film formation from nano-sized polystyrene latex particles

POLYMERS FOR ADVANCED TECHNOLOGIES

Polym. Adv. Technol. 2005; 16: 405–412

Published online 28 February 2005 in Wiley InterScience (www.interscience.wiley.com). DOI: 10.1002/pat.597

Film formation from nano-sized polystyrene

latex particles

Saziye Ugur1, Abdelhamid Elaissari2 and Onder Pekcan3*1Department of Physics, Istanbul Technical University, 80626 Maslak, Istanbul, Turkey2Macromolecular Systems & Human Immunovirology, CNRS-bioMerieux, UMR-2142 ENS de Lyon, 46 allee d’Italie, 69364 Lyon Cedex, France3Department of Physics, Isik University, 34398 Maslak, Istanbul, Turkey

Received 18 August 2004; Revised 23 November 2004; Accepted 3 January 2005

This work reports on the steady state fluorescence (SSF) technique for studying film formation from

surfactant-free, nano-sized polystyrene (PS) latex particles prepared via emulsion polymerization.

The latex films were prepared from pyrene (P)-labeled PS particles at room temperature and

annealed at elevated temperatures in 5, 10, 15, 20 and 30min time intervals above the glass transi-

tion temperature (Tg) of PS. During the annealing processes, the transparency of the film was

improved considerably. Monomer and excimer fluorescence intensities, IP and IE respectively,

from P were measured after each annealing step to monitor the stages of film formation. Evolution

of transparency of the latex films was monitored by using photon transmission intensity, Itr. Void

closure and interdiffusion stages were modeled and related activation energies were determined

and found to be 10.3 and 50.3 kJmol�1. Void closure temperatures, Tv, were determined from the

minima of Itr value. Copyright # 2005 John Wiley & Sons, Ltd.

KEYWORDS: voids; interdiffusion; excimer; fluorescence; polystyrene

INTRODUCTION

Paints, paper coatings, carpet backing,1 textiles, coatings for

drug delivery,2 foam mattresses3 and composites have been

well known as applications of latex systems. Film formation

from these latexes is complicated, multistage phenomenon

and depends strongly on the characteristics of the colloidal

particles. Latex films are generally formed by coalescence of

submicron polymer particles in the form of a colloidal disper-

sion, usually in water. The term ‘‘ latex film’’ normally refers

to a film formed from soft latex particles (with a glass transi-

tion temperature, Tg, below room temperature) where the

forces accompanying the evaporation of water are sufficient

to compress and deform the particles into transparent, void-

free film. Aqueous dispersion of soft latex particles are called

low-Tg, while non-aqueous dispersion of hard polymer par-

ticles is generally referred to as high-Tg. High-Tg latex parti-

cles remain essentially discrete and undeformed during

drying. Film formation from these dispersion can occur in

several stages. In both cases, the first stage corresponds to

the wet initial state. Evaporation of solvent leads to the sec-

ond stage in which the particles form a close packed array.

If the particles are soft, they are deformed to polyhedrons.

Hard latex, however, stay undeformed at this stage. Anneal-

ing of soft particles causes diffusion across particle–particle

boundaries which leads the film to a homogeneous continu-

ous material. Annealing of hard latex systems, deformation

of particles first leads to void closure4,5 and then, after the

voids disappear, diffusion across particle–particle bound-

aries starts, i.e. the mechanical properties of hard latex films

can be evolved by annealing; after all solvent has evaporated

and all voids have disappeared.

After the void closure process is completed, the mechanism

of film formation, by annealing of hard latex films is known as

interdiffusion of polymer chains followed by healing at the

polymer–polymer interface. In general, when two identical

polymeric materials are brought into contact at a temperature

above their Tg value, the junction surface gradually dis-

appears and becomes indistinguishable from any other

surface that might be located within the bulk material.

