Colloids and Surfaces A: Physicochem. Eng.

Aspects 436 (2013) 881–889

Contents lists available at ScienceDirect

Colloids and Surfaces A: Physicochemical and

Engineering Aspects
journal homepage: www.elsevier.com/locate/colsurfa

Synthesis and physicochemical properties of silicon-based

gemini surfactants
Li-Huei Lin a,∗ , Chee-Chan Wang a , Keng-Ming Chen b , Po-Chang Lin b
a
Department of Cosmetic Science, Vanung University, 1, Van Nung Road, Chung-Li City, Taiwan, ROC
b
Department of Polymer Engineering, National Taiwan University of Science and Technology, 43, Keelung Road, Section 4, Taipei, Taiwan, ROC

h i g h l i g h t s g r a p h i c a l a b s t r a c t

• Product 2C12 PSi possesses identical As the products’ concentration and the chain lengths of the hydrophobic groups increased, the magnitude
foam-flowing height and stabiliza- of surface tension reduction varied: when the concentration exceeded the CMC, the surface tension
tion height. value was shown to approach stability, indicating that the liquids’ surface tensions achieved a stable
• The I1 /I3 ratio was reduced only when equilibrium.
the chain length of the hydrophobic
groups increased.
• Product 2C12 PSi had the smallest par-
ticle size and possessed the largest
surface activity.
• Adding the products triggered the
dye to disaggregate, which ultimately
improved its absorbance rate.

a r t i c l e i n f o a b s t r a c t

Article history: In this study, polydimethylsiloxane, polyethylene glycol, and various fatty alcohol (m = 0, 6, 12, 18) were
Received 15 June 2013 employed to produce a series of functional silicon-based gemini surfactants (2Cm PSi). Subsequently,
Received in revised form 10 August 2013 surface properties such as surface tension, contact angle, fluorescence, foaming property, dispersion, and
Accepted 12 August 2013
emulsion ability were tested. The surface excess concentration ( CMC ) and the surface area occupied
Available online 21 August 2013
by the surfactant molecule (ACMC ) were calculated. Furthermore, we used UV–vis spectroscopy to study
the interactions of dye with the silicon-based Gemini surfactants in aqueous solution. The experimental
Keywords:
results show that the series of products all possess good surface activity, and the product with 12 carbon
Silicon-based gemini surfactants
Surface activity
chains is best one. In addition, products with long hydrophobic chains and dispersed dyes merge into a
Micelle complex, shifting the maximum absorption (max ) toward long wavelengths to produce a red shift effect.
Interaction
© 2013 Elsevier B.V. All rights reserved.

1. Introduction such as the ability to aggregate adsorption, wetting, foam abil-

ity, disperse, or emulsify. Because traditional surfactants lose their
Surfactants can be made from one or more hydrophilic or functionality under specific conditions, to improve their deficiency
hydrophobic groups. Based on specific conditions, the ratio of the and further expand the extent of their usage, researchers abroad
hydrophilic or hydrophobic groups of surfactants can be altered to have endeavored to develop numerous functional surfactants. In
become soluble in water, oil, or other solvents to reduce the sur- fact, dimethylsiloxane (DMS)-based [1], gemini-based [2–6], and
face tension of liquids. They also cause different surface activities, polymer-based surfactants [7] have all garnered interests in recent
years.
Polydimethylsiloxane (PDMS) can be used in a wide variety of
∗ Corresponding author. Tel.: +886 3 4515811x51736; fax: +886 3 4514814. applications, including lubricants, defoamers, and water repellents
E-mail address: lihuei@mail.vnu.edu.tw (L.-H. Lin). [8]. However, because PDMS is not water-soluble, it is inconvenient

