition, this paper used the prepared membrane in LFA.
Non-solvent-induced phase separation (NIPS) is a common method for preparing
PVDF membranes. It involves pouring a polymer solution onto a suitable carrier and then
immersing it in a coagulation bath containing a non-solvent. The exchange of the solvent
Membranes 2023, 13, x FOR PEER REVIEW 3 of 13

in the polymer solution with the non-solvent from the coagulation bath leads to phase
Membranes 2023, 13, 91 separation. Vapor-induced phase separation (VIPS) is a process in which the3 ofwet 14 mem-
brane is first exposed to a gaseous non-solvent at a given temperature and humidity for a
period of time, and then immersed in a non-solvent solidification bath. If exposure time
issolvent in thethe
moderate, polymer
phasesolution with the mechanism
transformation non-solvent from thea coagulation
will be combination bath leads and
of VIPS to NIPS
phase separation.
(i.e., N-VIPS). Vapor-induced phase separation (VIPS) is a process in which the wet
membrane is first exposed to a gaseous non-solvent at a given temperature and humidity
2.forExperimental
a period of time, and then immersed in a non-solvent solidification bath. If exposure
Procedure
time is moderate, the phase transformation mechanism will be a combination of VIPS and
2.1.
NIPS Material
(i.e., N-VIPS).
PVDF 6010 (Mw = 600,000) powder was purchased from Shanghai Solef Co., Ltd.,
2. Experimental Procedure
Shanghai, China. Dimethylacetamide (DMAc) (>99.8%) used as solvent was purchased
2.1. Material
from Shanghai Aladdin Reagent Co., Ltd., Shanghai, China. Polyvinylpyrrolidone (PVP
PVDF 6010 (Mw = 600,000) powder was purchased from Shanghai Solef Co., Ltd.,
K90, Mw = 360,000) was purchased from TCI Co., Ltd. Shanghai, China. Polyethylene gly-
Shanghai, China. Dimethylacetamide (DMAc) (>99.8%) used as solvent was purchased
col (PEG 600) was purchased from Beijing OKA Biological Technology Co., Ltd., Beijing,
from Shanghai Aladdin Reagent Co., Ltd., Shanghai, China. Polyvinylpyrrolidone (PVP
China.
K90, Mw Bovine albumin
= 360,000) was (BSA, A1933-5G)
purchased from TCIwas purchased
Co., from Anhui
Ltd. Shanghai, China. Senrise Technology
Polyethylene
Co., Ltd. Fuyang, China.
glycol (PEG 600) was purchased from Beijing OKA Biological Technology Co., Ltd., Beijing,
China. Bovine albumin (BSA, A1933-5G) was purchased from Anhui Senrise Technology
2.2.
Co.,PVDF Membrane
Ltd. Fuyang, Preparation
China.
A quantity
2.2. PVDF of PVDF
Membrane 6010 and additives (PVP K90 and PEG 600) was dissolved in
Preparation
DMAc in a flask, with the temperature set at 60 °C to promote full dissolution, and stirred
A quantity of PVDF 6010 and additives (PVP K90 and PEG 600) was dissolved in
for
DMAc12 h,in in orderwith
a flask, to obtain a homogeneous
the temperature set at 60 ◦casting solution.
C to promote The mass and
full dissolution, fraction of PVDF
stirred
was 16%,
for 12 h, inthe mass
order to fraction
obtain a of DMAc wascasting
homogeneous 74% and the total
solution. The mass
massfraction
fractionof
ofadditives
PVDF was
10%. The the
was 16%, solution was then
mass fraction degassed
of DMAc untiland
was 74% it became clear fraction
the total mass of bubbles. A desktop
of additives was coater
(with the knife
10%. The height
solution was adjusted to 250-μm
then degassed until itand speed
became setof
clear tobubbles.
1.0 m∙min A −1) was used
desktop to scrape
coater
(with the knife height adjusted to 250-µm and speed set to 1.0 m · min −1 ) was used to scrape
the membrane. Both glass and nascent membrane were then placed on a water bath at
the membrane.
90% humidity Both at 60glass and exposed
°C and nascent membrane wereThe
for a while. thenexposure
placed onwas a water bathatatexchanging
aimed 90%
humidity atwith◦
60 Cwater
and exposed
the solvent vapor. for a while.
Then The was
the glass exposure
placedwasinaimed
ambientat exchanging
deionizedthe water (DI
solvent with water vapor. Then the glass was placed in ambient deionized water (DI water)
water) for further solvent exchange. Finally, the resulting membranes were washed sev-
for further solvent exchange. Finally, the resulting membranes were washed several times
eral times with DI water to remove residual DMAc, and then dried in air. The detailed
with DI water to remove residual DMAc, and then dried in air. The detailed process is
process
shown inisFigure
shown2 and
in Figure 2 and Table 1.
Table 1.