Brownian motion drives the polymer chains across the

junction until all traces of the original interface are lost; at

this point one may say that junction has ‘‘healed’’. Many

years ago Voyutskii6 suggested that the formation of a

continuous, strong and water-impermeable film involves

polymer diffusion across the junction of identical polymer

particles. When polymer chains are much longer than a

certain length, diffusion of chains is pictured as a worm-like

motion described by the reptation model, proposed by de

Gennes.7 Prager and Tirrell8 derived a relation for the

crossing density of the chains by using the reptation model

during the healing process. Wool and O’Connor9 employed

reptation to study crack healing in terms of several stages,

including wetting, diffusion and randomization, where at the

end of the wetting stage, potential barriers associated with

the inhomogenities at the interface disappear and chains are

free to move across the interface by a randomization process.

The fluorescence spectrum of pyrene consist of two

components; there is a structured emission band between

Copyright # 2005 John Wiley & Sons, Ltd.

*Correspondence to: O. Pekcan, Department of Physics, IsikUniversity, 34398 Maslak, Istanbul, Turkey.E-mail: [email protected]

370 to 450 nm which is characteristic of excited monomer

molecules and a structureless red shifted, broad band. This

blue emission band originates from excited dimers called

excimer, formed by the association of excited and unexcited

monomer molecules.10 As the concentration of pyrene

molecules is increased, the monomer intensity, IP, of pyrene

monomer decreases and the excimer intensity, IE, increases.

The IE/IP is proportional to the pyrene concentration.11 The

absorption spectrum is independent of pyrene concentration

and is characteristic of the monomer, showing that the dimers

are not present in the ground state. The first study of

intramolecular pyrene excimer formation in small molecules

was reported by Zachariasse and Kuhule.12 Their observation

indicates that the extent of excimer formation depends both

on the conformational and the dynamic properties of the

hydrocarbon chains. Pyrene excimer formation was used to

probe the end-to-end cyclization dynamics in polymers.13,14

The morphology of non-aqueous particles was studied by

using pyrene excimer formation excimer formation method

by labeling particles with pyrene molecules.15

Small-angle neutron scattering (SANS) method was used

to study latex film formation at the molecular level by

Sperling and coworkers on compression-molded polystyrene

(PS) film.16 Direct-non-radiative energy transfer (DET)

method was employed to investigate the film formation

process from dye-labeled polymeric particles.17–19 Steady

state fluorescence (SSF) technique combined with DET was

used to examine healing and interdiffusion processes in the

dye labeled poly(methyl methacrylate) (PMMA) latex sys-

tems.20,21 More recently photon transmission method has

been performed to study latex film formation from PMMA

and PS particles, using the UV-vis (UVV) technique as a

function of temperature and time.22–24

In this work, the evolution of film formation from

surfactant-free, nano-sized pyrene labeled PS particles was

studied by monitoring monomer (IP) and excimer emission

(IE) intensities and by using the SSF technique. Latex films

were prepared by annealing PS particles above theTg value of

PS in 5, 10, 15, 20 and 30 min intervals at temperatures

ranging from 90 to 3508C. Transmitted photon intensity, Itrwas monitored to study the evolution of transparency.

Increase in IE/IP ratio by increasing the annealing tempera-

tures was attributed to the void-closure process. Decrease in

IE/IP was attributed to the interdiffusion processes. The

maximum of IE/IP was interpreted as the healing point

during the film formation process.

EXPERIMENTAL

Pyrene labeled polystyrene particles were produced via sur-

factant free emulsion polymerization process. The polymeri-

zation was performed batch-wise using a thermostatted

reactor equipped with a condenser, thermocouple, mechani-

cal stirring paddle and nitrogen inlet. The agitation rate was

400 rpm and the polymerization temperature was controlled

at 708C. Water (100 ml), styrene (5 g) and the 1.133 mg of

fluorescent 1-pyrenylmethyl methacrylate (PolyFluor1

394) were first mixed in the polymerization reactor where

the the temperature was kept constant (at 708C), Potassium

Peroxodisulfate (KPS) initiator (0.1 g) dissolved in a small

amount of water (2 ml) was then introduced in order to

induce styrene polymerization. Sodium dodecyl sulfate

(SDS) (2.5 g m�1) was added in the polymerization process

to reduce the particle size. The polymerization was con-

ducted for 18 hr. Here it has to be mentioned that pyrenes

are exclusively labeled near the surface of the particles.