0927-7757/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.colsurfa.2013.08.036
882 L.-H. Lin et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 436 (2013) 881–889

in practical applications. Therefore, the properties of PDMS were The residual solvent and ECH were then removed using a vacuum
changed to functional silicon (Si)-based surfactants [9,10]. Because oven. This process produced the step 1 product. The structure of
of their unique molecular structure, which is dissimilar from the step 1 product may be determined by infrared analysis. The
traditional surfactants, their surface activity is less affected by general transformation was the reaction of the OH group of PEG
temperature. This ensures good surface activity under high temper- with ECH, leading to the formation of the characteristic adsorption
atures while possessing the ability to mitigate, prevent, or stabilize of C O C at 1050–1100 cm−1 . Next, the step 1 product (0.02 mol,
foam. The toxicity of Si-based surfactants is extremely low and are 162.24 g), 300 ml of acetone, 30% NaOH aqueous solution (0.1 mol,
commonly used in cosmetics and related industries [11]. 1 g), and TBAB (0.003 mol, 1 g) were placed into a 1-L four-necked
Gemini-based surfactants are made from two or more reaction flask equipped with a stirring rod and a thermometer.
hydrophilic or hydrophobic groups, which are connected to form The compound was then stirred uniformly for 30 min at 70 ◦ C.
a structure with symmetrical sides. [12–15] Compared to tra- After the temperature was reduced to 55 ◦ C, 300 ml of n-hexane
ditional surfactants, gemini-based surfactants exhibit superior and PDMS (0.01 mol, 34 g) were added into the flask and reacted
surface activities in practical applications. This includes the follow- for 5 h.
ing features: (1) lower critical micelle concentration (CMC) values; At 55 ◦ C, the reaction products slowly deposited various layers
(2) better foam stability; and (3) better emulsion properties. at the bottom of the flask, exhibiting clear signs of insolubility in the
The extreme flexibility of the Si O Si linkage allows the methyl acetone and n-hexane solution. The purification process involved
groups of siloxane surfactants to position at the interface advanta- multiple extractions using acetone and n-hexane in 60 ◦ C aqueous
geously enhancing their surface activity, which differentiates them solution. These solvents removed the unreacted PDMS, phase trans-
from traditional surfactants that contain only hydrocarbon bonds. fer catalyst TBAB, and NaOH within the compound. Subsequently, a
The primary functions of Si-based surfactants include the follow- pressure-reducing condenser and vacuum oven were used to pro-
ing: (1) good defoaming ability; (2) surface property remains active, duce the step 2 product (2C0 PSi).
even when dissolved in a solvent; (3) soft molecular chain segments The 2C0 PSi (0.02 mol, 392.4 g) and 30% NaOH aqueous solution
that allow tight surface arrangements; and (4) excellent wetting (0.1 mol, 1 g) were placed into a 1-L four-necked reaction flask
ability [8,9]. equipped with stirring rod and a thermometer. The compound was
In this study, PDMS was adopted as the intermediate and then heated to 70 ◦ C for the compound to dissolve. Next, the tem-
polyethylene glycol (PEG) as the hydrophilic groups. Hydrocar- perature was maintained, and an excess of carbon chain alcohol
bon bonds with various chain lengths (m = 0, 6, 12, and 18) were (m = 6, 12, 18) was added to react for 5 h.
attached to ends of the hydrophilic groups to form the hydrophobic Once the reaction was complete, the product was poured from
groups. By combining these substances, the compound became a the container for purification. The product (ca. 60 g) was dissolved
surfactant that was DMS-based, gemini-based, and polymer-based. in acetone (150 ml) and extracted twice with saturated Na2 CO3
Subsequently, the compound’s surface properties were tested, such solution to remove any unreacted fatty alcohol. Finally, a pressure-
as surface tension, contact angle, fluorescence, foaming, dispersion reducing condenser and vacuum oven were employed to produce
ability, and emulsion ability. We also investigated the interactions the final product (2Cm PSi).
between dyes and micelles of the silicon-based Gemini surfactants
in aqueous solutions.
2.3. Analysis

