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Electrospun composites nanofibers from cellulose acetate/carbon black as

efficient adsorbents for heavy and light machine oil from aquatic
environment

Article  in  Journal of the Iranian Chemical Society · June 2022

DOI: 10.1007/s13738-022-02510-1

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Journal of the Iranian Chemical Society
https://doi.org/10.1007/s13738-022-02510-1

ORIGINAL PAPER

Electrospun composites nanofibers from cellulose acetate/carbon

black as efficient adsorbents for heavy and light machine oil
from aquatic environment
Nehad A. Elmaghraby1 · Ahmed M. Omer2 · El‑Refaie Kenawy3 · Mohamed Gaber3 · Ahmed El Nemr1 

Received: 29 May 2021 / Accepted: 21 January 2022

© The Author(s) 2022

Abstract
The feasibility of preparing cellulose acetate/carbon black (CA/CB) composite nanofiber in one step through electrospinning
process and investigating its potential oil absorbability and application for machine oil removal from aquatic environment
was reported. Different CA/CB composite nanofibers were fabricated by electrospinning of cellulose acetate (CA) solution
containing different loads of 0.7, 1.5, and 2.2% CB relative to the weight of CA and labeled as CA/CB0.7, CA/CB1.5, and
CA/CB2.2. The scanning electron microscope (SEM) images showed continuous and smooth fiber with submicron diameter
ranging from 400–900 nm with good adhering of CB into CA nanofiber. Furthermore, the CA/CB composite nanofibers
exhibited high surface area compared with CA nanofiber, which reached 3.057, 2.8718 and 8.244 m ­ 2/g for CA/CB0.7, CA/
CB1.5 and CA/CB2.2, respectively. Oil adsorption tests were performed with heavy and light machine oils. The CA/CB
composite nanofibers showed higher affinity for oil removal from an aqueous solution than pure CA nanofiber. The CA/CB1.5
composite nanofiber has an exceptional performance for the adsorption of both oils, and the maximum oil adsorbed reached
10.6 and 18.3 g/g for light and heavy machine oils, respectively. The kinetic of machine oils adsorption was fitted well by
the pseudo-second-order model. Besides, CA/CB composite nanofiber exposed good adsorption properties and respectable
reusability after regeneration for four consecutive cycles. The results advocate the excellent potential of as-fabricated CA/
CB composite nanofiber as a promising reusable oil adsorbent for oil spill cleanup applications.

Keywords  Cellulose acetate · Carbon black · Composite nanofiber · Oil spill removal · Recyclability

* El‑Refaie Kenawy
[email protected]
Introduction
* Ahmed El Nemr
Oil pollution mainly results from offshore oil production,
[email protected];
[email protected] frequent oil spill accidents, marine transportation, petro-
chemical, and food industries [1–3]. Oil spills may have
Nehad A. Elmaghraby
[email protected] long-term negative consequences for the ecosystem, affect-
ing marine life survival and human economic activity [4, 5].
Ahmed M. Omer
[email protected] Oil was cleaned using traditional methods such as in situ oil
burning on water, skimming, ultrasonic separation, mechani-
Mohamed Gaber
[email protected] cal extraction, chemical oxidation, flotation, centrifugation,
and gravity separation [1, 6, 7]. Each of these methods has
1
Environmental Division, National Institute of Oceanography its own limitation [8]. The cleanup technique can be used
and Fisheries, El-Anfoushy, Kayet Bey, Alexandria, Egypt to separate oil/water-free mixtures in most situations, but it
2
Polymer Materials Research Department, Advanced has drawbacks such as poor separation performance, high
Technology and New Materials Research Institute energy costs, and secondary emissions [9–11]. The latter
(ATNMRI), City of Scientific Research and Technological
Applications (SRTA-City), New Borg El‑Arab City, involves the production of smoke and dust as a result of
P.O. Box: 21934, Alexandria, Egypt in situ oil burning on water, as well as contamination by
3
Department of Chemistry, Faculty of Science, University toxic substances as a result of the use of industrial chemical
of Tanta, Tanta 31527, Egypt dispersants [1, 12], and they are also ineffective for oil/water