Figure
Figure 2. Schematic
Schematicdiagram
diagramof of PVDF
PVDF membrane
membrane preparation.
preparation.
Membranes 2023, 13, 91 4 of 14

Table 1. Membrane codes for different additive ratios, exposure times and vapor temperatures.

Additive Ratio
Membrane Code Exposure Time (min) Vapor Temperature (◦ C)
(PVP:PEG)
M1 4:6 5 60
M2 6:4 5 60
M3 8:2 5 60
M4 8:2 0.25 60
M5 8:2 0.5 60
M6 8:2 1 60
M7 8:2 3 60
M8 8:2 5 60
M9 8:2 10 60
M10 8:2 5 50
M11 8:2 5 60
M12 8:2 5 70

2.3. PVDF Membrane Characterization

The surface and cross-sectional morphologies of the prepared PVDF dry membranes
were observed by cold field emission scanning electron microscope (FESEM, S-4800, Hitachi
Limited, Tokyo, Japan). All samples were freeze-fractured in liquid nitrogen and sputtered
with gold membranes.
A X-ray diffractometer (XRD, Miniflex 600, Rigaku Corporation, Tokyo, Japan) with
a Cu target was used to determine the crystallinity of the prepared PVDF membranes.
Operating parameters included tube current and acceleration voltage of 15 mA and 40 kV,
respectively; angle range of 5–60◦ ; and scan speed of 5◦ ·min−1 .
The functional groups in the prepared membranes were analyzed using a Fourier
Transform infrared spectrometer (FTIR, Nicolet 8700, Thermo Fisher Scientific, Waltham,
MA, USA). In this section, a diaphragm of a certain size was placed on the sample rack and
scanned 32 times in attenuated total reflection (ATR) mode with a resolution of 4 cm−1 and
a test wave number ranging from 500 to 4000 cm−1
An electrokinetic analyzer (SurPASS 3, Anton-Paar, Graz, Austria) was used to deter-
mine the surface charge of the membranes. Prior to analysis, the membrane was air-dried
and the machine was cleaned with DI water. Then, 0.015 g potassium chloride (KCl) was
dissolved in 250 mL deionized water to prepare KCl electrolyte solution. The streaming
potential was determined by using 0.1 M HCl and NaOH to adjust the pH.
The porosity of PVDF membrane was measured by the gravimetric method. The
sample was soaked in kerosene for 24 h until the membrane was completely wetted, and
then the kerosene on the surface of the membrane was wiped away, leaving only the
kerosene remaining in the membrane holes. The weight of the dry membrane and the wet
membrane were recorded as m0 and m1 , respectively. The following formula was used to
calculate the porosity of the membrane:
m1 − m0
ρk
ε= m1 − m0 × 100% (1)
ρk + mρ p0

Here, ρk and ρp are the density of kerosene (about 0.81 g/cm3 ) and PVDF (about
1.78 g/cm3 ), respectively.
A tensile testing instrument (HLD 1000, Handpi, Jinhua, China) was used to measure
the mechanical properties of prepared membranes. Each sample was first cut into 5 cm
long and 1 cm wide strips using a Japanese knife mold. The thickness of each sample was
measured by an electronic digital membrane thickness meter before the test. Both ends of
the sample were fixed and stretched at a constant rate of 5 mm/min (25 ◦ C). The electronic
tension meter was set to zero and the original length of the sample L0 (cm) was recorded.
It was slowly stretch until the test sample broke. The sample length L (cm) at this time
 tension meter was set to zero and the original length of the sample L0 (cm) was recorded.
Membranes 2023, 13, 91
It was slowly stretch until the test sample broke. The sample length L (cm) at this time and
5 of 14
the tension data F (N) shown by the tension meter were recorded. The formula for calcu-
lating the elongation at break and tensile strength of the membrane are as follows:
and the tension data F (N) shown by the 𝐿 tension
− 𝐿0 meter were recorded. The formula for
𝜃 tensile
calculating the elongation at break and = × 100%
strength of the membrane are as follows: (2)
𝐿0
L − L0
θ= × 100% (2)
L0 𝜎 = 𝐹 (3)
𝐴
F
The pore size of prepared PVDF membranes σ= was determined using a Liquid–Liquid (3)
A
Pore Size
TheDistribution Meter (GaoQ-PSMA-10,
pore size of prepared PVDF membranes GaoQ, Nanjing,using
was determined China).
a Liquid–Liquid
TheSize
Pore capillary migration
Distribution Meter rate of the prepared
(GaoQ-PSMA-10, GaoQ,membrane was measured by the follow-
Nanjing, China).
ing steps.
TheThe sample
capillary was cut
migration into
rate 2 cm
of the wide membrane
prepared by 6 cm long
was pieces
measuredandbyDI
thewater was used
following
as the migration
steps. The samplemedium. Experiments
was cut into 2 cm wide bywere
6 cmperformed
long piecesat room
and temperature
DI water (27the°C) and
was used as
migration medium. Experiments were performed at room ◦
ambient pressure. The measurement started when thetemperature
membrane(27 wasC)inand ambient
contact with de-
pressure. The measurement started when the membrane was in contact
ionized water and the water migrated along the membrane surface for about 5 mm, andwith deionized
water and the water migrated along the membrane surface for about 5 mm, and stopped
stopped when the water migrated to the membrane surface for 4 cm. The experimental
when the water migrated to the membrane surface for 4 cm. The experimental process is
process
shownisinshown
Figurein
3. Figure 3.