2. Materials and methods 2.3.1. Surface tension measurement

First, a series of sample solutions with various concentra-
2.1. Materials tions were prepared. Next, the Japan CBVP-A3 surface tensiometer
(Kyowa Kaimenkagaku) was calibrated. The platinum disk of the
PEG 8000 (Hayashi Pure Chemical Ind., Ltd., MW), reagent tensiometer was cleaned using acetone to remove any impurities
grade, PDMS (Send Fine Chemical Co., Ltd.), industrial grade, adsorbed on the surface before being burned to red using an alcohol
Epichlorohydrin, (ECH; Hayashi Pure Chemical Ind., Ltd.), 1- lamp. After cooling, the platinum disk was hung on a hook. Then,
hexanol, 1-dodecanol, 1-octadecanol, and tetrabutylammonium a glass dish was rinsed and dried before pouring in the test solu-
bromide (TBAB) were purchased from Acros Organics. Olive oil, tion until the dish was approximately 80% full. Finally, the switch
food grade (Olitalia Corporate), CaCO3 (Hayashi Pure Chemical Ind., was turned on and the surface tension of the liquid was tested
Ltd.), reagent grade. The fluorescence reagents used in this study using the platinum disk. This was repeated five times to ensure
were pyrene (Sigma, USA). The disperse dyes used were dispersol reproducibility.
blue B-R (C.I. disperse blue 56; BASF, Germany).

2.3.2. Contact angle measurement

2.2. Synthesis A series of sample solutions with various concentrations were
prepared. Contact angles were measured using a FACE CA-5 contact
The synthesis of silicon-based gemini surfactants is presented angle meter (Kyowa Kaimenkagaku). PMMA and Teflon plates were
in Fig. 1. PEG 8000 (0.05 mol, 400 g) and 300 ml of acetone were placed on the test station. Next, the product solution was extracted
placed into a 1-L four-necked reaction flask with a stirring rod using a syringe, and 20 mm size droplets were injected onto the
and a thermometer. Next, the compound was stirred uniformly at plates. The droplets were then left to stablize for 1 min before being
70 ◦ C for 30 min. After the temperature was reduced to 55 ◦ C, exces- observed and record the angle. This process was repeated five times
sive amounts of ECH (0.20 mol, 18.51 g) were added into the flask to ensure reproducibility.
and reacted for 5 h. Subsequently, a 30% NaOH aqueous solution
(0.1 mol, 1 g) was added before stirring the product for an additional
30 min. 2.3.3. Foamability measurement
After the reaction period, the compound was poured from the 500 ml of 40 g/l aqueous solution was prepared and inserted
container and the reduced pressure filtration method was applied into the reagent tank. The flow rate from the motor was set at
to remove NaCl from the compound. The pressure-reducing con- 400 ml/min. After being ejected by the circulation pump, the aque-
denser eliminated the majority of the solvent and excessive ECH. ous solution was retained by the nozzle and continued to circulate.
 L.-H. Lin et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 436 (2013) 881–889 883

Fig. 1. Synthesis of silicon-based gemini surfactants.

The foam height was recorded after 1 h and again after 5 min of spectrometer, the excitation and emission wavelengths were mea-
stabilization. sured at 335 nm and 350–450 nm.

2.3.5. Emulsion ability measurement

2.3.4. Fluorescence measurement The measuring instrument was calibrated and the sample con-
A 0.0100 g measurement of pyrene was collected and dissolved tainer was rinsed. Three-hundred grams of the forty grams per
in 500 ml of alcohol. Then, 0.2 ml of the solution was extracted liter sample solution was prepared, where 30 g of the solution
and placed it into a 100 ml beaker before drying it in an oven at was removed before adding 30 g of olive oil. The compound was
40 ◦ C for later use. Next, a series of solutions with various con- mixed using the IKA Labortechnik Ultra-Turrax T25 homogenizer
centrations were prepared, and 20 g of each solution was injected at 11,000 rpm for 10 min. Subsequently, it was left to stabilize for
into beakers containing pyrene before being vibrated for 15 min a further 10 min. The emulsion was poured into the sample con-
in an ultrasonic oscillator. The emission spectra of the solutions tainer where parameters such as dielectric constant and particle
were measured using an Aminco–Bowman Series 2 luminescence density were set at 3.1 and 0.912 g/ml, respectively. By operating
884 L.-H. Lin et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 436 (2013) 881–889

65

2C0PSi 60

55
2C0PSi
2C6PSi

Surface Tension (mN/m)

Transmittance (a.u.)

