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Mechanical properties of melamine-formaldehyde microcapsules

Article  in  Journal of Microencapsulation · July 2001

DOI: 10.1080/02652040010019541 · Source: PubMed

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j. microencapsulation, 2001, vol. 18, no. 5, 593±602

Mechanical properties of melamine-formaldehyde

microcapsules

G. SUN and Z. ZHANG*

School of Chemical Engineering, The University of Birmingham, Edgbaston,
Birmingham B15 2TT, UK

(Received 16 June 2000; accepted 26 October 2000)

The mechanical properties of melamine-formaldehyde (M-F) microcapsules

were studied using a micromanipulation technique. Single microcapsules with
diameters of 1±12 mm were compressed and held between two parallel planes,
compressed and released, and compressed to burst at diŒerent speeds, whilst
the force being imposed on the microcapsules and their deformation were
measured simultaneously. This force increased as single microcapsules were
compressed and then relaxed slightly as they were held. When the
microcapsules were repeatedly compressed and released, a pseudo yield point
was found for each microcapsule. Before the microcapsules were compressed to
this point, the deformed microcapsules recovered to their original shape once
the force was removed. However, when the deformation was beyond the `yield
point’ there was profound hysteresis and the microcapsules showed plastic
behaviour. As the microcapsules were compressed to burst at diŒerent speeds,
ranging from 0.5±6.0 mm/s, it was found that their mean bursting forces did not
change signi®cantly. The deformations at the pseudo yield point and at bursting
were also independent of the compression speed. On average, these melamine-
formaldehyde microcapsules reached their `yield point’ at a deformation of
about 19 § 1%, and burst at a deformation of 70 § 1%.

Keywords: Microcapsules, melamine-formaldehyde, micromanipulation,

mechanical property, hysteresis.

Introduction

Melamine-formaldehyde microcapsules prepared by in situ polymerization

have impermeable walls. They have been widely used in carbonless copy paper,
by far the largest commercial application for the microcapsules (Kroschwitz 1995),
and other pressure-sensitive products such as carriers for fragrant oils (Hong and
Park 1999), pest repellents (Boh et al. 1999), and adhesives (Giroud et al. 1995).
For all these applications, understanding of the mechanical properties of the
microcapsules is essential for improving the quality of the products. However,
little such information is available, mainly because of their small sizes, typically 1±
10 mm in diameter when used for carbonless copy paper.
A few researchers have endeavoured to measure the mechanical properties or
strength of micropcapsules using indirect or direct methods. The former includes
evaluation of nylon microcapsule strength by quantifying their breakage in a
turbine reactor (Poncelet and Neufeld 1989) and in a bubble column (Lu et al.

* To whom correspondence should be addressed; e-mail: z.zhang@bham.ac.uk

Journal of Microencapsulation ISSN 0265±2048 print/ISSN 1464±5246 online # 2001 Taylor & Francis Ltd
http://www.tandf.co.uk/journals
DOI: 10.1080/02652040010019541
594 G. Sun and Z. Zhang

1992). The results from the indirect methods are di cult to use since the
mechanical damage to the microcapsules was determined not only by their
mechanical strength, but also by the hydrodynamics of the processing equipment,
and the latter is still not well understood. One of the earliest attempts to directly
measure the mechanical properties was made by Jay and Edwards (1968), who
used a micropipette technique to measure the force required to cause certain
deformation of single nylon microcapsules of diameter 50±260 mm. More recent
eŒorts include measuring between two parallel plates the strength of multiple
polyurethane microcapsules (Ohtsubo et al. 1991), the mechanical properties of
single polyurethane microcapsules (Liu et al. 1996), the stability of alginate-
chitosan microcapsules (Gaserod et al. 1999), and the mechanical resistance of
alginate-oligochitosan microcapsules (Bartkowiak and Hunkeler 2000). Unfortu-
nately, all these direct methods are not capable of determining the mechanical
properties including the strength of single microcapsules smaller than 50 mm in
diameter. Recently a micromanipulation technique has been developed to measure
the bursting force, diameter of single melamine±formaldehyde microcapsules, and
the relationship between the force imposed on the single microcapsules and their
deformation (Zhang et al. 1999). The microcapsules investigated were as small as
1 mm in diameter. This technique has been further used to measure the mechanical
properties of single melamine±formaldehyde microcapsules, which include elastic,
visco-elastic or plastic behaviours, and the results are presented.