Five different latex films were prepared from the disper-

sion of particles by placing the same number of drops on a

glass plate with a size of 0.8� 2.5 cm2 and allowing the water

to evaporate. Then samples were separately annealed above

theTg value of PS (1058C), for 5, 10, 15, 20 and 30 min intervals

at temperatures ranging from 90 to 3508C. The temperature

was maintained within �28C during annealing.

After annealing at room temperature, each sample was

placed in the solid surface accessory of a Perkin–Elmer

Model LS-50 fluorescence spectrometer. Pyrene (P) was

excited at 345 nm and monomer and excimer fluorescence

emission spectra were detected between 300–600 nm. All

measurements were carried out in the front-face position at

room temperature. Slit widths were kept at 8 nm during all

SSF measurements. The sample position, incident light, I0, IPand IE emission intensities are shown in Fig. 1(a).

Photon transmission experiments were carried out using

model DU 530 Life Science UVV spectrometer from Beckman.

The transmittances of the films were detected between 300

and 400 nm. A glass plate was used as a standard for all UVV

experiments and measurements were carried out at room

temperature after each annealing processes. The sample

position and the Itr value are presented in Fig. 1(b). Atomic

force microscopy (AFM) images were obtained using a SPM-

9500-J3 Shimadzu scanning probe microscope.

RESULTS AND DISCUSSION

Monomer and excimer emission spectra of latex film

annealed in 10 min at elevated temperatures are shown in

Fig. 2 where it is seen that IE value increased as annealing tem-

perature is increased. In the mean time the IP-value from the

latex film decreased by indicating the computation with the

Figure 1. Schematic illustration of sample position and (a)

incident light (I0), monomer (IP) and excimer (IE) emission

intensities, (b) transmitted light intensity (Itr).

Copyright # 2005 John Wiley & Sons, Ltd. Polym. Adv. Technol. 2005; 16: 405–412

406 S. Ugur, A. Elaissari and O. Pekcan

excimer formation during the first stage of film formation.

Further annealing of the latex film, caused a decrease and

an increase of IE and IP intensities, respectively. The plot of

IE/IP ratios versus annealing temperature, T at 10, 15 and

30 min annealing time intervals are shown in Fig. 3(a)–3(c),

where it is seen that as the time interval is increased the max-

ima of the IE/IP ratio shifted to low temperatures. The Itrvalues versus annealing temperatures are also plotted in

Fig. 4(a)–4(c) for the films annealed at 10, 15 and 30 min inter-

vals, respectively. Upon annealing Itr values started to

decrease by presenting a minima and then increase again.

This minima moves to the lower temperature region as the

annealing time interval is increased. The sharp decrease at

the single temperature for Itr can be named as void closure

temperature, Tv. However, the temperature where IE/IP ratio

is reached to the maximum is called the healing temperature,

Th. Both Tv and Th values are moved to the low temperature

region as the annealing time interval is increased.