13
Vol.:(0123456789)
 Journal of the Iranian Chemical Society

emulsion separation [1, 13]. As a result, oil adsorbents that of oil pollution [19, 20]. Fiber surface structure, surface
are both reliable and cost-effective as a mechanical extrac- adsorption, and capillary voids action all play a role in the
tion tool are a promising way to deal with oil spills [4]. oil adsorption process. Esterification is commonly used to
The synthetic inorganic minerals materials, natural fiber increase the hydrophobicity of fibers in order to improve
materials, and organic polymers are the three classes that their oil adsorption ability [46]. By simply manipulating
covered the adsorbent materials used in oil spill cleanup a few parameters, solid or internally porous fibers, or a
[12–16]. The high uptake capacity, hydrophobicity, and smooth or rough fiber surface, composite mats can be
oleophilicity, as well as good recoverability, are very impor- manufactured, and nanoparticles can be incorporated by
tant to select the ideal adsorbent material for oil removal simply adding the necessary nanoparticles to the polymer
[17, 18]. Significant research on natural organic adsorbents solution [13, 15, 47].
has recently been conducted such as the use of Kapok fiber Cellulose is one of the world's most plentiful and long-
[23, 24], cotton, and rice husks [25], cotton cellulose acetate lasting biopolymers, and it can be processed into a valuable
[26], carbon nanofiber grafted polyurethane [23], cellulose cellulose acetate derivative with a wide range of industrial
acetate nanofiber membranes [20], raw flax fiber [18], and uses [48–50]. Cellulose is inexpensive, biocompatible, and
acrylic acid-grafted pre-plasma nanofibers [25]. Despite biodegradable, and it has many unique properties such
the fact that natural organic adsorbents are mostly biode- as high strength, light weight, and chemical modification
gradable, some of them adsorb both water and oil, reducing capacity [51, 52]. Cellulose acetate (CA, an acetate ester of
separation efficiency, and others can sink during adsorption cellulose) has been of increasing interest in the past decade
in harsh sea conditions [26]. Water softening can also be in the area of nanofibers [53, 54]. Because of their biocom-
done with a polymeric-clay-magnetite hybrid resin [27] and patibility, biodegradability, and high affinity with other sub-
manufacturing of pH-sensitive PVA/PVP/MWCNT and stances, electrospinning of cellulose and its derivatives has
PVA/PEG/MWCNT nano-composites for application as received a lot of attention [55]. Since cellulose is difficult
drug release [28]. to dissolve in traditional solvents, CA is often used as a cel-
On the other hand, synthetic adsorbents designed to com- lulose substitute [56–59]. It can be used in high-value appli-
bat oil spillages are non-biodegradable man-made materials cations including chromatography [60], fuel cells [61, 62],
and they can trigger serious disposal issues after their use enzyme bioreactors [63], self-cleaning textiles [64], photo-
[13, 15, 29, 30]. The most famous and widely used synthetic chromic devices [65], water treatment [66], and biosensors
adsorbents for oil removal are polyurethane (PU), polyethyl- [67]. Due to its high hydrophobicity, strong solubility in a
ene (PE), and polypropylene (PP) [31]. Chen and Pan [32] variety of solvent systems, and low cost, the CA polymer is
and Pavía-Sanders et al. [33] fabricated different oil adsor- one of the most commonly used polymers in the preparation
bent materials having magnetic properties for easy re-pick of nanofiber membranes [53, 68].
after the oil adsorption. The β-cyclodextrin oil adsorbents Recently, several attempts have been made to increase
were reusable where the adsorbed oil can be desorbed by a electrospun cellulose nanofiber performance for oil treat-
chemical extraction method [34]. ment. There has been a study on a super hydrophilic gra-
Electrospinning is a rare, flexible, and efficient technique phene oxide-electrospun cellulose composite nanofiber
for producing nanofiber materials on the sub-micrometer membrane for high-efficiency oil/water separation [69]. The
scale, ranging from approximately 50 nm to many microm- oil/water separation properties of modified cellulose acetate
eters, with fiber diameters ranging from tens of nanometers nanofibers with perfluoroalkoxy silanes have been investi-
to micrometers [35, 36]. The electrospun nanofiber mats that gated and reported by Arslan et al. [70]. For oil/water sepa-
result have remarkable properties such as extremely large ration, a cellulose nanofiber (CNF) aerogel was fabricated
specific surface areas, porous nanostructures with high and modified by sodium periodate oxidation [71].
degrees of interconnection, and modifiable natures [37]. Carbon black has attracted much interest since 1990s,
Because of these properties, electrospun fibers are suitable practically in the field of chemistry, physics, and materials
candidates for applications such as filtration [38], drug deliv- science. It is a form of elemental carbon that consists of
ery [39], chemical and biological protection sensors [40, finely particles of carbon produced by incomplete combus-
41], tissue engineering [42], tissue repair [43], lithium-ion tion of heavy petroleum products, and it is one of the most
batteries [36] and solar cells [44]. stable chemical products [72]. Porous characteristics such
The electrospinning technique is an excellent method as surface area, pore depth, and pore size distribution give
for creating unique wet-able surfaces [18, 35, 45]. it high absorption capacities. In the rubber industry, carbon
Recently, a rapid expansion of the nanofibers materials has black (CB) has been used to strengthen rubber to increase its
been fabricated as an effective oil/water separation because resistance to abrasion, fatigue, tear, and flexing [73]. Many
fibers can be easily reused, as well as this type of fib- elastomers' tensile strength and processing characteristics
ers shows a good prospect of application in the treatment are also improved (natural and synthetic) [74].