50

2C12PSi 45

40
2C18PSi
2C6PSi
35

2C18PSi
30

25
2C12PSi
20
0.01 0.1 1 10
4000 3500 3000 2500 2000 1500 1000 500
-1 Log C (mmol/L)
Wavenumber (cm )
Fig. 3. Surface tension versus concentration of silicon-based gemini surfactants.
Fig. 2. Infrared spectra of silicon-based gemini surfactants.

the ZetaProbe (Colloidal Dynamics) instrument, the zeta poten- Table 1

tial values of the emulsion as a result of changes in pH could be CMC, Gibbs free energy, average equilibrium surface tension, surface excess con-
centration, and surface area occupied by the surfactant molecule of silicon-based
obtained.
gemini surfactants.

Compound 2C0 PSi 2C6 PSi 2C12 PSi 2C18 PSi

2.3.6. Interaction measurement
The dyes were produced using a fine recrystallization method CMC (mmol/L) 2.141 1.574 0.061 0.835
before making them into a solution containing a set level of concen-  CMC (mN/m) 53.8 36.7 22.1 32.2
G (kcal/mol) −3.640 −3.822 −5.747 −4.198
tration. A series of product solutions with various concentrations  CMC (mmol/m2 ) 0.338 0.953 1.299 1.235
were prepared and mixed using a dye solution (1:1 ratio) before ACMC (×102 nm2 /molecule) 0.492 0.174 0.128 0.135
using the Shimadzu UV-240 spectrophotometer to measure the UV
absorption of the solution.
energy needs to be reduced. Consequently, the hydrophobic groups
3. Results and discussion in the solution begin attracting and gathering molecules, form-
ing the so-called micelles. The concentration formed by micelles
3.1. Preparation is called the CMC. When the concentration of the surfactants is less
than the CMC, the hydrophobic groups are unable to tightly align on
The structures of the products (2Cm PSi) were analyzed using the liquid’s surface. This causes the forces to be unevenly exerted on
an infrared spectrometer (FT-IR) and a nuclear magnetic reso- the liquid’s surface, and causes an ineffective reduction in surface
nance spectrometer (1 H NMR). Fig. 2 shows the infrared spectra tension [16].
for the series of products. From the spectra, it can be observed In this study, the relationship between the series of products
that no obvious OH group peak signals were detected in the and surface tension were investigated, and surface tension was
3200–3600 cm−1 in the products’ molecular structure, indicating used to evaluate the products’ surface activity. Fig. 3 shows a dia-
that no unreacted alcohol groups were in the products. The bending gram of the products’ surface tension by concentration. As shown
vibrations for Si CH3 in the structure were observed in the inter- in the diagram, the series of the 2Cm Psi products were all capa-
vals between 1222–1321 cm−1 and 772–893 cm−1 ; for OCH2 they ble of reducing the surface tension. As the products’ concentration
were observed in the interval between 1426 cm−1 and 1536 cm−1 . and the chain lengths of the hydrophobic groups increased, the
The C O C stretching vibrations were recorded at the interval magnitude of surface tension reduction varied: when the concen-
between 989–1220 cm−1 and 893–991 cm−1 , whereas the stretch- tration exceeded the CMC, the surface tension value was shown
ing vibrations and bending vibrations for CH2 were recorded to approach stability, indicating that the liquids’ surface tensions
at 2643–3115 cm−1 and 1321–1402 cm−1 , respectively. Based on achieved a stable equilibrium. Among all of the products, Product
the 1 H NMR spectral analysis on the series of products, the chemi- 2C12 PSi possessed the strongest water surface tension reduction
cal shifts for R-CH2 , CH2 , and CH2 CH2 O were recorded at ı ability. For Product 2C18 PSi, despite having the longest hydropho-
0.5–1.3, 1.2–1.4, and 3.2–3.8 ppm, respectively. bic group chains, the surface tension reduction ability was weaker.
This is because the molecular chains were too long; consequently,
3.2. Surface tension the molecules tangled, creating an uneven layer of molecule distri-
bution on the liquids’ surface. Areas on the liquids’ surface classified
The reason surfactants are able to reduce the surface tension as thin were susceptible to greater internal attraction, causing the
in solutions is because of the hydrophilic and hydrophobic groups surface tension to increase [17]. Furthermore, when a C18 chain was
they possess. The chemical arrangements where the hydrophilic appended, the CMC increased, presumably because the hydropho-
groups remain in water and the hydrophobic groups protrude the bic chain was long enough to curl up, making the micelles more
surface of the water form a molecular layer that reduces the inter- difficult to form [18,19].
nal force pulling the solution’s surface molecules. When forcing Table 1 shows the CMC, free energy, average equilibrium surface
hydrophobic groups to dissolve, free energy is created at the liquid’s tension, surface excess concentration, and surface area occupied by
surface. As the system drives to achieve stability, the surface’s free the surfactant molecule for the series of products. From the table,
 L.-H. Lin et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 436 (2013) 881–889 885