Figure 3. Diagram
Figure 3. Diagramofofcapillary
capillary flow ratetest.
flow rate test.

TheThe membrane-binding ability

membrane-binding abilitywas
wasevaluated
evaluatedby by
a model protein
a model BSA. BSA.
protein Each sample
Each sample
was cut into 1 cm wide by 2 cm long membrane strips and put into a conical beaker
was cut into 1 cm wide by 2 cm long membrane strips and put into a conical beaker con-
containing 4 mL of BSA solution (1 mg/mL). The mixture was incubated at 37 ◦ C for 5 h
taining 4 mL of BSA solution (1 mg/mL). The mixture was incubated at 37 °C for 5 h with
with a shaking speed of 100 rpm. Each membrane was measured three times and averaged.
a shaking speed of 100 rpm. Each membrane was measured three times and averaged.
3. Results and Discussion
3.1. Additive
3. Results andRatios
Discussion
The morphologies
3.1. Additive Ratios of the membranes prepared with different additive ratios are shown
in Figure 4a. The morphologies of membranes M1 and M2 are relatively similar, with
The morphologies
a sponge-like structure of the membranes
in cross prepared
section, whereas M3 haswith a largedifferent additive
micron-scale cavityratios
in are
shown in Figure
the cross section.4a.This
Theismorphologies
because when the of membranes
PVP content is M1 and
low, theM2 are relatively
liquid–liquid phasesimilar,
with a sponge-like
separation structure
occurs mainly in casting
in the cross section, whereas
liquid, and M3 to
it is easier has
forma large micron-scale
spongy pores [9,10]. cavity
It iscross
in the also because
section.the addition
This of PEGwhen
is because will increase
the PVPthe flatnessisoflow,
content the membrane and the phase
the liquid–liquid
uniformity of the membrane. As shown in Table 2, with the increase
separation occurs mainly in the casting liquid, and it is easier to form spongy pores in PVP content, the [9,10].
viscosity of the casting liquid increases, which slows down the exchange of solvent and
It is also because the addition of PEG will increase the flatness of the membrane and the
non-solvent [11]. At this time, PVP is a high-molecular-weight additive, which increases
uniformity of the
viscosity, and membrane.
delays the phase As shown After
separation. in Table 2, with
partially the increase
aggregated PVP isin PVP acontent,
eluted, large the
viscosity of theappears
cavity shape casting[12,13].
liquid increases, which slows down the exchange of solvent and
non-solvent [11]. At this time, PVP
The pore size distributions is a high-molecular-weight
of membranes prepared with different additive,
additivewhich increases
ratios are
viscosity,
shown in and delays
Figure 4b. the
When phase separation.
the ratio of PVP toAfter
PEG is partially aggregated
4:6 and 6:4, PVP of
the pore sizes is the
eluted, a
prepared
large cavitymembranes
shape appears are about 1.3 microns and 1.2 microns, respectively; when the ratio
[12,13].
reaches 8:2, the pore size of the prepared membrane is about 7 microns, which is consistent
with the SEM photos. This is because when the ratio of PVP and PEG is relatively close,
the viscosity of the casting solution is not much different, but when the ratio of PVP and
PEG reaches 8:2, the viscosity of the casting solution increases significantly, hindering the
phase separation kinetics. The hydrophilicity significantly improves the thermodynamics
of phase separation. For the polymer-solvent-non-solvent ternary system, hydrophilic PVP
Membranes 2023, 13, 91 6 of 14

with larger molecular weight can replace part of the polymer and increase the miscible
region; the affinity with polymers and solvents is changed, increasing the thermodynamic
in-stability of the casting film; and the binodal curve becomes closer to the (polymer)–
(solvent/non-solvent) axis. PEG with smaller molecular weight can be regarded as a weak
non-solvent. When replacing part of the solvent in the casting solution, the difference in
the composition of different parts of the casting solution caused by the diffusion rate in
Membranes 2023, 13, x FOR PEER REVIEW
the film-forming process can be reduced. The effect is to reduce the time difference in the 6 of 13
phase-separation process and improve the uniformity of the membrane aperture.