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Journal of the Iranian Chemical Society

A new effective eco-friendly cellulose acetate and car- Electrospinning of CA/CB solutions
bon black (CA/CB) composite nanofiber for the removal
of machine oil from water bodies was attempted in this Using a 20 mL syringe fitted with a blunt-ended metal nee-
study. In order to allow their exponential advantages to dle, electrospinning was performed in horizontal orienta-
be combined, CA and CB were simultaneously fabricated tion at an applied voltage of + 26 kV and –10 kV using a
into one mat via electrospinning technique under optimum Bioinicia, FLUIDNATEK LE-50 electrospinning unit. The
preparation conditions. The CA/CB composite nanofiber temperature was 24 °C, and humidity was less than 20% [76,
was characterized using various characterization tools, 77]. The composite polymer solution was subjected to elec-
while its oil adsorption capacity was assayed under dif- trospin using a 20-mL syringe pump operating at 10 mL/h
ferent adsorption conditions. Moreover, kinetics of the oil and 10 cm distance far from the collector. Webs were col-
adsorption process and the aptitude of the developed com- lected on cylinder aluminum collector with rotation speed of
posite nanofiber to reuse were also explored. 500 rpm. The electrospun samples were removed from the
collector and washed with ethanol to complete removal of
PEG and then dried in a vacuum oven at 50 °C for 24 h and
labeled as CA/CB0.7, CA/CB1.5, and CA/CB2.2 [78]. The
Materials and methods electrospin was continued for 10 h for each concentration.

Materials Characterization of the electrospun CA/CB

composites nanofibers mats
CA (acetyl content: 29–46%, Mn: 50,000) was pur-
chased from ALPHA Chemie, India. N-Hexane 95% from FTIR spectroscopy of the samples was conducted in the
M-TEDIA. Carbon black (mesoporous of 10 ± 1 nm aver- wave number range from 400 to 4000 ­cm–1 by using Bruker
age pore diameter, BET surface area of 150 ­m2/g, and par- VERTEX70 connected to platinum ATR unit (model
ticle size of 45 ± 5 µm) from ASMA dye, Egypt. Polyeth- V-100), Germany. Surface area and pore size distribution
ylene glycol (PEG) from ACROS Organic (Mwt = 200). of fabricated CA/CB composite nanofibers were carried out
Acetone for HPLC grade from Central Drug House, assay by nitrogen adsorption–desorption isotherms measured at
99.8%. N,N-dimethylacetamide (DMAA) from Merck. 77 K using BELsorp mini II, BEL Japan, Inc., Japan. The
Ethyl alcohol from International Company for sup & Brunauer–Emmett–Teller (BET) equation was used to meas-
MED, Industries, Egypt. Exxon Mobil, Egypt (Fully Syn- ure the real surface area from the ­N2 adsorption isotherm,
thetic Motor Oil 5 W-50, Rally formula) provided heavy and the single point total pore volume was determined from
(Viscosity 32 cSt at 40 °C) and light machine oil (Viscos- the nitrogen sum adsorbed at 0.95 relative pressure. A scan-
ity 5.5 cSt at 40 °C), and all chemicals were used without ning electron microscope (SEM) was used to investigate the
further purification. morphology and scale of the samples (JEOL, Model JSM
6360LA, Japan). Sample was coated by a gold thin layer for
SEM analysis. An Image-G program was used to calculate
Preparation of CA/CB solution the average fiber diameter (AFD) of the electrospun fibers.
Thermogravimetric analysis (TGA) of the fabricated CA/CB
CA (12 percent w/v) was dissolved in a DMAA/acetone nanofiber was analyzed by SDT 650 Simultaneous Thermal
binary solvent mixture (4:1 v/v) to produce homogene- Analyzer, the USA. Each powdered sample was heated by
ous solutions. PEG was used to help the electrospinning 10 °C/min. Up to 900 °C, about 15 mg of each samples was
process resolve the surface tension of the solution. (The taken in silica crucible and subjected to pyrolysis under ­N2
ratio of PEG/CA was 1:1 w/w.) Three different concentra- flow [79].
tions of carbon black (CB) were added to CA solution
(0.7, 1.5 and 2.2 w % of CA) to obtain CA/CB composite Water uptake capacity
electrospun. Further increase of the CB percentage led to
precipitate of the excess CB and close the needle. Com- The ability of CA/CB composite nanofiber mats to adsorb
plete polymer dissolution in the co-solvent was prepared water was investigated in order to better understand how
by continuously stirring at room temperature for 2 h in water molecules diffuse into the nanofiber mats, which is
500 mL conical flasks, and then, polymer solutions were critical for oil removal. The nanofiber mats (0.6 g; fiber
ultrasonicated overnight at room temperature. After mix- shape) were immersed directly in certain amount of three
ing, the polymer solutions were left undisturbed for a day water medium of pH values 3, 6 and 11 at room temper-
to facilitate the release of air bubbles in the solution [75]. ature for 24 h, and then, the samples were taken out and
dried gently with filter paper to remove the excess water and