The increase in IE/IP in all likelihood corresponds to the

void closure process up to the Th point where the healing

process takes place.25,26 Decrease in IE/IP above Th can be

understood by the interdiffusion processes between polymer

chains. The behavior of IE/IP can be explained with the

schematic diagrams in Fig. 5. In Fig. 5(a), at the early stage of

film formation the powder film posses many voids and

pyrene monomers emit fluorescence. Figure 5(b) present a

film in which interparticle voids have disappeared due to

annealing and some excimer emission has started, because

more pyrenes become nearest neighbors. As soon as the voids

are filled, healing process takes place and most of the pyrenes

from pairs which emit solely excimer fluorescence (see

Fig. 5c). At this stage IE/IP reaches its maximum value. Then

due to further annealing, interdiffusion process occurs and

pyrenes are fully mixed throughout the latex film and they

start to emit solely monomer fluorescence by presenting a

decrease in IE/IP ratio. However, at the end of void closure

process, i.e. before the particle–particle interfaces are

disappeared most of the incident light is scattered which

results in the lowest Itr value. Then, during interdiffusion,

film becomes transparent and Itr increases at high annealing

temperatures.

AFM images of the latex film before and after annealing at

1708C are presented in Fig. 6(a) and 6(b), respectively, where

it is seen in Fig. 6(b) that all interfaces are removed by

annealing processes.

Void closureIn order to quantify the behavior of IE/IP below its maxima

the phenomenological void closure model can be introduced.

Latex deformation and void closure between particles can be

induced by shearing stress which is generated by surface ten-

sion of the polymer, i.e. polymer–air interfacial tension. The

Figure 2. Monomer (IP) and excimer (IE) spectra of latex

films after being annealed for 10 min at (a) 100, (b) 150 and

(c) 2508C.

Figure 3. Plot of IE/IP versus annealing temperature for the

films annealed in (a) 10, (b) 15 and (c) 30 min time intervals.

Film formation from nano-sized polystyrene 407


void closure kinetics can determine the time for optical trans-

parency and latex film formation.27 In order to relate the

shrinkage of spherical void of radius, r, to the viscosity of

the surrounding medium, Z, an expression is derived and

given by the following relation:27

dr

dt¼ � �

2�

1

�ðrÞ

� �ð1Þ

where g is surface energy, t is time and r(r) is the relative

density. It has to be noted that here surface energy causes

a decrease in void size and the term r(r) varies with the

microstructural characteristics of the material, such as the

number of voids, the initial particle size and packing. If

the viscosity is constant in time, integration of Eqn. (1) gives

the relation as:

t ¼ � 2�

�

ðrro

�ðrÞdr ð2Þ

where ro is the initial void radius at time t¼ 0.

The dependence of the viscosity of the polymer melt on

temperature is affected by the overcoming of the forces of

macromolecular interaction which enables the segments of

the polymer chain to jump from one equilibration position to

another. This process happens at temperatures at which free

volume becomes large enough and is connected with the

overcoming of the potential barrier. Frenkel–Eyring theory

produces the following relation for the temperature depen-

dence of viscosity:28,29

� ¼ A exp ð�H=kTÞ ð3Þ

where DH is the activation energy of viscous flow, i.e. the

amount of heat which must be given to one mole of material

in order that there is movement from one position to another

during viscous flow. Here A represents a constant for the

related parameters which do not depend on temperature.

Combining Eqns. (2) and (3) and assuming that the interpar-

ticle voids are of equal size and number of voids stay constant

during film formation (i.e. r(r)/ r�3, then integration gives

the following relation:

t ¼ 2AC

�exp

�H

kT

� �1

r2� 1

r20

� �ð4Þ

where, C is a constant related to relative density r(r). As was

stated before, a decrease in void size (r) causes an increase in

IE/IP ratios. If the assumption is made that IE/IP ratio is inver-

sely proportional to the sixth power of void radius, r then

Eqn. (4) can be written as25,26

IEIPðTÞ ¼ SðtÞ exp � 3�H

kBT

� �ð5Þ

where S(t)¼ (gt/2AC).3 Here, ro�2 is omitted from the rela-

tion since it is very small compared to r�2 values after the

void closure process has started.

As has already been argued earlier, the increase in IE/IPoriginates due to the void closure process, then Eqn. (5) was

Figure 4. Plot of Itr versus annealing temperatures for the

film annealed in (a) 10, (b) 15 and (c) 30 min time intervals.