(a) (b)
Figure
Figure 4. (a)
4. (a) SEMSEM images
images of PVDF
of PVDF membranes
membranes prepared
prepared with different
with different additive
additive ratios
ratios of (A,B)of4:6,
(A,B) 4:6,
(C,D) 6:4 and (E,F) 8:2. (b) Pore size distribution of PVDF membranes prepared with
(C,D) 6:4 and (E,F) 8:2. (b) Pore size distribution of PVDF membranes prepared with different different ad-
ditive ratios.
additive ratios.

Viscosity
Table 2.The poreofsize
casting solution with
distributions of different
membranes additive ratios. with different additive ratios are
prepared
shown in Figure 4b. When the ratio of PVP to PEG is 4:6 and 6:4, the pore sizes of the
Additive Ratio (PVP:PEG) Viscosity (cp)
prepared membranes are about 1.3 microns and 1.2 microns, respectively; when the ratio
4:6 7230 ± 42
reaches 8:2, the pore 6:4
size of the prepared membrane is about 7 microns, which is consistent
12,660 ± 85
with the SEM photos. 8:2 This is because when the ratio of 21,930 PVP and± 127PEG is relatively close,
the viscosity of the casting solution is not much different, but when the ratio of PVP and
PEG reaches 8:2, the viscosity of the casting solution increases significantly, hindering the
The combined effect of PVP K90 on thermodynamic and kinetic phase-separation
phase separation
mechanisms kinetics.
can explain The hydrophilicity
the significant increase in significantly
membrane pore improves
size. Duethetothermodynamics
the expan-
of phase separation. For the polymer-solvent-non-solvent
sion of the molecular chain, the fluidity of the PVP K90 chain is limited, so ternary system, hydrophilic
the outflow
PVP
rate of with
PVP inlarger molecular weight
the solidification bath iscan replace
slower. part ofthe
However, thepresence
polymerof and increase
a large the misci-
amount
ofble
PVPregion;
in the the affinity
solution with polymers
increases the phaseand solventsrate,
conversion is changed,
resulting increasing the thermody-
in a large pore size.
Innamic in-stability
addition, of the
some of the casting
retained film; and
molecules the binodal
of PVP K90 leave curve becomes
the primary closer to and
membrane the (poly-
mer)–(solvent/non-solvent)
dissolve axis. forming
in water after delamination, PEG with smaller
further poresmolecular
within theweight
polymer can be regarded as
membrane.
Inaaddition, the significant
weak non-solvent. When increase in pore
replacing partsize is due
of the to the
solvent slowcasting
in the rate ofsolution,
non-solvent
the differ-
exchange during the VIPS process, and nucleation plays a crucial role in the dilute
ence in the composition of different parts of the casting solution caused by the diffusion phase of
the polymer, contributing to the formation of large-pore-size membranes [14].
rate in the film-forming process can be reduced. The effect is to reduce the time difference
in the phase-separation process and improve the uniformity of the membrane aperture.
The combined effect of PVP K90 on thermodynamic and kinetic phase-separation
mechanisms can explain the significant increase in membrane pore size. Due to the expan-
sion of the molecular chain, the fluidity of the PVP K90 chain is limited, so the outflow
rate of PVP in the solidification bath is slower. However, the presence of a large amount
of PVP in the solution increases the phase conversion rate, resulting in a large pore size.
 Table 2. Viscosity of casting solution with different additive ratios.

Additive Ratio (PVP:PEG) Viscosity (cp)