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 Journal of the Iranian Chemical Society

subsequently weighed to define weight of swollen nanofiber free oil dripping out for 5 min before being weighted. The
(Ws) and after the swollen product was dried at 50 °C to a samples were then moved to the piston, where the adsorbent
constant weight (weight of dried nanofiber, Wd). Following was pressed five times through the press to remove the oil.
Eq. (1) is used to measure the percentage of swelling ratio A small amount of n-hexane was applied to the press dur-
of the sample [80]. ing the pressing stage to aid in the extraction of the oil. By
using the centrifuge technique defined in ASTM D1696-91,
Ws − Wd
Swelling ratio% = × 100 (1) the liquid was collected in a graduated centrifuge tube for
Wd
water content determination [83]. Each sample was tested
for 3 times, and only the mean values were reported. The oil
Determination of oil adsorption capacity adsorption capacity (g/g) is calculated according to Eq. (4).
and retention capacity (static test) ( )
W S − W W − Wi
Oil sorption capacity = (4)
The oil adsorption ability and retention were calculated Wi
using the standard procedure defined in ASTM 726–06,
where W S is the weight of saturated adsorbent
“Standard Test Method for Absorbent Performance of
(water + oil + adsorbent), WW is the weight of adsorbed
Adsorbents.” The fibers (0.5 g in mass) of CA/CB0.7, CA/
water, and Wi is the initial dry weight of adsorbent [84].
CB1.5, and CA/CB2.2 composites nanofibers were placed
into 250 mL glass beaker for 1 h, and the samples were
weighed and then slowly immersed in 30 mL oil (heavy or
Kinetics studies
light machine oils) at room temperature (24 ± 2 °C). After
soaking for the desired time, the samples were taken out and
The experimental data were further analyzed using a pseudo-
left to drain for 5 min followed by lifted for 24 h through a
first-order model and a pseudo-second-order model, as
wire mesh to remove any loosely attached liquid and free
expressed in linear forms in Eqs. (5) and (6), respectively, to
oil dripping out then weighed for each time. All of the tests
better understand the adsorption mechanism [19, 20, 85–87]:
were repeated three times, with the average value used to
determine the final results. The oil uptake capacity of the K1
(5)
( )
log qe − qt = log qe − t
samples was also carried out to measure the amount of heavy 2.303
or light machine oil taken by the samples. The oil adsorption
capacity (Q) and retention capacity are calculated according t 1 t
to Eqs. (2) and (3) [22, 81]. qt
= 2
K2 × qe
+
q (6)
e
W5 − Wi
Oil sorption capacity(Q) = (2) where qt (g/g) and qe (g/g) are the amount of oil adsorbed
Wi at time t (min) and equilibrium, respectively, and K1 and K2
are the adsorption rate constants.
W24 − Wi
Oil retention capacity = (3)
W5 − Wi
Reusability test
where Wi is the initial mass of sample before adsorption (g),
W5 is the mass of oil wetted sample at 5 mind ripping (g), From an economic standpoint, reusability is one of the
and W24 is the mass of oil wetted sample at 24 h dripping (g). most important considerations to consider when choos-
ing products. At room temperature, 0.5 g of dried CA/CB
Adsorption capacity determination (oil/water composite nanofiber samples were immersed in 30 mL oil
solution) (Dynamic test) for 1 h. The samples were then drained for 5 min until the
wet sample was weighed. Finally, the oil was removed
The adsorption test was carried out using light and heavy from the oil-saturated samples by centrifugation, followed
machine oils as model oils, with the aim of determining if by washing with 3  mL hexane and centrifugation four
structured fiber could be used to selectively absorb spilled times. After 10 min, the samples were put in a 60 °C oven
oil from water surfaces [22, 81, 82]. Machine oil (30 mL) for 24 h before being reused. The process was replicated
was poured over 50 mL of seawater, and then, 0.4 g struc- in a water/oil system with 0.4 g of fiber in 50 mL seawater
tured fiber was put in the 250 mL jar containing the oil sam- and 30 mL oil for 15 min for heavy machine oil and 1 h
ple and the seawater was mounted in a shaker at 200 rpm. for light machine oil, and the oil adsorption capacity of the
The samples were taken out at various intervals (5, 10, 15, sample was measured after each cycle as described above.
30, and 60 min), then raised and put on a wire mesh with

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Journal of the Iranian Chemical Society

Result and discussion obvious that very few CB particles were adhered to the
surface of the fibers. This finding revealed that the pres-
Characterization of cellulose/carbon black ence of a small amount of carbon black has a minor impact
composites nanofibers on nanofiber diameter. When a small amount of carbon
black is added to cellulose acetate nanofiber, the diameter
Scanning electron microscope of the nanofiber increases. Surprisingly, SEM research
revealed that the surface of nanofibers appeared dense and
The morphologies and fiber diameter distribution of CA, relatively homogeneous tiny particles, indicating that CB
CA/CB0.7, CA/CB1.5, and CA/CB2.2 composites nanofib- adhered to the surface. There are also several pores on the
ers are exhibited in Fig. 1. The morphology structure was fiber's surface, which resulted from the removal of PEG
bead-free cylindrical and smooth fibers with submicron from the surface. [88] (Chen et al. 2009).
diameters. Fiber diameter of the composites nanofibers
increases with increasing of CB content. AFD for CA, FTIR spectra
CA/CB0.7, CA/CB1.5, and CA/CB2.2 were 495, 628,
727, and 831 nm, respectively, as calculated as an average Figure 2 shows the FTIR spectra of CA, CB and the CA/
value from 20 measurements using ImageJ software. It was CB0.7, CA/CB1.5, and CA/CB2.2 composites nanofibers.
Cellulose acetate and composite samples exhibited same

