Cellulose (2024) 31:6897–6909

https://doi.org/10.1007/s10570-024-06020-6

ORIGINAL RESEARCH

Cellulose formulations for hair modelling

José Pedro Carvalho · Madalena Martins ·
Artur Cavaco‑Paulo

Received: 13 February 2024 / Accepted: 18 June 2024 / Published online: 3 July 2024
© The Author(s) 2024

Abstract Chemical processes to change the hair the surface of the hair fiber. ATR-FTIR corrobo-
shape can lead to damaged hair fibre. Here, we pro- rate the presence of functional groups of cellulose
pose benign formulations based on different types of on the coated hair fiber. SEM images revealed that
cellulose using imidazolium ionic liquids (ILs) and the treated hair fiber preserved it structural integ-
a commercial serum as solvents. Formulations with rity, especially for the 3% CMC formulation. Those
concentrations at 3% and 0.5% of HEC (Hydroxy- formulations also presented good mechanical wear
ethyl cellulose) and CMC (Carboxymethylcellulose) determined by mass loss percentage. The novelty of
showed the best results after washing, around 10% this work is the methodology established associated
of curling effect. Images from fluorescence micros- with the cellulose formulation for hair modelling up
copy enable to observe the coating layer formed on to three washes.

J. P. Carvalho · A. Cavaco‑Paulo
Centre of Biological Engineering (CEB), University
of Minho, Campus of Gualtar, Braga 4710‑057, Portugal

J. P. Carvalho · M. Martins (*) · A. Cavaco‑Paulo (*)

Solfarcos, Pharmaceutical and Cosmetic Solutions, Braga,
Portugal
e-mail: mms@solfarcos.com
A. Cavaco‑Paulo
e-mail: artur@deb.uminho.pt

A. Cavaco‑Paulo
LABBELS – Associate Laboratory, Braga/ Guimarães,
Portugal

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Graphical Abstract

Keywords Cellulose · Hair fibre · Shape · involves two steps, reduction and oxidation. In the
Mechanical fatigue reduction step, thioglycolates which are toxic and car-
cinogenic are widely used to break the disulfide bonds
of keratin hair fibers to allow shaping of the hair fiber
into the desired form. In the oxidation step, the new
Introduction hair shape is fixed by re-forming the disulfide bonds
in the presence of an oxidizing agent, like hydrogen
The increased interest for benign and friendly cos- peroxide (Kuzuhara 2007; Pienpinijtham et al. 2018).
metic products to the hair fibre associated with con- Given the drawbacks of conventional methods it is
cerns related to their environmental impact have important to found advanced methodologies to mod-
led to constant innovative investigation and respond ify physical characteristics of the keratin hair fiber
to consumers wishes. Chemical styling processes including shape and color.
such as colouring or permanent waving make per- Cellulose is considered to be one of the most abun-
manent changes to the hair cortex, destroying parts dant bio-renewable and biodegradable polymers,
of its structure, tend to weaken and dry hair, mak- showing potential to be used in diverse areas with
ing it brittle. Those treatments are made in individ- great economic importance, such as in paper, tex-
ual procedures and contain harmful chemicals, for tile, pharmaceutical, food and cosmetic areas (Lun-
instance ammonium thioglycolate, sodium hydrox- dahl et al. 2017; Felgueiras et al. 2021). Cellulose is
ide, potassium hydroxide, hydrogen peroxide, ammo- a linear polymer composed of repeated glucose units
nia, sodium carbonate, pigments, lithium hydroxide generating specific and large range of reactivities
or sodium sulfate. Side effects of these treatments and functions (Klemm et al. 2005). Cellulose chains
come from the harsh chemicals in the formulations, are stiffened by numerous inter- and intramolecular
duration of treatment and frequency of applications. hydrogen bonding interactions caused by the pres-
Current hair perming methods in the market usually ence of hydroxyl groups as well as weak van der