Materials and methods

Preparation of melamine-formaldehyde microcapsules
Melamine-formaldehyde microcapsules were prepared based on the formula-
tion procedure recorded in a UK patent (Sinclair 1981). However, certain
modi®cations on this procedure were made.
The core material encapsulated was a 10:1 (w/w) mixture of HB40 and
kerosene, the former being a mixture of technical grade partially hydrogenated
terphenyls (Monsanto Limited, Brussels, Belgium). The microcapsule wall was
formed by R1144 copolymer, a technical grade acrylamide/acrylic acid copolymer
(Allied Colloids Ltd., Bradford, UK), and technical grade BC336 melamine-
formaldehyde precondensate (British Industrial Plastics Ltd., Birmingham,
UK). Microcapsules were prepared according to the following procedures:

(a) 23 g of R1144 copolymer was mixed with 20 g of BC336 precondensate and

280 g of deionized water,
(b) the pH of the solution was lowered to 4.3 by adding acetic acid then stirred
for 105 min,
(c) at 15 8C, 90 g of the core material was added into the solution, and the
mixture was emulsi®ed at 2500 rpm for 30 min,
(d) stirred the dispersion for 30 min at 15 8C,
(e) the temperature was increased to 55 8C. At this temperature, the dispersion
was continually stirred for 3 h. The microcapsules were then found to have
formed, and
(f) raised the pH of the dispersion to 10 by adding 20% NaOH solution.
 Mechanical properties of melamine-formaldehyde microcapsules 595

Figure 1. Schematic diagram of the micromanipulation rig.

Micromanipulation technique
The mechanical properties of melamine-formaldehyde microcapsules were
determined using a micromanipulation rig, as shown in ®gure 1.
The probe, shown in ®gure 1, had a diameter of 50 mm and was positioned
perpendicular to the bottom of a chamber. The microcapsules were dried in
the chamber and observed through side-view and bottom-view cameras.
Single microcapsules were compressed by the probe as it was driven downward
at a given speed. Details of this technique are described elsewhere (Zhang et al.
1999).
Experiments were carried out according to three stages. Firstly, single micro-
capsules were compressed at a speed of 1 mm/s to a certain deformation and held
under the probe. Secondly, single microcapsules were compressed and released at
the speed of 1 mm/s. Finally, the microcapsules were compressed up to burst at
diŒerent speeds of 0.5, 1.0, 3.0 and 6.0 mm/s. During all these operations, the force
being imposed on the microcapsules was measured simultaneously by a force
transducer (Model 403A, Auora Scienti®c Inc., Canada).

Results and discussion

Compress and hold
Figure 2 shows the force versus sample time as a M-F microcapsule was
compressed to diŒerent deformations, and held afterwards. Curve a 0 a corresponds
to the probe moving in air, ab to the microcapsule being compressd, bc to the
deformed microcapsule being held under the probe. Clearly, the force being
imposed on the microcapsule increased when it was deformed, and decreased
gradually when it was held. The larger the ®nal deformation, the greater the
corresponding force being imposed on the microcapsule, as expected. Such results
indicate that the microcapsules exhibited a visco-elastic behaviour.
596 G. Sun and Z. Zhang

Figure 2. Force versus time as a single M-F microcapsule was compressed and held.
Microcapsule diameter = 15 mm and compression speed = 1 mm/s.
 Mechanical properties of melamine-formaldehyde microcapsules 597

(a)

(b)

Figure 3. Force vs. dislacement as single M-F microcapsules were compressed and released.

Compress and release

Figure 3 presents typical relationships between the force and displacement
when single M-F microcapsules were compressed and released at 1 mm/s. As
demonstrated in ®gure 3(a), only a marginal hysteresis was found when the
microcapsules had a small deformation (12% in this case). The force being imposed
on the microcapsules dropped to zero only when the probe returned to its original
position. Therefore, the microcapsules can be considered to be visco-elastic for
such small deformations, which is consistent with the experimental results of
`compress and hold’. However, when the microcapsules underwent a relatively
large deformation (39% in this case), there was a more profound hysteresis, and the
598 G. Sun and Z. Zhang

force had already reduced to zero even if the probe was still far away from its
original position (see ®gure 3(b)). This indicates that the microcapsules had a
permanent (plastic) deformation after the force on them was completely released.
Since the microcapsules were visco-elastic at small deformations, and were plastic
at relative large deformations, there may be a yield point at which the plastic
behaviour began to occur. As shown in ®gure 3(b), the shape of the loading curve
changed from concave to convex at point B, which may be de®ned as a pseudo
`yield point’. Mathematically, the pseudo `yield point’ may be determined by the
following equation:

d2 F
ˆ0 …1†
dh2 at pseudo yield point

(Rektorys 1969), where F is the force and h is the displacement.

Compress microcapsules to burst

Figure 4 presents the relationship between the force and the probe moving
distance for compressing a single microcapsule to burst. Corresponding to the
curve A 0 A, the probe moved in air. At point A, the probe began to touch the
microcapsule. The force increased as the microcapsule was compressed (curve
ABC). At point C, the microcapsule was burst. Then, the force soon dropped to
zero and the probe was still moving until it hit the bottom of the chamber when the
force began to increase sharply. The force versus displacement corresponding to
the curve ABC in ®gure 4 is shown in ®gure 5. Similar to ®gure 3(b), there exists a
pseudo `yield point’ (point B) on the curve in ®gures 4 and 5.

Figure 4. Force versus probe moving distance as a single M-F microcapsule was com-
pressed to burst.
 Mechanical properties of melamine-formaldehyde microcapsules 599

Figure 5. Force versus displacement corresponding to curve ABC in ®gure 4.