Fig. 1  Images of SEM for a

CA nanofiber, b CA/CB1.5
composite nanofiber, c CA/
CB0.7 composite nanofiber, d
CA/CB2.2 composite nanofiber
and e surface morphology of
the distribution of CB into CA
nanofiber for CA/CB2.2 using
15 kV and 5000X magnification

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 Journal of the Iranian Chemical Society

100%
95% 99%
98%
Transmiance [%]

Transmiance [%]
85%
97%
96%
75%
95%

65% 94%
93%
55% 92%
(a) CA 91% (b) CB
45% 90%
3400 2400 1400 400 3400 2400 1400 400
Wavenumber cm–1 Wavenumber cm–1

95% 95%

85% 85%

Transmiance [%]
Transmiance [%]

75% 75%

65% 65%

55% 55%

45% 45%
(c) CA/CB0.7 (d) CA/CB1.5
35% 35%
3400 2400 1400 400 3400 2400 1400 400
Wavenumber cm–1 Wavenumber cm–1

100%
95%
90%
85%
Transmiance [%]

Transmiance [%]

80%
75%
70% (f)
65%
CA
60% 55% CACB0.7
CACB1.5
50% 45% CACB2.2
(e) CA/CB2.2 CB
40% 35%
3400 2400 1400 400 3400 2400 1400 400
Wavenumber cm–1 Wavenumber cm–1

Fig. 2  FTIR spectra of a CA;, b CB, c CA/CB0.7, d CA/CB1.5, e CA/CB2.2, f a-e in one plot

peaks as broad band around 3394 ­cm−1 assigned to O–H three composites. The adsorption peak at 1737 ­cm−1 origi-
stretching vibration and small peak at 2943 ­cm–1 assigned nates from C = O stretching vibration of ester [89]. C-O and
for C-H stretching vibration in CA was highly increased in C-H bending vibrations are responsible for the bands around
the composite nanofiber samples and appeared as two peaks 1228 and 1368 ­cm–1, respectively. C-O stretching in cellu-
at 2921.4 and 2872.6 ­cm–1 due to the presence of CB in the lose acetate was given a wide band at 1050 ­cm–1. The FTIR

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Journal of the Iranian Chemical Society

spectra of CB exhibited three peaks at 850 ­cm–1 assigned capillary condensation in the mesoporous nanofiber. Since
to (C–C) carbon skeleton, 1530 ­cm–1 assigned to stretching the surface properties of the adsorbents are important, BET
(C–C) and 2395 ­cm–1 originate from C ­ O2. By comparison measurements were used to calculate the surface area,
FTIR spectra of CA/CB composite fibrous with that of pure
CA fibrous, there is no change on the peaks.

Surface area analysis Table 1  Surface area, total pore volume and mean pore diameter of
composite samples

Adsorption–desorption plot of CA, CB, CA/CB0.7, CA/ Sample SBET Vm Mp (nm) Smi Vmi ­(cm3/g)
CB1.5, and CA/CB-2.2 is shown in Fig. 3. All samples code ­(m2/g) ­(cm3/g) ­(m2/g)
belong to type V isotherms corresponding to IUPAC clas- CB 47.422 0.1339 11.297 52.011 0.1328
sification indicating that they are low energy, homogeneous CA 25.593 0.0253 3.961 23.115 0.0301
solid surface possessing mesoporosity [90, 91]. It can be CA/ 3.0571 0.0094 12.307 3.596 0.0099
achieved using mesoporous or microporous adsorbents with CB0.7
weak adsorbent–adsorbate interactions. Besides, isothermal CA/ 2.8718 0.0086 12.516 3.3795 0.0095
loop deceleration does not stabilize at relative pressures CB1.5
near saturation vapor pressure, indicating that mats contain CA/ 8.244 0.0178 9.1128 7.919 0.0204
CB2.2
slit-like pores. The hysteresis loop was brought about the

Fig. 3  a ­N2 gas adsorption – desorption isotherms. b BET analysis, and c BJH analysis of CA, CB, CA/CB0.7, CA/CB1.5, and CA/CB2.2
nanofiber composite

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 Journal of the Iranian Chemical Society