4:6 7230 ± 42
6:4 12,660 ± 85
Membranes 2023, 13, 91 8:2 21,930 ± 127 7 of 14

3.2. Exposure Time

3.2. The
Exposure Time
morphologies of membranes prepared with different exposure times are shown
in Figure
The5a. When the exposure
morphologies of membranestime was 15 s, with
prepared the membrane showedtimes
different exposure a finger-like
are shown struc-
in
Figure
ture with5a.a When
dense the exposure
layer on top.timeDuewas to the15 short
s, the exposure
membranetime, showed the acasting
finger-like
liquidstructure
quickly
with a the
entered denseNIPS layer on top.
process. RapidDueexchange
to the shortoccursexposure
because time,
of a the
highcasting
affinityliquid
betweenquickly
non-
entered the NIPS process. Rapid exchange occurs because of a high
solvent and solvent. Therefore, the solvent flowing out into the coagulation bath brought affinity between non-
solvent
the and solvent.
polymer chains toTherefore, the solvent
the top surface of theflowing out intoresulting
membrane, the coagulation bath brought
in a higher polymer
the polymer chains to the top surface of the membrane, resulting
concentration on the top surface of the membrane, forming a dense skin layer [15]. in a higher polymer
When
concentration on the top surface of the membrane, forming a dense
the exposure time was 30 s, pores began to appear on the surface, finger-like pores still skin layer [15]. When
the exposure time was 30 s, pores began to appear on the surface, finger-like pores still
appeared on the cross section, and large cavities began to appear. When the exposure time
appeared on the cross section, and large cavities began to appear. When the exposure
was 1 min, macropores began to appear on the surface of the membrane, and the cross-
time was 1 min, macropores began to appear on the surface of the membrane, and the
section showed a micron-scale cavity structure. With the increase in exposure time, the
cross-section showed a micron-scale cavity structure. With the increase in exposure time,
number of pores on the surface of the membrane increased, and the exposure time of 3–
the number of pores on the surface of the membrane increased, and the exposure time of
103–10
minmin
hadhadlittle effect on the cross section, and all showed micron-scale cavity structure.
little effect on the cross section, and all showed micron-scale cavity structure.
This is because as
This is because as the theexposure
exposure timetime increases,
increases, especially
especially whenwhen the exposure
the exposure time is
time is greater
greater thanminutes,
than three three minutes, the casting
the casting film solution
film solution entersenters
the NIPSthe process
NIPS processfrom thefrom the pre-
previous
vious
state very quickly, and thus it first goes through a longer VIPS process and then enters then
state very quickly, and thus it first goes through a longer VIPS process and the
enters
NIPS the NIPStherefore,
process; process; therefore,
the solventthe andsolvent and non-solvent
non-solvent exchange rates exchange
slow down,rates slow down,
and pores
and pores
begin begin toon
to appear appear on the membrane
the membrane surface. surface. The cross-sectional
The cross-sectional structurestructure
changes changes
from a
from a finger-like
finger-like macroporous
macroporous structurestructure to a sponge-like
to a sponge-like structurestructure
[16,17].[16,17].
However, However,
due to the due
tohigh
the high molecular
molecular weightweight
of PVP,of PVP, agglomeration
agglomeration occursoccurs
with thewith the increase
increase in VIPS in time,
VIPS time,
so a
solarge
a large amount
amount of PVP
of PVP is eluted
is eluted duringduring the NIPS
the NIPS process,
process, resulting
resulting in largein large cavities
cavities in thein
cross-sectional structure.
the cross-sectional structure.

(a)

Figure 5. Cont.
Membranes 2023, 13, x FOR PEER REVIEW 8 of 13

Membranes 2023, 13, 91 8 of 14

(b)
Figure 5. (a) SEM images of PVDF membranes prepared with different exposure time of (A,B) 15 s,
Figure 5. (a) SEM images of PVDF membranes prepared with different exposure time of (A,B) 15 s,
(C,D) 30 s, (E,F) 1 min, (G,H) 3 min, (I,J) 5 min and (K,L) 10 min. (b) Pore size distribution of PVDF
(C,D) 30 s, (E,F) 1 min, (G,H) 3 min, (I,J) 5 min and (K,L) 10 min. (b) Pore size distribution of PVDF
membranes prepared with different exposure times.
membranes prepared with different exposure times.

The effect of exposure

The effect of exposure time on timetheonmembrane
the membrane pore sizeporedistribution is shown
size distribution in Fig- in
is shown
ure 5b, which
Figure 5b, also
which includes the morphologies
also includes the morphologiesof the of membranes
the membranesafter drying. It canItbe
after drying. can
seen befrom thefrom
seen figure
thethat
figurethethatporethe size distribution
pore of the membranes
size distribution prepared
of the membranes with dif-
prepared with
ferent exposure
different times istimes
exposure narrow, and from
is narrow, andthe morphologies
from the morphologiesof the membranes
of the membranesafter dry-
after
ing, it can be seen that the membranes prepared with the exposure
drying, it can be seen that the membranes prepared with the exposure time of−115 time of 15 s min s−are
1 min