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Waals forces. It also has a high degree of polymeriza- In hair cosmetic industry, the action of amino
tion (Zhu et al. 2006; Gautam et al. 2010; Chen et al. acids and proteins is of high relevance and impor-
2015). It has advantages of high strength and superior tance because it helps in preserving the integrity of
mechanical properties, however has particularly limi- the hair fiber, in the alignment of cuticles and hair
tation on dissolution in water and most organic sol- follicles, in preventing hair loss, in smoothness,
vents (Zainal et al. 2021). The dissolution of cellulose shine, elasticity, hydration, conditioning and regula-
has been addressed in industrial scale through the tion moisture. In fact, they are constituents of many
application of conventional processes that often use hair products such as capillary resistance masks,
aggressive solvents, such as sodium hydroxide, car- shampoos, and conditioners.
bon disulfide and sulfuric acid, (Olsson and Westm Hair modelling constitute an important matter
2013; Alves et al. 2016) and thus a safer and sustaina- in hair cosmetics. Current perming chemical meth-
ble exploitation of those processes is essential (Zheng ods contain harsh chemicals harmful to the envi-
et al. 2019). ronment and to humans causing serious adverse
Ionic liquids (ILs) are a group of salts with an effects on consumer health and on the hair (Song
inorganic or organic anion and organic cation. et al. 2016; Barreto et al. 2021). This study, aims to
ILs possess unique features such as high thermal provide a method using cellulose formulations for
and chemical stability, high polarity, vapor pres- curling hair, in particular formulation with fewer
sure negligible, high polarity, and non-flammabil- harsh chemicals for the hair fibre in order to reduce
ity (Phanthong et al. 2017). Due to their specific adverse health and hair fibre effects. No previous
properties are considered to be environmentally studies were found on the superficial modifica-
friendly solvents (Sidat et al. 2019; Zainal et al. tion of keratin hair fibre using cellulose derivatives
2021). Despite their large potential, they have major for hair modelling purposes. Alternatives without
limitations regarding their use related to their non- harmful chemicals are vital to promote the discus-
selectivity toward the skin layers and their toxicity sion and the development of new formulations to
(Dharamdasani et al. 2020). Combining Ils with achieve healthier formulations for hair modelling.
other formulation strategies, the topical application
is seen to be improved overcoming those limitations
(Dobler et al. 2016; Navti et al. 2022). Ionic liquids Materials and methods
have gained significant interest in the dissolution of
carbohydrates and other properties (El Seoud et al. Materials
2007; Morais et al. 2020).
In last years, ILs have been used for direct cel- Asian hair samples were kindly provided by Inter-
lulose dissolution without derivatization. Their out- national Hair Importers & Products Inc. (Glendale,
standing dissolving properties allowed to disrupt New York U.S.A.). The kit for the permanent chemi-
and break hydrogen bonds network of cellulose cal waving (oxidizing and neutralizing product, Real
followed by the formation of new hydrogen bonds Natura Cosmetics) were commercially available and
between ionic liquid anions with hydroxyl oxygen were used according to the manufacturer instruc-
and ether oxygen of cellulose to increase it disso- tions. Choline chloride (ChCl), urea and glucose
lution.(Lu et al. 2014; Ibrahim et al. 2015) Known were supplied from TCI Europe. 5-([4,6-Dichlo-
to their physicochemical properties Imidazolium- rotriazin-2-yl] amino) fluorescein hydrochloride
based ILs are benign solvents for cellulose disso- (DTAF), cysteine, propylene glycol and benzyl alco-
lution. Among those that have been investigated, hol were purchased from Sigma-Aldrich. Microcrys-
room temperature ionic liquids stand out namely talline cellulose (MCC, + 97% pure; CAS 9004-34-
1-ethyl-3-methylimidazolium acetate [EMIMOAc] 6, product nº 435,236), Carboxymethyl cellulose
or 1-butyl-3-methylimidazolium [BMIM] which (CMC, + 90% pure; CAS 9004-32-4, product nº
are liquids at room temperature, have lower melt- 21,902) and Hydroxyethyl cellulose (HEC, + 98%
ing point, lower viscosity, lower corrosiveness, and pure; CAS 9004-62-0, product nº 308,633, average
non-toxic properties (Bystrov et al. 2019; Shamsuri Mw ~ 380,000) were purchased from Merck, Ger-
et al. 2021). many. The ionic liquids: 1-ethyl-3-methylimidazolium