average pore diameter, and pore volume of the CA and CA/ and CA/CB2.2, respectively, corresponding to the loss of
CB composites nanofibers, and the results are shown in moisture, while at higher-temperature (i.e., 350 –400 °C)
Table 1. gave weight losses 73.01, 77.7, 75.47, and 74.69% for CA,
The surface area of the CA was noticed to be slightly CA/CB0.7, CA/CB1.5 and CA/CB2.2, respectively. In addi-
decreased with increasing CB content in the composite tion, the residues of samples after thermal decomposition
nanofiber up to 1.5% and then further increasing CB content at 900 °C were 16.67, 11.34, 12.21, 11.56%, and 16.67%
up to with 2.2% CB. These observations could be ascribed for CA, CA/CB0.7, CA/CB1.5, and CA/CB2.2, respectively.
to the surface irregularities of the CA/CB. The specific sur- Differential scanning calorimetry (DSC) analysis is used
face area values of CA and CB were 25.593 and 47.422 to have specific information onto thermal transitions state
­m2/g, respectively. Besides, the specific surface area of CA [93, 94]. Via monitoring the heat flow over temperatures, it
nanofiber was found to be higher than that reported by Goetz offers insight into a material’s phase changes (melting point,
et al. [92] as 2.73 m­ 2/g for CA nanofiber. The specific sur- boiling point, and fusion), glass transition temperatures
face area (SBET) values of CA/CB0.7, CA/CB1.5 and CA/ (Tg), and the heat capacity (Cp). DSC analysis of pure CA
CB2.2 composites nanofibers were 3.057, 2.8718 and 8.244 nanofiber and CA/CB composites nanofibers with different
­m2/g, respectively. The mean pore diameters (Mp) of 10.638, CB loadings is shown in Fig. 4b. All samples exhibited a
12.307, 12.516, and 9.1128 nm were determined for CA/ endopeak represented a temperatures at 61.07, 84.82, 85.99
CB0.7, CA/CB1.5 and CA/CB2.2 composites nanofiber and 78.74 °C for CA, CA/CB0.7, CA/CB1.5 and CA/CB2.2,
mats, respectively (Fig.  3). Meanwhile, the maximum respectively, that are attributed to water loss from the sam-
micropore surface area (Smi) and micropore volume (Vmi) of ple. Similarly, the melting peak represented a degradation
CB, CA, CA/CB0.7, CA/CB1.5 and CA/CB2.2 nanofiber temperatures was 575.17, 609.65, 478.65 and 453.89 °C for
mats were 52.011, 23.115, 3.596, 3.3795, 7.919 m ­ 2/g and CA, CA/CB0.7, CA/CB1.5 and CA/CB2.2, respectively [54,
3
0.1328, 0.0301, 0.0099, 0.0095, and 0.0204 c­ m /g, respec- 95].
tively. These results showed that the surface area and pore
volume were dramatically decreased by addition of carbon Swelling behavior
black to the cellulose acetate.
The swelling activity of the pure CA and composite CA/CB
Thermogravimetric analysis (TGA) fibrous mats was investigated further (Fig. 5). The swelling
properties of CA and CA/CB composites were studied in
TGA in a nitrogen atmosphere was used to assess the ther- media of different pH values (3, 6 and 11) for 24 h. The max-
mal stability of the electrospun fibers. Figure 4 shows the imum swelling ratio of pure CA mat was 130.4% at pH 6,
TGA curves of pure CA nanofiber, and CA/CB nanofiber and all of the CA/CB composite fiber mats exhibited higher
composites with different CB loadings. All samples fiber values of swelling at the same pH for CA/CB0.7 (166.1%),
mat exhibited two steps thermal transitions, with the low- CA/CB1.5 (188.9%) and CA/CB2.2 (153.3%). As a result,
temperature(i.e., 50–150  °C) gave weight losses 10.32, the swelling ratio was lowest in pH 3 and significantly
10.97, 12.31, and 13.76% for CA, CA/CB0.7, CA/CB1.5, higher in neutral and alkaline environments. The alkaline

Fig. 4  (a) TGA, b DSC curves of the CA, CA/CB0.7, CA/CB1.5, and CA/CB2.2 composites nanofibers at temperature ranged between 50 and
900 °C under flow of N
­ 2 (100 mL/min)

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Journal of the Iranian Chemical Society

200 PH 3 Basically, the high viscosity can improve the oil adsorption
180 PH 6 process through boosting the adhered oil molecules on the
PH 11 adsorbent surface [61, 62]. On the other hand, light machine
160
oil was more ready to drip out from the stain steel mesh
140 than heavy machine oil [22, 98]. The synthetic fibers demon-
Swelling %

120 strated high oil adsorption and retention capabilities which

100 adsorbed more than 12 times the mass of oils over their own
weight and retained more than 76% of the oil adsorbed after
80
24 h of dripping. Furthermore, CA nanofibers with differ-
60 ent CB contents showed a high oil capacity than neat CA
40 nanofiber. The results referred that CA fiber with 2.2% CB
20 (CA/CB2.2) was preferable to obtain higher oil adsorption
0
performance, and however, more oil retention was observed
CA CA/CB0.7 CA/CB1.5 CA/CB2.2 for CA fiber with 1.5% CB (CA/CB1.5). Introducing more
Nanofibers amounts of CB to the composite nanofibers may reduce the
ability of the composite nanofibers to retain oil molecules
Fig. 5  Swelling equilibrium behaviors of the CA, CA/CB0.7, CA/
in the fibers [32, 99].
CB1.5, and CA/CB2.2 composites nanofibers at pH 3, 6, and 11 at
room temperature Batch adsorption experiments