Table 2
Contact angles of silicon-based gemini surfactants.
80
2C0PSi
Compound Contact angle (degrees)

Teflon PMMA 2C6PSi

Contact Angle (degree)

70 2C18PSi
H2 O 106.0 86.8
2C0 PSi 93.6 78.8
2C6 PSi 80.2 72.4
2C12 PSi 48.2 43.0
60
2C18 PSi 78.4 71.0

it can be observed that the products’ surface activity was related to 50

average equilibrium surface tension (), and that a lower surface
tension value indicated that a product possessed stronger surface 2C12PSi
tension reduction ability for water. Largest surface activity also sig-
nified smaller CMC values, which meant that the Gibbs free energy 1
(G) required to form the micelles was relatively smaller. The prod- Log C (mmol/L)
ucts’ surface tension, conversely, was related to the liquids’ surface
Fig. 4. Contact angle versus concentration of silicon-based gemini surfactants.
excess concentration ( CMC ) and surface area occupied by the sur- (PMMA as the solid wetted).
factant molecule (ACMC ). Higher surface adsorption per unit area
indicated a smaller area occupied by each molecule on the liq-
uids’ surface, which also implies a tighter arrangement between diminished the effective concentration and inhibited the formation
the molecules. The level of tightness in the molecular arrange- of additional micelles, thereby preventing a decrease in the contact
ment also affected the value of the surface tension [20,21]. Using angles [22]. The products, listed in descending order by their sur-
this value, the degree of surface activity for the series of products face activity and ability to effectively reduce contact angles, are
was obtained, where Product 2C12 PSi exhibits the smallest ACMC of 2C12 PSi, 2C18 PSi, 2C6 PSi, and 2C0 PSi. Despite having an identical
12.8 nm2 molecule−1 and possesses the largest surface activity. This concentration, the liquids that were dripped onto the Teflon and
is because it possessed a tighter molecular arrangement in compar- the PMMA produced various contact angles. This was because the
ison to the other products, and that its free energy requirement to fluoride within the Teflon structure caused the Teflon to possess a
form micelles was the smallest. smaller surface tension than the PMMA. The smaller the difference
between the surface tension of the liquid and the solid indicates
3.3. Contact angles it is more difficult for a liquid to wet the solid; consequently, the
contact angle of the Teflon was ultimately greater than that of the
Surface tension is a measurement of the rate of attraction PMMA [23].
between molecules. Because the molecular attraction on the sur- Fig. 4 shows the contact angle versus concentration of silicon-
face of liquids is greater than in the air, the molecules on the surface based gemini surfactants. From the table, it can be observed that as
of the liquids are subject to the attraction exerted by the liquids’ the level of concentration increases, the products’ contact angles
internal molecules. This creates a force that attempts to reduce decrease. However, once the level of concentration exceeds a
the liquids’ surface area whenever possible (this principle explains specific threshold, the contact angle stops decreasing and stabi-
why water drops are spherical). Similar to the surface molecules of lizes, forming a noticeable break point in line. This break point
liquids, surface molecules of solids also experience intermolecular is the CMC. The surface activity of the products is closely related
attractions. Therefore, solids also possess surface tension capable to the contact angles, where smaller angles denote a stronger
of adsorbing gases and liquids. Normally, a layer of air is adsorbed ability for the products to diminish contact angles, and that the
on the surface of solids; therefore, for liquids to expand on the sur- greater the surface activity is, the smaller the CMC possesses.
face, they must first push out the existing air. This phenomenon This phenomenon is similar to surface tension, this is due to the
is called wetting. It is typically very difficult for water to dampen enlargement of the hydrophilic portion of the surfactant molecule,
glasses with waxed surfaces. However, this problem can be solved resulting in a decrease in concentration of surfactant at the liquid
by adding surfactants in the water. The liquids’ ability to wet a surface [24].
solid’s surface can be determined by observing their contact angles,
where smaller contact angles imply less difficulty wetting a solid’s 3.4. Foamability
surface.
Table 2 shows the contact angles of silicon-based gemini sur- When gas is blown into an aqueous surfactant solution, to stabi-
factants. From the table, it can be observed that the contact angles lize the gas and the liquid, a large amount of surfactant molecules
for the series of products were all smaller than those for water, adsorbs on the two interfaces; the hydrophilic groups adsorb on the
indicating that all of the products possessed favorable wetting on gas, whereas the hydrophobic groups adsorb on the liquid. How-
the Teflon and the PMMA. In addition, the ability to reduce the ever, because air is lighter than liquid, it continues to rise until it
contact angles by increasing the length of the hydrophobic group reaches the surface of the liquid; because the adsorption condi-
chains was even more noticeable. Theoretically, the longer the tion of the air within the liquid is different from the air outside of
hydrophobic group chains, the stronger the ability to reduce con- the liquid during the resurfacing process, once the foam reaches
tact angles. Among all of the products, Product 2C12 PSi possessed the surface, it forms a bimolecular membrane. The strength of the
the greatest surface activity. For Product 2C18 PSi, despite having foam membrane is related to the thickness of the bimolecular layer,
the longest hydrophobic group chains, it did not possess the great- which is determined by the amount of surfactants adsorbed on
est surface activity. This is attributable to the possible reasons: (1) the membrane. The amount of adsorption and the adsorption sur-
the hydrophobic group chains were too long, which caused the face area of the foam membrane can be determined based on the
molecules to become tangled on the surface of the liquids, thereby level of surface tension. Theoretically, a greater amount of adsorp-
preventing liquid drops from spreading, and (2) poor solubility tion and a smaller adsorption surface area on the surface of the
886 L.-H. Lin et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 436 (2013) 881–889