all curled.
are allThe reason
curled. Theisreason
that when is thatthewhen
exposure time is short,
the exposure time isthe PVPthe
short, in the
PVPcasting
in the solu-
casting
tion does not does
solution aggregate and may and
not aggregate diffuse
mayout in a large
diffuse out in amount
a largeduring
amount theduring
phase the separa-
phase
separation
tion process, process,
whereas withwhereas with the
the increase increase
in the in thetime,
exposure exposure
the PVP time, the PVP and
aggregates aggregates
par-
and in
ticipates participates
the membrane in theformation.
membraneBecause formation.PVPBecause PVP is a additive
is a hydrophilic hydrophilic
[18],additive
the mem- [18],
the membrane flatness is high after drying. The change of exposure
brane flatness is high after drying. The change of exposure time not only changes the com- time not only changes
the composition
position of the castingofsolution,
the casting butsolution, but also
also changes the changes
aggregated the aggregated
structure ofstructure
the polymer of the
polymer in the casting solution. The influence of humidity is obvious.
in the casting solution. The influence of humidity is obvious. Chen et al. found that at low Chen et al. found that
at low humidity, the membrane aperture changed little
humidity, the membrane aperture changed little with the increase in exposure time, with the increase in exposure time,
whereas
whereas at high
at high humidity,
humidity, the membrane
the membrane aperture
aperture increased
increased withwith
thethe increase
increase in in exposure
exposure
time [19]. Dehban et al. reported that in the indoor environment, the membrane aperture
time [19]. Dehban et al. reported that in the indoor environment, the membrane aperture
showed a trend of first increasing and then decreasing and then increasing with the increase
showed a trend of first increasing and then decreasing and then increasing with the increase
in exposure time [20]. Therefore, there is no specific relationship between exposure time
in exposure time [20]. Therefore, there is no specific relationship between exposure time and
and aperture and the effect of exposure time on the pore size of the membrane is unclear.
aperture and the effect of exposure time on the pore size of the membrane is unclear.
3.3. Vapor Temperature
3.3. VaporTheTemperature
morphologies of membranes prepared at different vapor temperatures are shown
The
in morphologies
Figure 6. The crossof membranes
sections prepared
of membranes at different
prepared vapor
at different temperatures
vapor temperatures areare
shownnotinvery
Figure 6. Theand
different, cross
all sections
of them areof membranes preparedand
partially sponge-like at different vapor
contain larger temper-
micron-scale
atures are notbut
cavities, verythedifferent,
surface ofand allprepared
the of them are partiallyissponge-like
membrane and contain
slightly different. As thelarger
vapor
temperature
micron-scale increases,
cavities, thesurface
but the pores ofon the
the prepared
surface ofmembrane
the membrane first become
is slightly slightly
different. As
smaller
the vapor and then increase.
temperature Thisthe
increases, may be because
pores on the when
surfacetheofsolvent evaporation
the membrane temperature
first become
is lower
slightly thanand
smaller the dissolution
then increase.temperature,
This maythe bemass transfer
because when ratethe
of the VIPS process
solvent is slow,
evaporation
so that a large amount of PVP is eluted on the membrane surface.
temperature is lower than the dissolution temperature, the mass transfer rate of the VIPS When the evaporation
temperature
process is slow, so is that
higher than the
a large dissolution
amount of PVPtemperature,
is eluted onthe thephase-transition
membrane surface. mechanism
When is
mainly the combination of VIPS and NIPS, which also leads to the elution of a large amount
of PVP.
 tion mechanism
Membranes 2023, 13, x FOR PEER REVIEW is mainly the combination of VIPS and NIPS, which also leads to
9 ofthe
13 elu
tion of a large amount of PVP.

the evaporation temperature is higher than the dissolution temperature, the phase-transi-
Membranes 2023, 13, 91 9 of 14
tion mechanism is mainly the combination of VIPS and NIPS, which also leads to the elu-
tion of a large amount of PVP.

Figure 6. SEM images of PVDF membranes prepared at different vapor temperatures. (A,B) 50 °C
(C,D) 60 °C and (E,F) 70 °C.
Figure 6.
6. SEM
SEM images of
images ofPVDF
PVDFmembranes
membranesprepared
prepared at
atof different vapor
different temperatures.
(A,B)(A,B) 50 °C;
◦ C;
Figure
Figure
(C,D) 60 °C 7a
andshows
(E,F) the
70 °C. pore size distribution PVDFvapor temperatures.
membranes prepared 50at differen
◦
(C,D) 60 C and (E,F) 70 C.◦
vapor temperatures. It can be seen from the figure that the pore size distribution of the
membrane
Figureprepared
Figure showsat
7a shows the
the
the vapor
pore
pore temperature
sizedistribution
size distributionofofofPVDF
PVDF 60membranes
°Cmembranes
is the most concentrated,
prepared
prepared around
at different
at different
8 microns.
vapor In addition,
vapor temperatures. the
It can
temperatures. It membranes
can be
beseen
seenfrom prepared
fromthe
thefigure
figure at
that 50
that °C
thethe and
pore
pore 70
sizesize°C are concentrated
distribution
distribution of the a
of the
membrane prepared at ◦
membrane
around 16 andprepared atthe
20 microns,thevapor
vaportemperatureThisofisof
temperature
respectively. 60consistent
60C°Cis the most
is the concentrated,
most
with around
concentrated,
the SEM photo around
results.
◦ ◦
88microns.
microns. In
In addition,
addition, the
themembranes
membranesprepared
prepared at at
5050C°C
and 70 70
and C °C
are are
concentrated at at
concentrated
around 16 and 20 microns, respectively. This is consistent with the SEM photo results.
around 16 and 20 microns, respectively. This is consistent with the SEM photo results.