Batch adsorption experiments in oil/water mixtures were

condition obviously increased swelling, whereas the acidic used to determine the maximum oil adsorption capacities of
condition decreased swelling, and this finding is consist- CA/CB0.7, CA/CB1.5, and CA/CB2.2 for machine oil. The
ent with that reported in the literature [96, 97]. The swell- results clarified that CA/CB0.7, CA/CB1.5 and CA/CB2.2
ing ratio of CA/CB composite nanofiber was higher than exhibited fast adsorption rate during the initial 5 min in case
that of native CA nanofiber. This is because the presence of heavy and light machine oil (Fig. 6). Moreover, the maxi-
of CB increases the inter-spaces between the CA chains, mum oil adsorption capacity for heavy and light machine
which improves the penetration of water molecules into the oils was recorded after 15 min as 18.37 and 10.621 g/g,
nanofiber network, and as a result, the swelling ratio rises respectively, using CA/CB1.5 composite nanofibers. The
[80]. However, increasing the amount of CB to 2.2% in the oil adsorption potential increases marginally within the first
composite reduced the swelling that might be attributed to 15 min of contact time, and then, the adsorption process
the possibility that excess CB might block pores in the fiber becomes relatively sluggish for all adsorbents, which can
network and thus reduce water adsorption. be due to the fact that the oil on the outside of the fibers
slowly penetrates into the adsorbent material's hollow cavity.
Oil adsorption and retention capacity This observation is consistent with the findings reported by
Thompson et al. [100] and Wang et al. [19, 20].
Oil adsorption and retention capability are two critical
properties of an adsorbent used to recover spilled oils [1]. Kinetics studies
Table 2 lists the oil adsorption and retention capacity values
for the fabricated composites. In general, heavy machine oil The kinetics of oil adsorption defines the rate of oil absorp-
adsorbs significantly more than light machine oil. This may tion by fiber; this rate determines the operation, and it is nec-
be explained by the fact that heavy machine oil is viscous essary to determine the optimum operating conditions. The
in comparison to light machine oil in the same unit volume. kinetic parameters provide critical information for designing

Table 2  Oil capacity and oil Sample code Heavy machine oil Light machine oil
retention of heavy and light
machine oil in 20 mL oil with Oil adsorption capac- Oil retention capacity Oil adsorption capac- Oil retention
0.5 g of CA nanofiber and CA/ ity (g/g) (%) ity (g/g) capacity (%)
CB composites nanofibers for
1 h (dynamic test) CA 5.89 76 4.45 80
CA/CB0.7 12.31 76 10.62 82
CA/CB1.5 12.56 84 12.01 83
CA/CB2.2 12.73 72 12.95 81

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 Journal of the Iranian Chemical Society

(a) (b)
20 12

Oil Adsorpon Capacity (g/g)

Oil Adsorpon Capacity (g/g)

18
10
16
14 8
12 CA/CB0.7
CA/CB0.7
CA/CB1.5
10 CA/CB1.5 6 CA/CB2.2
CA/CB2.2 CA
8
CA 4
6
4 2
2
0 0
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
Time (min) Time (min)

Fig. 6  Oil adsorption capacity of a heavy machine oil, b light machine oil (5 mm of oil thickness on 400 mg of adsorbent) at room temperature

(a) 5.0 (b)

CA/CB0.7 8.0 CA/CB0.7
4.5 CA/CB1.5 7.0 CA/CB1.5
4.0 CA/CB2.2
6.0 CA/CB2.2
t/qt (min g/mg)

t/qt (min g/mg)

3.5
3.0 5.0
2.5 4.0
2.0
3.0
1.5
2.0
1.0
0.5 1.0
0.0 0.0
0 10 20 30 40 50 60 70 0 10 20 30 40 50 60 70
Time (min) Time (min)

Fig. 7  The Plot t/qt versus t of the pseudo-second-order model for removal of a heavy machine oil, b light machine oil (5 mm oil thickness) by
CA/CB composites nanofibers at room temperature

Table 3  The first- and Parameter First-order kinetic model Second-order kinetic model
second-order adsorption rate
3 2
constants, as well as measured Sample Machine Oil qe(exp.) k1×10 qe(calc.) R k2×103 qe(calc.) h R2
and experimental qe values for
heavy and light machine oils, CA/CB0.7 Heavy 13.11 117.22 122.18 0.455 40.37 13.97 7.88 0.999
were compared using CA/CB CA/CB1.5 18.37 167.66 1948.04 0.455 30.36 19.19 11.18 0.999
composite nanofibers CA/CB2.2 14.05 114.46 88.23 0.34 45.20 14.90 10.04 0.999
CA/CB0.7 Light 9.061 14.74 1.98 0.369 41.09 10.28 4.34 0.998
CA/CB1.5 10.11 -0.69 1.00 0.0003 66.79 10.70 7.64 0.997
CA/CB2.2 8.89 18.65 2.39 0.414 13.21 9.52 2.83 0.994

and modeling oil adsorption processes. As a result, the kinet- is more applicable to the kinetics of oil adsorption. The
ics of oil adsorption on the prepared fiber were investigated pseudo-second-order kinetics model was expressed via plot
using pseudo-first-order (Eq. 5) and pseudo-second-order of t/qt versus t, where k2 and qe obtained from the intercept
(Eq. 6) kinetic models. The value of the correlation coef- and slope of the plot (Fig. 7). The linear plots of t/qt versus t
ficients expresses the applicability of a kinetic model (R2, show good agreement between experimental and calculated
values close or equal to 1). The model with the higher value qe values for different samples for heavy and light machine

13
Journal of the Iranian Chemical Society

oils (Table. 3). The R2 values for the pseudo-second-order the stability and chemical composition of the fibers. The
kinetic model are > 0.994. Based on these findings, it is findings suggest that the CA/CB composite nanofibers can
assumed that the pseudo-second-order kinetic model, as be reused and recycled several times using the centrifuge
opposed to the pseudo-first-order kinetic model, offered a process. As a result, they are highly promising oil-absorbing
better correlation for oil adsorption onto fiber. materials for oil spill cleanup.