Table 3 1.15
Foaming properties of silicon-based gemini surfactants.
1.10
Compound Maximum height (cm) Stabilized height (cm)

2C0 PSi 0.5 0 1.05

2C6 PSi 0.6 0
2C12 PSi 1.0 1.0 1.00
2C18 PSi 1.0 0
0.95

I1/ I3
0.90
foam membrane signify a more organized and tighter arrange-
0.85
ment of molecules, which subsequently increases the thickness and
2C18PSi
strength of the foam membrane. The molecular arrangement also 0.80
2C0PSi
affects the strength of the foam membrane. When the molecular
0.75
arrangement is chaotic, the foam membrane’s contact with the air 2C6PSi
causes the foams to burst. This subsequently results in defoaming 0.70
2C12PSi
and foam-inhibiting-related studies by other researchers [25].
0.65
Table 3 shows the maximum foam height and the stabilized
0.0 0.5 1.0 1.5 2.0 2.5 3.0
foam height of silicon-based gemini surfactants after sitting for
5 min. As shown in the table, their foam heights were less than Concentration (mmol/L)
2 cm; consequently, they are categorized as low foaming products.
Fig. 5. Fluorescence intensity ratio versus concentration of silicon-based gemini
The height of the flowing foams increased in conjunction with the surfactants.
chain length of the hydrophobic groups, and the stabilized foam
height after sitting for 5 min was zero, which also indicates traits
of low foamability. Among all the products, Product 2C12 PSi pos- exceeded the CMC has the largest I1 /I3 ratio. Among all of the prod-
sesses identical foam-flowing height and stabilization height. This ucts, Product 2C12 PSi at the concentration exceeded the CMC had
is attributable to the following reasons: (1) the texture of the foams the lowest I1 /I3 ratio, indicating a neater and tighter arrangement
formed from Product 2C12 PSi were delicate and small, which shows within the molecular layer adsorbed on the pyrene, which sub-
good foam stability, and that the foams are not prone to burst- sequently contributed to the greatest nonpolarity of the micelles.
ing over time; (2) the hydrophobic group chains prevented the Despite having the longest hydrophobic group chains, the I1 /I3 ratio
molecules from forming a stable and uniform bimolecular layer on of Product 2C18 PSi was higher than Product 2C12 PSi. This was pri-
the foam membrane. The excessively long molecular chains tangled marily because the hydrophobic group chain length was too long,
on the foam membrane, creating empty holes and uneven bimolec- which caused the tangling and chaotic arrangement of molecules
ular layer thickness, which ultimately caused the foams to burst adsorbed on the pyrene. This resulted in the uneven thickness of the
[26]. molecular layer adsorbed on the pyrene, and reduced the intensity
of the nonpolarity, while increasing the I1 /I3 ratio [28].
3.5. Aggregation properties
3.6. Emulsification
The interaction between surfactants and pyrene affects the
properties of the system, such as the surfactants’ aggregation or During the emulsification process, surfactants are called emul-
dissolving of pyrene. When this occurs, the initial properties of sifiers that can take on the following two forms: (1) surfactant
the surfactants are altered. Therefore, the study of the interaction molecules are adsorbed on the oil particles, where the hydrophilic