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Fig. 1  Schematic illustration about dyeing process marking the HEC cellulose with a fluorescent dye (DTAF)

chloride (Emin Cl), 1-ethyl-3-methylimidazolium The cellulose formulations consist in the dissolution
diethyl phosphate (Emin DEP) and 1-ethyl-3-methyl- of different types of cellulose (MCC, CMC and HEC)
imidazolium acetate (Emin AC) were acquired from at 0.5% or 3% of concentration added to the different
TCI Europe, with 95% and 96% pure. types of Ils (Emin Cl, Emin DEP and Emin Ac) or in
Non-corrodible steel balls (50WW-0015/B/S/A) a serum formulation by stirring at 80 ºC during 1 h.
were supplied from Roaches International (Birstall, The serum formulation is based on 1.5% propylene
West Yorkshire, England). Membrane filters Isopore glycol, 10% ethanol, and 0.5% benzyl alcohol (Cruz
(5.0 μm pore size, hydrophilic polycarbonate mem- et al. 2017). These variables allowed to optimize the
brane, 47 mm diameter) were purchased from Merck methodologies implemented. Each formulation (1
Sigma, Spain. All the other reagents were used as mL) was applied on hair tress until is well covered for
received. different times of incubation. The incubation time for
each method is detailed below. The washing step was
Fluorescence microscopy the same for all methods. To that, was used a com-
mercial shampoo containing the base ingredients like
In order to investigate the effect of the cellulose on Sodium Laureth Sulfate, Cocamidopropyl Betaine,
the surface of the hair fiber, the cellulose was labelled Sodium Citrate and Sodium Xylenesulfonate. The
with a fluorescent dye for further fluorescence analy- washing step was performed dipping the hair tresses
sis. To that, HEC cellulose (0.5 g) was dyed in a solu- in a shampoo solution of 0.1% while massaging the
tion with 0.2 wt % DTAF dye in distilled water, at 50 hair for 1 min, and then rinse thoroughly with water
ºC. After 15 min was added to the solution 20 g/L of for about two min. Then, place the hair in the adsor-
sodium sulphate, and after 30 min was added 15 g/L bent paper to remove the excess of water and let the
of sodium carbonate, maintaining at 50 ºC of tem- hair sample dry at room temperature (RT) for 24 h
perature for more 35 min, Fig. 1 represent the dyeing or dry with a blow drier with (out) a diffuser (Dyson
process. Dialysis procedure was performed to remove Airwrap™, Singapore). The temperature of the blow
the free dye from the solution, collecting only the dryer was around 60–80ºC at a distance of 10–15 cm.
labeled HEC-DTAF. The humidity conditions, for a dimensional perfor-
For the fluorescence analysis, the labeled HEC- mance at wet and dry states were performed for two
DTAF, 0.5% and 3%, was applied to the hair strands. consecutive cycles. For the wet state, the samples
The hair fibers were embedded into an epoxy resin were sprayed with water, and for the dry state, the
followed by transversal cuts of the fibers (16 μm samples were dried with diffuser.
width) using a microtome (Microtome Leitz). The All hair samples were washed (washing step) and
fiber cross sections were analyzed using a LEICA dried at room temperature before use.
DM 5000B fluorescence microscope (Leica) at a In the first method each type of cellulose was added
magnification of 10x. in the different Ils. The mixtures were stirred until com-
plete dissolution, as mentioned above. Then, the cel-
Hair curling procedure lulose formulations were applied on hair tresses for an
incubation period of 30 min at room temperature, and
The hair curling procedure to change the shape of the finally the hair was dried with a diffuser. After drying,
hair from straight to curly was tested in different types was made two cycles of wet-dry conditions consist-
of application development of four methodologies. ing in a wet spraying of water followed by drying with