(a) (b)
(a) (b)
Figure 7. Cont.
Membranes 2023, 13, x FOR PEER REVIEW 10 of 13

Membranes 2023, 13, 91 10 of 14

(c) (d)

(e) (f)

(g)
Figure 7. (a)7.Pore
Figure sizesize
(a) Pore distribution,
distribution, (b) XRDspectra,
(b) XRD spectra,
(c) (c) FT-IR
FT-IR spectrum,
spectrum, (d) zeta(d) zeta potential,
potential, (e) capil-
(e) capillary
lary flow rate and porosity, (f) tensile strength and elongation at break and (g) protein
flow rate and porosity, (f) tensile strength and elongation at break and (g) protein adsorption capacity adsorption
capacity of PVDF
of PVDF membranes
membranes prepared
prepared at different
at different vapor temperatures.
vapor temperatures.

Figure 7b shows the result of XRD study of the prepared membranes. The crystallites
of the membranes prepared at different vapor temperatures are a mixture of α and β forms.
The XRD patterns of the prepared membranes show that the PVDF crystallites have three
characteristic peaks at ca. 18.3° (α), 20.1° (β), and 26.56° (α). Polarized FTIR spectra (Figure
7c) were used to characterize the crystalline characteristic peaks of the PVDF membranes.
Membranes 2023, 13, 91 11 of 14

Figure 7b shows the result of XRD study of the prepared membranes. The crystallites
of the membranes prepared at different vapor temperatures are a mixture of α and β
forms. The XRD patterns of the prepared membranes show that the PVDF crystallites
have three characteristic peaks at ca. 18.3◦ (α), 20.1◦ (β), and 26.56◦ (α). Polarized FTIR
spectra (Figure 7c) were used to characterize the crystalline characteristic peaks of the PVDF
membranes. The characteristic peaks appear at 762, 796, 876, 1070, 1178 and 1423 cm−1 ,
which are similar to those observed on PVDF membranes mainly containing α phase,
whereas other crystal characteristic peaks at 840 and 1402 cm−1 can be attributed to the β
phase [21,22].
Figure 7d shows the zeta potentials of PVDF membranes prepared at different vapor
temperatures. At pH = 7, the surface of the membrane prepared at 60 ◦ C had the greatest
negative charge. Since the pore size of the membrane prepared at 60 ◦ C is relatively small,
it indicates that more PVP was involved in the membrane formation on the membrane
surface. PVP is a hydrophilic material [15], which reduces the absorption of negative ions
on the membrane surface in the electrolyte solution, thereby reducing the negative zeta
potential of the membrane surface [23].
The capillary flow time and porosity of membranes prepared at different vapor tem-
perature are shown in Figure 7e. With the increase in the vapor temperature, the capillary
flow time shows a gradually decreasing trend. The porosity of several membranes is not
very different, but due to the increase in temperature, the mass-transfer rate increases [24],
and the exchange rate of solvent and non-solvent increases during the VIPS process,
which improves the internal connectivity of the membrane, thereby decreasing its capillary
flow time.
The tensile strength and elongation at break of membranes prepared with different
vapor temperatures are shown in Figure 7f. As the vapor temperature increases, the tensile
strength shows a slightly increasing trend, which is similar to the findings of Zhao et al. [25].
This may be because the formation of spherulites in the PVDF membrane is inhibited with
increasing vapor temperature, resulting in increased membrane strength. The elongation at
break shows a trend of first increasing and then decreasing.
Figure 7g shows the protein-binding capacity of PVDF membranes prepared at dif-
ferent vapor temperatures. It can be seen from the figure that there is little difference in
the protein adsorption capacity of several membranes, at about 15 µg/cm2 . The protein
adsorption capacity of the membrane is related to many factors, such as pore size, porosity
and crystal form [6]. The protein adsorption capacity of these membranes is low and close,
because the porosity of the membranes is similar and the pore size is larger, and the protein
cannot be fixed in the pores of the membranes.
Figure 8 shows the application of PVDF membranes prepared at different vapor
temperatures in the actual colloidal gold test strips. As can be seen from the figure,
compared with the commercially available NC membrane, the test line T of the self-made
membrane did not develop color, and the quality-control line C developed a light color.
This may be because the protein adsorption capacity of these membranes was low, and the
surface had less negative charge, and could not form stable binding with the antibodies
immobilized on the surface. The capillary flow rate is too fast, making it difficult for
unadsorbed antibodies to be firmly anchored on the membrane surface. It is easily washed
away by the sample to be tested, resulting in an inconspicuous line display [3].
 did not develop color, and the quality-control line C developed a light color. This may be
because the protein adsorption capacity of these membranes was low, and the surface had
less negative charge, and could not form stable binding with the antibodies immobilized
on the surface. The capillary flow rate is too fast, making it difficult for unadsorbed anti-
bodies
Membranes 2023, 13, 91 to be firmly anchored on the membrane surface. It is easily washed away by the 12 of 14
sample to be tested, resulting in an inconspicuous line display [3].