Reusability
Conclusion
The material's reusability is also an effective indicator for
removing unintentionally spilled oil. Using n-hexane extrac- The current study found that cellulose acetate/carbon black
tion, the oil-saturated samples were recycled for multiple composite nanofibers absorbed more oil than pure cellulose
adsorption/desorption cycles. The centrifuge method of acetate in oil and oil/water mixtures. The chemical com-
recovering oil from adsorbent material is both cost-effective positions, surface morphology, and thermal stability of the
and practical. As a result, the recovery of the oil from the formed composite nanofibers were investigated using FTIR,
adsorbent material, as well as the feasibility of reusing the SEM, and thermal analysis tools. A pseudo-second-order
adsorbents, was investigated. The changes in oil adsorption model can be used to suit the relevant kinetics data. This
capacity of CA/CB0.7, CA/CB1.5, and CA/CB2.2 for oil/ indicated that CA and CB had synergetic effect. In addi-
water system are displayed in Fig. 8 and Table. 4 for static oil tion, the CA/CB composites nanofibers showed a good oil-
adsorption indicated that the fibers show higher oil uptake absorption capacity with a decent reusability for 4 repeated
in the first cycle, and then, its adsorption capacity decreased cycles. Based on these findings, there is no question that
and remain constant in the other cycles. Teli and Valia [101] the adapted fibers can be used as a promising replacement
reported that hexane extraction did not considerably affect for traditional oil adsorbents in the cleanup of oil spills in

(a) 100 (b) 100

90 90
oil retenon capacity %

oil retenon capacity %

80 80
oil capacity (g/g)

oil capacity (g/g)

70 70
CA/CB0.7 oil capacity CA/CB0.7 oil capacity
60 60
CA/CB0.7 oil retenon CA/CB0.7 oil retenon
50 CA/CB1.5 oil capacity 50 CA/CB1.5 oil capacity
40 CA/CB1.5 oil retenon 40 CA/CB1.5 oil retenon
CA/CB2.2 oil capacity 30 CA/CB2.2 oil capacity
30
CA/CB2.2 oil retenon CA/CB2.2 oil retenon
20 20
10 10
0 0
0 1 2 3 4 5 0 1 2 3 4 5
Cycle of sorpon Cycle of sorpon

Fig. 8  The reusability (oil capacity and oil retention) of CA/CB composites nanofibers for a heavy machine oil/water, b light machine oil system
for 4 cycles

Table 4  The reusability of CA/ Cycles Heavy machine oil Light machine oil
CB composites nanofibers for
dynamic oil (4 cycles) for heavy CA/CB0.7 CA/CB1.5 CA/CB2.2 CA/CB0.7 CA/CB1.5 CA/CB2.2
and light machine oils
OC OR OC OR OC OR OC OR OC OR OC OR

0 12.09 82.92 12.56 83.89 13.70 71.73 10.62 82.27 12.01 82.95 13.62 81.40
1 11.97 85.02 10.33 85.87 11.40 80.20 9.20 84.63 9.89 84.82 10.43 91.75
2 9.95 88.52 9.35 88.45 9.36 91.92 7.29 90.70 8.20 86.41 7.36 92.44
3 8.47 90.63 8.54 91.61 7.47 93.72 7.08 95.52 6.57 88.94 6.75 95.98
4 8.47 90.63 8.54 91.61 7.47 93.72 7.14 95.12 6.41 88.76 6.81 95.42

OC oil capacity (g/g); OR oil retention (%)

13
 Journal of the Iranian Chemical Society

aqueous environments. The maximum oil adsorption capac- New York. [ISBN-10: 1608764877, ISBN-13: 9781608764877].
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partial financial support of this work (Project No. CB-4874, CB-22816 Environ. Prot. 154, 155–167 (2021). https://​doi.​org/​10.​1016/j.​
and IG-34795). psep.​2021.​08.​009
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efficient oil/water separation. Process Saf. Environ. Prot. 139,
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Innovation Funding Authority (STDF) in cooperation with The Egyp- 10. A. Jamsaz, E.K. Goharshadi, Flame retardant, superhydrophobic,
tian Knowledge Bank (EKB) for its partial financial support of this and superoleophilic reduced graphene oxide/orthoaminophenol
work (Project No. CB-4874, CB-22816 and IG-34795). polyurethane sponge for efficient oil/ water separation. J. Mol.
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