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diffuser. After 24 h, the hair was washed with shampoo Where Li is the length of the hair before treatment
and dried at room temperature. and Lf is length of the hair after treatment.
The second method consists in the application of
those cellulose formulations as in the first method,
differing in the drying step. For that, the hair was Evaluation of hair resistance to mechanical wear
rolled in a glass rod and blow-dried after 15 min
of incubation on the glass rod at RT. After that, The effect of the formulations on the hair resistance to
two wet-dry cycles were carried out in those hair the mechanical wear was expressed in terms of hairs
samples, and finally hair samples were washed with mass loss after the mechanical insult (Ribeiro et al.
shampoo and dried at room temperature. 2021). To that, 10 mg of each hair sample was cut in
After these experiments were investigated the effect 0.5 cm fragments and were incubated with five hard-
of a swelling agent (benzyl alcohol and urea) as a first ened steel balls and 700 µL of distilled water in 2 mL
step followed by the cellulose formulations’ application Eppendorf tubes. The samples were vortexed (Vortex 3
and drying process as the second step. This optimiza- IKA, Germany) under 2500 rpm during 12 h at room
tion incorporates the 3th and 4th application method. temperature, and the reaction mixtures were filtered
The third method consisted in the application of using a membrane pore size of 5.0 μm. All Eppen-
formulation U (3% of urea in serum formulation) dorf’s’ tubes were washed five times with 700 µL of
during 30 min at room temperature, as a first step, on distilled water in order to prevent material loss. The am
hair tresses. In this step was also tested the effect of hair loss was determined according Eq. 2:
polar agents as benzyl alcohol or serum (as a solvent) ( )
plus urea 3% plus keratin-based peptide (0.01%, KP Hi − Hf
Hair mass loss(%) = × 100 (2)
peptide with high affinity to the hair (Cruz et al. Hi
2017). Followed the application of cellulose formu-
Where, Hi corresponds to the initial amount of hair
lation S (HEC cellulose in ionic liquid for 10 min,
and Hf to the final amount of hair present in the poly-
as the second step. In this case was tested the HEC
carbonate membrane filter after drying at 40 °C for
cellulose at 3% in Emin DEP ionic liquid and in the
12 h.
Serum. Then, the hair was dried with a diffuser and
The resistance to wear expressed in percentage
two cycles of wet-dry conditions were performed. In
was calculated according Eq. 3:
the final, the hair samples were washed with sham-
poo and dried at room temperature. Resistance to wear(%) = 100% − Hair mass loss(%)
Finally, the fourth method consists in the applica- (3)
tion of the formulation U (3% of urea in serum for-
mulation during 10 min at room temperature) on Scanning electron microscopy (SEM) analysis
hair tresses following the application of the formula-
tion S (CMC and HEC in Serum at 0.5% and 3% for Morphologic characterization of the treated and
10 min). The hair samples were dried using a blow untreated hair samples were conducted using a desk-
drier. The final stage was the washing step with a top Scanning Electron Microscope (SEM) (Phenom
commercial shampoo and dried at room temperature. ProX, Netherlands). All results were acquired using
To evaluate the curly efficiency of the formulations the ProSuite software. The treated hair samples were
in each hair sample was measure the length of the hair added to aluminium pin stubs with electrically con-
fiber after (Lf) and before treatment (Li). The length ductive carbon adhesive tape (PELCO Tabs™).
of hair samples was measured with a ruler from one Samples were coated with 2 nm of Au Samples were
end to other of the hair fiber without stretching. The sputter coated with 2 nm of Au ((desk sputter DSR1),
formula used to calculate the curl efficiency was in Nano-Structured Coating Co) for 10 min to improved
percentage (Eq. 1). conductivity for improved conductivity. The alumin-
Li − Lf ium pin stub was then placed inside a Phenom Stand-
𝐂𝐮𝐫𝐥 𝐟𝐨𝐫𝐦𝐚𝐭𝐢𝐨𝐧(%) = × 100 (1) ard Sample Holder. The analysis was conducted at
Li
5 kV with intensity image.