effect between surfactants and molecules on medical treatment, groups face toward the water, whereas the hydrophobic groups
dye operation, and various other industries is exceptionally cru- face toward the oil, thereby reducing the surface tension between
cial. By using fluorescence analysis to observe the interaction effect the two phases; and (2) the surfactant molecules are arranged and
between pyrene and surfactants, the polarity and CMC of the adsorbed on the oil particles, forming a solid protective layer. The
micelles prior to and after formation were investigated. The flu- surfactant molecules cause the oil to carry zeta potential, where the
orescence spectrograph shows that the main characteristic peaks zeta potential within the particles forces them to repel, and sub-
were the first and third peak (374 and 384 nm, respectively), and sequently separate. However, to improve emulsion stability and
that the fluorescence intensity ratio (I1 /I3 ) affected the polarity of prevent oil and water from stratifying, the zeta potential value
the microenvironment [27]. Investigations were conducted on the between the particles must be amplified so that they can sepa-
relationship between the change in concentration and the I1 /I3 for rate the particles through repellence. In addition to increasing the
various products with different hydrophobic group chain lengths, zeta potential value, the thickness and strength of a molecular layer
where smaller ratios indicate greater nonpolarity in the formed adsorbed on the oil particles should be enhanced. This is because
micelles. For pyrene surrounded and adsorbed by neatly arranged greater molecular layer thickness and strength prevents particles
molecules, the nonpolarity intensity of their micelles increased. from aggregating in a collision [29].
Conversely, for pyrene surrounded by chaotic molecules or those Fig. 6 shows the zeta potential as a result of the change in pH of
containing poorer surface activity, their I1 /I3 ratio increased. silicon-based gemini surfactants. As shown in the diagram, the zeta
Therefore, the I1 /I3 ratio could be used to indicate the level of potential for the series of products was negative. Under acidic con-
neatness and tightness of a molecular layer adsorbed on the ditions, the zeta value was close to zero, which changed to −100 mV
pyrene. when the conditions were basic. This was because after being dis-
Fig. 5 shows the I1 /I3 ratio of silicon-based gemini surfactants. sociated in water, the alkalis would increase the negatively charged
As shown in the table, the I1 /I3 ratio for the series of products layer, making collisions less likely because of the repulsion between
dropped as the level of concentration increased. The I1 /I3 ratio particles. Nonionic surfactants can adsorbed onto the colloids, cre-
began stabilizing once the level of concentration exceeded the CMC, ating steric hindrance, which interferes with ionic mobility and
where the I1 /I3 ratio was reduced only when the chain length of thus with zeta potential. As the pH value increases, the zeta poten-
the hydrophobic groups increased, 2C18 PSi at the concentration tial value is decreased, thereby increasing the negative charge. An
 L.-H. Lin et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 436 (2013) 881–889 887