Figure 5. Pictorial representation of film formation from PS

particles (a) before annealing, (b) film with no voids, (c) film

with no particle–particle interfaces and (d) film after inter-

diffusion process is completed.



applied to IE/IP below Th for the film samples. Figure 7(a)–

7(c) present the ln(IE/IP) versus T�1 plots for the films

annealed at 10, 15 and 30 min time intervals from which DHactivation energies were obtained and are listed in Table 1. It

is seen that activation energies do not change much by

increasing annealing time interval, i.e. the amount of heat

which was required by one mole of polymeric material to

accomplish a jump during viscous flow do not change by

varying the annealing time interval. The observed DH values

are found to be three times smaller than the values produced

from the films formed by 1 mm large PS latex particles.25 From

here it is understood that energy needed for viscous flow for

nano-sized particles are much smaller than micron-sized

systems during film formation.

Since the minima positions of Itr in Fig. 4 correspond to the

void closure point (tv, Tv), then Eqn. (4) can be written as:

tv ¼ SðrvÞ exp ð�Hv=kBTvÞ ð6Þ

where S(rv)¼ 2AC/grv2. Here rv is the minimal void radius at

which Itr becomes minimum and tv corresponds to the

annealing time interval at Tv. The behavior of tv versus Tv

and their logarithmic form are shown in Fig. 8(a) and 8(b),

respectively. As seen in Fig. 8(a) when the annealing tempera-

ture is increased, tv values decreased as expected, i.e. at high

temperatures shorter annealing times are required for the

void closure processes. The slope of the linear relation in

Fig. 8(b) gives DHv¼ 27.9 kJ mol�1 which is three times larger

than the value obtained from the excimer data. At this stage of

the work it is difficult to interpret this difference between DHand DHv values, which are measured using IE/IP and Itr data,

respectively.

Healing and interdiffusionThe decrease in IE/IP has already been explained earlier, by

the increase in monomer intensity from the latex film due to

interdiffusion. As the annealing temperature is increased

above Th, some part of the polymer chains may cross the

Figure 6. AFM micrograph of PS particles (a) before and (b)

after annealed at 1708C for 10 min.

Figure 7. Logarithmic plots of IE/IP data in Fig. 3 versus

inverse of annealing temperatures (T�1) for the films

annealed at (a) 10, (b) 15 and (c) 30 min time intervals.

Slopes of the straight lines produce DH values which are

listed in Table 1.



junction surface and particle boundaries disappear, as a

result IE decreases due to the disappearing of pyrene pairs.

In order to quantify these results, the Prager–Tirrell (PT)

model31,32 for the chain crossing density can be employed.

These authors used de Gennes’s ‘‘reptation’’ model to explain

configurational relaxation at the polymer–polymer junction

where each polymer chain is considered to be confined to a

tube which executes a random back and forth motion.32 The

total ‘‘crossing density’’ s(t) (chains per unit area) at junction

surface was calculated by PT from the contributions s1(t) due

to chains still retaining some portion of their initial tubes, plus

a remainder, s2(t). Here the s2(t) contribution comes from

chains which have relaxed at least once. Figure 9 shows the

pictoral representation of s1 and s2 contributions at the

particle–particle interface. Here the small segments repre-

sent the part of the polymer chain called the minor chain. In

terms of reduced time t¼ 2nt/N2 the total crossing density

can be given as:30,31

�ð�Þ=�ð1Þ ¼ 2��1=2�1=2 ð7Þ

here N is the number of freely jointed segments and n is the

linear diffusion coefficient given by the following relation:

� ¼ �o exp ð��E=kTÞ ð8Þ

here DE is defined as the activation energy for backbone

motion depending on the temperature interval. Combining

Eqns. (7) and (8) a useful relation is obtained as:

�ð�Þ=�ð1Þ ¼ Ro exp ð��E=2kTÞ ð9Þ

where Ro¼ (8not/pN2)1/2 is a temperature independent

coefficient. The decrease in IE/IP in Fig. 3 above Th is

already related to the disappearance of particle–particle

interface, i.e. as annealing temperature increased, more

chains relaxed across the junction surface and as a result

the crossing density increases. Now, it can be assumed

that IE/IP is inversely proportional to the crossing density

s(T) and then the phenomenological equation can be

written as:

IE=IPð1Þ ¼ R�10 exp ð�E=2kBTÞ ð10Þ

Logarithmic plots of IE/IP versus T�1 are presented in

Fig. 10(a)–10(c) for 10, 15 and 30 min annealing time inter-

vals, respectively. The DE value is produced by least squares

fitting the data in Fig. 10 to Eqn. (10) and the values are listed

in Table 1. The averaged value is found to be 50 kJ mol�1,

which is much larger than the void closure activation ener-

gies. This result is understandable because a single chain

needs more energy to execute diffusion across the

polymer–polymer interface than to be accomplished by the

Table 1. Activation energies

Annealing time interval, ta (min)

5 10 15 20 30 Average

DH (kJ mol�1) 7.3 8.9 11.5 10.6 13.0 10.3DE (kJ mol�1) 51.1 57.1 18.0 38.4 86.9 50.3

Experimentally produced activation energies:DHs, activation energyof viscous flow; DEs, activation energy of backbone motion.

Figure 8. Plot of (a) void closure time–temperature pairs

(tv, Tv) and (b) its logarithmic form.

Figure 9. Schematic illustration of interdiffusing chains

across the particle–particle interface. (a) Before annealing

and (b) after annealing.



viscous flow process. However, the producedDE value for this

nano-sized PS system is six times smaller than the micron-sized

PS system.25 This discrepancy most probably originates from

the high temperature annealing region of nano- sized PS sys-

tem, which requires much less energy for the chains to execute

reptation across the particle–particle interface.

The maxima in IE/IP were already attributed to the healing

point (th, Th) where (1� 1/e) of the minor chain crosses the

particle–particle interface. The (th, Th) pairs are plotted in

Fig. 11 where it is seen that as th is increased Th decreases to

execute the healing process using minor chains during film

formation. In order to interpret the data in Fig. 11, Eqn. (7) is

written at the healing point as:

th ¼ B exp ð�Eh=kBThÞ ð11Þ

where B ¼ �ðTÞ�ð1Þ

� ��N2

8�0

� �, which is constant for a given time

and temperature. Equation (11) can be used to produces heal-

ing activation energy DEh. The fit of Eqn. (11) to the data in

Fig. 11(a) is presented in Fig. 11(b), where the slope of the

straight line produces the DEh value as 38.5 kJ mol�1 which

is smaller than DE, as expected. Since the minor chain needs

smaller energy than the whole chain to accomplish its motion

across the polymer–polymer interface.

CONCLUSION

In conclusion, film formation processes of nano-sized PS

latexes were investigated using excimer and monomer fluor-

escence from the pyrene labeled polymer chain, in conjuga-

tion with the morphological evolution of the films at

elevated temperatures. It has been shown that simple kinetic

models for void closure, healing and interdiffusion mechan-

isms fit quite well to fluorescence data. Supporting

UVV experiments confirming the fluorescence measure-

ments and produce data to understand the film formation

mechanism.

Figure 10. Logarithmic plots of IE/IP and their fit to Eqn. (10)

above the healing point in Fig. 4 for (a) 10, (b) 15 and (c)

30 min time intervals. The slope of the linear relations

produces DE values, listed in Table 1.

Figure 11. Plots of (a) healing time–temperature pairs (th,

Th) and (b) their logarithmic form.



AcknowledgmentsThe authors would like to thank Mr Esat Pehlivan for helping

with the AFM micrographs. One of us also (OP) would like to

thank the Turkish Academy of Sciences (TUBA) for their

partial support.

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film formation from nano-sized polystyrene latex particles

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