Figure 6. Displacement at the pseudo `yield point’ versus diameter for single M-F micro-
capsules. Dotted lines represent the 95% con®dence intervals of the slope.

Deformation at pseudo yield point, at bursting and bursting force

Figures 6±8 show the displacement at the pseudo yield point, at bursting and
bursting force of microcapsules versus their diameter as they were compressed at a
speed of 3 mm/s. On average, the displacements at the pseudo yield point, at
bursting, and bursting force of the microcapsules increased with their diameter.
Their relationships are approximated by a linear regression through the origin in
®gures 6±8.
600 G. Sun and Z. Zhang

Figure 7. Displacement at bursting versus diameter for single M-F microcapsules. Dotted
lines represent the 95% con®dence intervals of the slope.

Figure 8. Bursting force versus diameter for single M-F microcapsules. Dotted lines
represent the 95% con®dence intervals of the slope.

Similar relatonships between the displacements at the pseudo yield point, at

bursting and bursting force of microcapsules and their diameter were found when
the microcapsules were compressed at the speed of 0.5, 1 and 6 mm/s. If their
relationships are expressed by

y ˆ Kx …2†

where y represents each of the former three parameters and x is the diameter, the
K values and the 95% con®dence intervals obtained at these diŒerent speeds are
presented in table 1.
 Mechanical properties of melamine-formaldehyde microcapsules 601

Table 1. K values including 95% con®dence intervals under diŒerent compression speeds.

K for displacement K for displacement K for bursting

Compression Number of at yield point at bursting force
speeds (mm/s) samples (mm/mm) (mm/mm) (mN/mm)

0.5 34 0.17 § 0.01 0.68 § 0.02 142 § 8

1.0 33 0.19 § 0.01 0.68 § 0.02 152 § 18
3.0 58 0.19 § 0.01 0.70 § 0.02 146 § 14
6.0 57 0.19 § 0.01 0.71 § 0.02 149 § 8
Average 0.19 § 0.01 0.70 § 0.01 148 § 6

As shown in table 1, the K values do not vary signi®cantly with the com-
pression speed within the experimental range. On average, melamine-formalde-
hyde microcapsules reached their yield point at the deformation of 19 § 1%, were
burst at the deformation of 70 § 1%, and the K value for correlating the bursting
force and diameter was 148 § 6 mN(mm)¡1 .
The compression speed did not aŒect the mean deformation at the pseudo yield
point, at bursting and bursting force of M-F microcapsules. This implies that the
viscous eŒect of the microcapsules on these three parameters is not signi®cant
although it existed. These results may be explained by comparing the magnitude
of the relaxation time, which may be determined from the `compression and
holding’ experimental results (®gure 2), and typical time for compressing single
microcapsules to burst. It has been estimated that the relaxation time from the data
in ®gure 2 was about 3 s (Ward and Hadley 1993), which is comparable to the
typical time for compressing single microcapsules to burst (¹0.2±20 s).
The bursting forces of the M-F microcapsules prepared for this work
(K ˆ 147 mN(mm)¡1 ) were signi®cantly greater than those in a previous report
(K ˆ 35 ¡ 47 mN(mm)¡1 , Zhang et al. 1999). This is because the current M-F
microcapsules had a much thicker wall (the amount of the wall materials used was
50% of the core materials in weight, compared with 15±20% for the previous
samples). The deformations at bursting of the microcapsules made of diŒerent wall
thickness were very similar (Zhang et al. 1999).
The relationship between the force and displacement for compressing single
microcapsules as shown in ®gure 5 may be modelled to determine other mechan-
ical property parameters, such as Young’s modulus (Liu et al. 1996) and yield
stress (Smith et al. 1998), by using appropriate constitutive equations (elastic,
visco-elastic or plastic) of the material. The experimental results from this work
have demonstrated that no simple constitutive equation can be applied to the
whole range of deformation, and provided a valuable guidance to choose appro-
priate constitutive equations for the modelling.

Conclusions

The mechanical properties of melamine-formaldehyde microcapsules were

determined by a micromanipulation technique. It has been found that the micro-
capsules exhibited a pseudo yield point under compression. Before being com-
pressed to this point, these M-F microcapsules showed a visco-elastic behaviour,
but after this point the microcapsules showed plastic characteristics. However, the
602 Mechanical properties of melamine-formaldehyde microcapsules

compression speed had no signi®cant eŒect on the deformation at the pseudo yield
point, at bursting and bursting force. On average, M-F microcapsules reached
their pseudo yield point when their deformation was 19 § 1%, and burst at the
deformation of 70 § 1%. It is believed that such information can help to determine
the stress±strain relationship from the micromanipulation measurement by using
appropriate constitutive equations of the material, and predict the rupture
behaviour of M-F microcapsules when they are used for making carbonless
copying paper or other pressure-sensitive products.

Acknowledgements

This research was supported by the Engineering and Physics Science Research
Council, UK. Arjo Wiggins Ltd., Allied Colloids Ltd. and British Industrial
Plastics Ltd. are thanked for providing chemicals for the preparation of melamine-
formaldehyde microcapsules.

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