50 °C

60 °C
3, 13, x FOR PEER REVIEW 12 of 13

70 °C

Figure 8. Application
Figureof8.colloidal goldoftest
Application strips gold
colloidal of PVDF membrane
test strips prepared
of PVDF at prepared
membrane differentatvapor
different
temperatures. vapor temperatures.

4. Conclusions
4. Conclusions
In this paper, we proposed a method to prepare large-pore-size PVDF membranes,
In this paper,
and we proposed
use them a method The
for immunoassay. to prepare large-pore-size
morphologies of the membranes PVDF membranes,
prepared at different
and use them for immunoassay.
additive The times
ratios, exposure morphologies of the membranes
and vapor temperatures prepared
were explored. at differ-
The results showed
ent additive ratios, exposure times and vapor temperatures were explored. The results
that when the ratio of PVP to PEG was 8:2, the pore size of the membrane was the largest,
showed that when because the high-molecular-weight
the ratio of PVP to PEG was 8:2, additives of PVP
the pore sizeagglomerated
of the membrane and formed
was the larger
cavities after elution. As the exposure time increased from 10 s to 1 min, the membrane
largest, because the high-molecular-weight additives of PVP agglomerated and formed
surface gradually changed from dense to porous because solvent and non-solvent exchange
larger cavities after
became elution.
slower;As the exposure
however, the effecttime increased
of exposure timefrom 10pore
on the s tosize
1 min, the
of the mem- is
membrane
brane surface gradually changedmorphology
unclear. Membrane from dense andtostructure
porous arebecause
similarsolvent
at differentand non-solvent
vapor temperatures,
exchange became andslower;
they exist however,
as a mixturetheofeffect
α andof exposure
β forms. When time
the on thetemperature
vapor pore size was 60 ◦ C,
of the
the membrane
membrane is unclear. Membrane had the most concentrated
morphology pore size distribution
and structure are similarand the greatest
at different negative
vapor
temperatures, andcharge.
theyAs the as
exist vapor temperature
a mixture of α increased,
and β forms. someWhenother properties
the vaporalso changed. The
temperature
capillary flow rate decreased and the strength and elongation at break increased. Finally,
was 60 °C, the membrane had the most concentrated pore size distribution and the greatest
the PVDF membrane we prepared has a certain capillary flow rate and protein adsorption
negative charge.performance,
As the vapor temperature
which proves to beincreased,
effective forsome other
colloidal properties
gold tests. The also changed.
protein adsorption
The capillary flow rate of
capacity decreased
the membrane and canthe be
strength
improved andby elongation at breakand
surface modification, increased. Fi- of
the influence
humidity should be further investigated. In addition, the
nally, the PVDF membrane we prepared has a certain capillary flow rate and protein ad- surface flatness of the self-made
membrane
sorption performance, whichis lower thanto
proves that
beof the commercial
effective membrane.
for colloidal Therefore,
gold tests. The itprotein
is necessary
ad- to
optimize the formula and improve the overall uniformity of the PVDF membrane.
sorption capacity of the membrane can be improved by surface modification, and the influ-
ence of humidity should
Author be furtherConceptualization,
Contributions: investigated. InX.W. addition,
and T.H.;the surface flatness
methodology, of the T.H.;
D.C.; software, self-vali-
made membrane is lower than that of the commercial membrane. Therefore, it is necessary
dation, L.T., Z.W. and Z.C.; formal analysis, X.W.; investigation, T.H.; resources, L.T.; data curation,
D.C.; writing—original draft preparation, X.W.; writing—review
to optimize the formula and improve the overall uniformity of the PVDF membrane. and editing, Z.W.; visualization,
D.C.; supervision, Z.C.; project administration, Y.Z.; funding acquisition, Z.C. All authors have read
and agreed to the published version of the manuscript.
Author Contributions: Conceptualization, X.W. and T.H.; methodology, D.C.; software, T.H.; vali-
dation, L.T., Z.W. and Z.C.; formal analysis, X.W.; investigation, T.H.; resources, L.T.; data curation,
D.C.; writing—original draft preparation, X.W.; writing—review and editing, Z.W.; visualization,
D.C.; supervision, Z.C.; project administration, Y.Z.; funding acquisition, Z.C. All authors have read
and agreed to the published version of the manuscript.
Funding: This research was funded by [the National Natural Science Foundation of China] grant
Membranes 2023, 13, 91 13 of 14

Funding: This research was funded by [the National Natural Science Foundation of China] grant num-
ber [22078146], [the Natural Science Foundation of Jiangsu Province] grant number [BK20200091],
and [the Materials-Oriented Chemical Engineering State Key Laboratory Program] grant num-
ber [ZK202007].
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available on request from the
corresponding author.
Conflicts of Interest: The authors declare no conflict of interest.

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