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ATR‑FTIR spectroscopy (Attenuated Total Reflection was examined through fluorescence microscopy. The
Fourier Transform Infrared Spectroscopy) cross-sectional images obtained from the labelled
HEC-cellulose attached to the hair fibre (Fig. 2)
ATR-FTIR is one of the powerful tools for a sin- showed a homogenous green layer deposited on the
gle human hair characterization and hair surface hair fibre surface.
characterization. It was acquired a spectrum from The cellulose deposited on the surface of the hair
the surface of the hair sample encompassing the fiber promoted a change in the dimensional stability
total reflected radiation at the interface between the of the hair fiber. This allowed it to acquire different
internal reflection element (IRE) and the sample. affinities with water in relation to the internal fiber,
The shallow penetration depth of the evanescent which led to dimensional changes in fiber length, trig-
wave makes ATR-FTIR spectroscopy a sensitive gered by the presence of moisture. This statement
surface technique (Feughelman et al. 2002). It is a was evidenced testing two different methodologies in
non-destructive analytical technique with minimal which the formulations were applied and dried in dif-
sample preparation. ferent steps.
The spectra of virgin and treated hair samples were Both methodologies show that the ionic liquid
acquired using a FTIR spectrometer Alpha II (Bruker, 1-ethyl-3-methylimidazolium acetate (Emim Ac)
German). The spectra were recorded at a wavelength and 1-ethyl-3-methylimidazolium chloride (Emin
from 4000 to 400 ­cm−1, with a resolution of 4 ­cm−1 Cl) with the different types of cellulose (MCC, HEC
and 24 scans. and CMC) induced highest curl efficiency on the
hair than DEP-methylimidazolium diethyl phosphate
Statistical analysis (DEP-MCC, DEP-HEC and DEP-CMC). Although
the application of the dissolved HEC cellulose in
Statistical comparisons were performed using one- water (H-HEC) on the hair achieved a curl forma-
way analysis of variance (ANOVA) with post-hoc tion quite similar or even better after washing than
Tukey method to identify significant differences the application with ionic liquids (Fig. 3). An impor-
between the results. Differences were considered stat- tant aspect is the viscosity of the solutions at room
ically significant at p- value < 0.05. temperature, since they should leave the hair after
application with a squeezable appearance. Besides,
the final appearance of the hair after those cellulose
Results and discussion formulations was slightly rigid. Figure 3 shown that
the H-HEC formulation (HEC in water) presented a
In this study formulations based on cellulose were good profile of hair curl formation. This HEC cel-
applied with different methodologies to promote hair lulose formulation exhibited consistent results curls
modelling. The cellulose was labelled with a fluores- formation after treatment and after cycles at wet-dry
cent dye for further investigation. Labelled cellulose conditions. HEC is the hydroxyethyl ether of cellu-
(DTAF dye-HEC cellulose) applied to the hair fibre lose which is a water binder and thickener in various

Fig. 2  DTAF dye labelled (a) HEC-cellulose at 3% (b) HEC-cellulose at 0.5%

HEC cellulose attached to
the hair fibre. Images cap-
tured with a fluorescence
microscope. Left (a) and
right images correspond
to the labelled HEC with
a concentration of 3% and
0.5%, respectively. a HEC-
cellulose at 3%, b HEC-
cellulose at 0.5%

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Fig. 3  Comparison of the curl formation using three ionic cellulose (HEC); Ac-MCC: 1-ethyl-3-methylimidazolium
liquids, 1-ethyl-3-methylimidazolium diethyl phosphate acetate (Ac)-Microcrystalline cellulose (MCC); Ac-CMC:
(DEP), 1-ethyl-3-methylimidazolium acetate (Ac) and 1-ethyl- 1-ethyl-3-methylimidazolium acetate (Ac)- Carboxymethyl
3-methylimidazolium chloride (Cl), with three different cel- cellulose (CMC); Ac-HEC: 1-ethyl-3-methylimidazolium ace-
luloses (MCC, CMC and HEC) on the hair fiber applying tate (Ac)- Hydroxyethyl cellulose (HEC); Cl-MCC: 1-ethyl-
method 1 and 2 followed by washing. Result is representative 3-methylimidazolium chloride (Cl)- Microcrystalline cellulose
for each condition. DEP-MCC: 1-ethyl-3-methylimidazolium (MCC); Cl-CMC: 1-ethyl-3-methylimidazolium chloride (Cl)-
diethyl phosphate (DEP)-Microcrystalline cellulose (MCC); Carboxymethyl cellulose (CMC); Cl-HEC: 1-ethyl-3-meth-
DEP-CMC: 1-ethyl-3-methylimidazolium diethyl phosphate ylimidazolium chloride (Cl)- Hydroxyethyl cellulose (HEC);
(DEP)-Carboxymethyl cellulose (CMC); DEP-HEC: 1-ethyl- H-HEC: water (H)-Hydroxyethyl cellulose (HEC)
3-methylimidazolium diethyl phosphate (DEP)-Hydroxyethyl