0 3
2C0PSi
2C12PSi
-20 2C18PSi
Zeta Potential (mV)

2C18PSi

Particle Size ( µm)

-40 2C6PSi
2

-60
2C12PSi

2C6PSi
-80

2C0PSi 1

-100
2 3 4 5 6 7 8 9 10 11 12
pH
0 2 4 6
Fig. 6. Changes in zeta potential as a result of the change in pH of silicon-based Time (hrs)
gemini surfactants.
Fig. 8. Average particle size of silicon-based gemini surfactants over time.

60 585 nm-590 nm
0.6
2C18PSi 2C0PSi 619 nm-624 nm
50
2C6PSi
2C12PSi 0.5

40
0.4
Volume (%)

Absorbance

30 0.3

20 0.2

10 0.1

0 0.0
0 1 2 3 4
400 500 600 700 800 900
Particle Size ( µm) Wavelength (nm)

Fig. 7. Particle-size distribution of silicon-based gemini surfactants. Fig. 9. Interaction effect between Product 2C0 PSi and Dye C.I. Disperse Blue 56.

In addition, larger particles moved up over time because of dif-

increase in the hydrophobic group chain length, however, dimin- ferences in density, thereby causing higher average particle size
ishes the negative charge’s increase. This shows that under basic distributions [31].
conditions, the zeta value for the series of products were greater,
making the particles much more dispersed and less likely to colli- 3.7. Interaction between dyes and the products
sion.
Fig. 7 shows the particle size distribution of the oil particles When dispersion dyes are added to water, they gather into a
emulsified by silicon-based gemini surfactants. As shown in the cluster because of their insolubility in water. This causes uneven
diagram, the particle size decreased as the length of the hydropho- dye spots. To improve the performance of the dyeing results, sur-
bic group chain increased, showing that the longer the hydrophobic factants must be added to dissolve the dyes so they are distributed
group chain is, the smaller the emulsion particle size become. The evenly in water and facilitate the dyeing process. When surfactants
size of the emulsion particles depends on the surface activity of the are added to a dye solution, they adsorb onto the surface of the dye
products. Based on the experiment, 2C12 PSi possessed the largest while wetting, dissolving, and dispersing the dye, eventually form-
surface activity among all products in the series; consequently, its ing a complex. Before adding the surfactants, dyes tend to gather
oil particles had the smallest particle size distribution. Fig. 8 shows and form an aggregate [32,33]. The addition of surfactants causes
that the average particle size of the series of silicon-based gemini the aggregate to break up, elevating the absorption intensity (εmax ).
surfactants increased over time. The reason why Product 2C12 PSi As stated above, the adding of surfactants to the dye creates a
had the smallest particle size was primarily because it possessed complex. As the surfactant concentration increases, the number of
the largest surface activity. For Product 2C18 PSi, despite having a the complex also increase, which prompts the rate of absorbance
greater surface activity than Products 2C0 PSi and 2C6 PSi, its emul- to change, led to generate a red shift or blue shift. Once a red shift
sion stability was relatively poorer. This is because the hydrophobic or blue shift occurs, the complex made from the surfactant and the
group chain was too long, which caused the product’s poor water dye changes the dye’s maximum wavelength (max ) [34].
solubility [30]. The undissolved contents in the emulsion also dis- Fig. 9 shows the interaction effect between Dye C.I. Disperse
rupted its stability, making the oil particles collide and rupture. Blue 56 and the silicon-based gemini surfactants. As shown in the
888 L.-H. Lin et al. / Colloids and Surfaces A: Physicochem. Eng. Aspects 436 (2013) 881–889

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