cosmetic formulations. It is easily dissolved in water ionic liquid or in water/serum. Here, was used the for-
giving translucent solutions with a variety of viscosi- mulations which attained better results using methods
ties depending on the concentration of HEC. Due to 1 and 2 previously tested (Fig. 4).
its high water solubility, HEC is widely used for a It was also tested the curly efficiency with formula-
variety of applications such as cosmetics, building tions at alkaline pH, in order to achieve better swell-
materials, film-forming materials and pharmaceutical ing of the fiber. However, the results showed that
productions (Arai and Shikata 2020). at neutral pH the efficiency was higher, which is in
It was tested the effect of a pre-treatment as a first accordance with previous results since the decapep-
step in the application process in order to improve the tide based on keratin also presents higher perfor-
swelling effect of the hair fiber and facilitate the cel- mance at neutral conditions (Cruz et al. 2017). This
lulose deposition on it, especially in formulation with peptide it is incorporated into the serum formulation.
Emin DEP. Consists in dissolving urea into the serum Our research group have developed this keratin-based
formulation based mainly in water (3% urea, desig- peptide for application on relaxed damaged hair with
nated as Formulation U). This pre-treatment allowed proven characteristics of recovering mechanical prop-
to obtain a better swelling of the hair fiber through erties of over-bleached damaged hair (Cruz et al.
the use of a polar solvent, as urea (Jiang et al. 2018). 2017). Products with this peptide penetrate easily in
This methodology was intitled as method 3 including the hair fiber and recreate disulfide bonds that have
two steps applications. The second step is the applica- been broken or damaged through bleaching, color-
tion of Formulation S, where cellulose is dissolved in ing, perming, or straightening process. Once inside

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 6904 Cellulose (2024) 31:6897–6909

Fig. 4  Visual curl formation on Asian hair using the meth- treatment containing cellulose in ionic liquid (DEP-HEC) and
odology application number 3 (after wash), including the first in Serum (Serum-HEC)
step pre-treatment with urea followed by a second step with

Fig. 5  Comparison between formulations with cellulose concentration at 3% and 0.5% (Carboxymethyl cellulose – CMC; Hydroxy-
ethyl cellulose - HEC), for curl formation (CF) efficiency after 1st and 3th wash

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the hair, peptide attaches to the hair protein replacing formulation maintain curls efficiency of the hair after
the broken bonds adding strength and elasticity (Cruz 3 washes. The curly results with HEC cellulose were
et al. 2017). quite similar for both concentrations after first wash,
The addition of urea promotes good swelling around 10%, however practically decreases by half
properties to the hair fiber and hydrates the keratin, after three washes. CMC cellulose formulations main-
depending on the concentration due to its denatur- tain curly effect after wash. This is a good indicator
ing ability (Zhao et al. 2020). The developed for- since this formulation allows to change the shape of
mulation was applied to the hair sample as a pre- the hair keratin for at least 3 washes. Since aggressive
treatment followed the formulation containing the chemical products were avoided in those formula-
cellulose dissolved in ionic liquid (DEP-methylim- tions, they showed promised results in hair modelling
idazolium diethyl phosphate) or in serum, results processes preventing serious damages in the hair fiber
shown in Fig. 4. and in the environment. Besides they contribute to an
The serum showed to be the most effective base economical and profitable formulation.
formulation. To make cellulose profitable, its concen- Those formulations based on HEC and CMC
tration was reduced from 3 to 0.5%, respectively. This cellulose at 3% and 0.5% dissolved in Serum were
reduction allowed to obtain a less viscous solutions. applied on hair samples using the method referred
Being the HEC a thickener agent (Omidian and Park as four, and after washing were tested in terms of
2017) and used at lower concentration, the formula- wear resistance (Fig. 6). In fact, they present a
tion becomes more fluidic which facilitates it use. good performance to fatigue resistance. The for-
MCC cellulose was not dissolved in serum formula- mulation containing 0.5% of CMC exhibited the
tion, formed to phases. A comparison between formu- highest value of fatigue resistance, statistically did
lations, with CMC and HEC cellulose at 3% and 0.5% not share a letter with controls means that is sta-
of concentration was studied reducing the time of hair tistically different. The hair samples treated with
incubation and dry it after incubation time (10 min in 3% of CMC, HEC at 3% and 0.5% formulation
each incubation step) (Fig. 5, method 4). The effect of also showed a good resistance to fatigue (above
the number of shampoo washes (until three washes) is 95%). These results indicate that the presence of
also provided in Fig. 5. cellulose improved the wear mechanical resist-
The curl efficiency obtained for the formula- ance to the hair fiber exhibiting lower weight
tion containing 0.5% of CMC was clearly showed mass loss during the fatigue assay. The mass loss
after wash. Besides, at a concentration of 3% CMC of the coated hair samples obtained after fatigue

Fig. 6  Effect of cellulose

(CMC and HEC) on the
resistance to mechanical
wear of coated hair fiber.
Grouping information using
Tukey test with 95% of con-
fidence meaning that do not
share a letter are significant
different

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Fig. 7  SEM images of the hair samples untreated and treated 0.5% CMC, 4-Asian Hair treated with 3% HEC, 5-Asian hair
with the cellulose formulations: 1-virgin Asian hair (control), treated with 0.5% HE. The scale bars correspond to 80 µm
2-Asian hair treated with 3% CMC, 3-Asian hair treated with

Fig. 8  ATR-FTIR spectra of treated hair samples with the different types of cellulose dissolved in with water and serum. Each value
represented in the spectra corresponds to a representative value of each condition tested

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experiment is related with the degradation degree the presence of HEC cellulose and for CMC at 3% of
of hair’s resistance to mechanical wear. The lower concentration. These results are in accordance with
degradation rate of the coated hair samples reflects wear resistance and SEM images exhibiting an effec-
higher resistance to mechanical wear and conse- tive coating on keratin fiber.
quently lower damages on the surface cuticle layer.
From Fig. 7 it is possible to observe that the
coated hair samples exhibited low patterns of Conclusions
damages corroborating the results attained in
the fatigue resistance. The treated hair sample The deposition of dissolved cellulose on the surface
coated with 3% CMC exhibited flat cuticle cells of hair fiber revealed an effective adhesion of the
overlaid on the surface, maintaining a smoother coating layer on the cuticle of the keratin fiber. This
and more intact appearance. This may indicate was observed by fluorescence microscopy and the
that this formulation with 3% CMC prevents the integrity of the structure of the fibers was confirmed
damage that can arise from the application of by resistance to fatigue presenting low weight mass
frictional forces. loss.
The coated hair samples were also evaluated by Formulations with HEC and CMC at 3% and 0.5%
ATR-FTIR microscopy to analyze changes in the dissolved in Serum formulation presented the higher
chemical structure of the hair fiber surfaces. A com- curl formation around 12%, using the application
pilation of the spectra of all evaluated formulations method number four. The resistance to washes was
was carried out (Fig. 8). As shown in Fig. 8, all the preserved for 3 washes with shampoo. The presence
treated hair samples showed the characteristics peaks of the mentioned cellulose induced hair modelling
at around 1640 cm-1 related to amide I, 1525 ­cm−1 and improved wear resistance of the hair fiber.
attributed to amide II and 1240 c­ m−1 to amide III.
The Amide I peak corresponds to the C = O elonga- Acknowledgements This study was supported by the Portu-
guese Foundation for Science and Technology (FCT) under the
tion and a small contribution from the N-H vibration. scope of the strategic funding of UIDB/04469/2020 unit and
The Amide II peak corresponds to both components, BioTecNorte operation (NORTE-01-0145-FEDER-000004)
the C-N elongation, and the N-H oscillation vibrations. funded by the European Regional Development Fund under the
While the N-H torsional vibration plus the C-N elon- scope of Norte2020.
gation vibration and the contribution of the O = C-N
Author contributions J.P.C methodology, investigation, pre-
bending vibration corresponding to the Amide III band. pared figures. M.M. writing—review and editing, A.C.P super-
The absorption bands recorded between 2850 ­cm−1 vision, All authors reviewed the manuscript.
were attributed to C-H stretching vibration, whereas
bands at around 1400 ­cm−1 correspond to C-H bend- Funding Not applicable.
ing strain vibration. The broad band appeared at
around 3280 ­cm−1 correspond to the stretching vibra- Data availability No datasets were generated or analysed
during the current study.
tions of -OH and -NH groups. Coated hair samples,
especially samples with HEC cellulose, present a Declarations
broader peak at 3280 ­cm−1 than the hair samples con-
trols (water and serum) which is related with inter- Ethical approval Not applicable.
molecular hydrogen bonding of the coated cellulose
on the hair fiber (Pienpinijtham et al. 2018) (Pien- Competing interests The authors declare no competing
pinijtham et al. 2018). This is more pronounced in interests.

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