Materials Letters 260 (2020) 126916

Contents lists available at ScienceDirect

Materials Letters
journal homepage: www.elsevier.com/locate/mlblue

Natural rubber latex foam production using air microbubbles:

Microstructure and physical properties
Sanit Sirikulchaikij a, Rungrote Kokoo b, Matthana Khangkhamano a,⇑
a
Department of Mining and Materials Engineering, Faculty of Engineering, Prince of Songkla University, Hat Yai, Songkhla 90112, Thailand
b
Department of Chemical Engineering, Faculty of Engineering, King Mongkut’s University of Technology North Bangkok, Bangkok 10800, Thailand

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

Article history: Natural rubber latex foams (NRLFs) are manufactured by Dunlop and Talalay processes. Although, Talalay
Received 3 October 2019 process offers the foams with better flexibility and physical properties than the Dunlop does, Dunlop pro-
Received in revised form 23 October 2019 cess is mainly used in Thailand because of low production cost. In this study, NRLFs with spherical cell-
Accepted 29 October 2019
shape and exceptional interconnective foam network were simply fabricated using an alternative process
Available online 31 October 2019
called Bubbling technique, instead of the complicated and expensive Talalay process. The Bubbling pro-
cess involves microbubble generation within the compound latex containing in a bubble column by flow-
Keywords:
ing air through a microporous diffuser. The inlet air flow rate was varied to alter cell size and physical
Natural rubber
Latex foam
properties of the bubbled foams.
Production Ó 2019 Elsevier B.V. All rights reserved.
Microbubbles

1. Introduction
Natural rubber latex foams (NRLFs) are cellular structure mate-
rials manufactured from concentrated latex compounds by the two
well-known batch processes; Dunlop and Talalay. Talalay process
offers considerably soft NRLFs with better flexibility and physical
properties than the Dunlop does. Even though that, in Thailand,
Dunlop technique has been mainly used for manufacturing latex
foam products such as pillows, cushions, and mattresses [1] due
to simpler and lower production cost than Talalay process. Dunlop
process uses a Hobert mixer to foam and gel the latex, whereas
Talalay process requires vacuum and freezing system [2]. More-
over, for modern factories with high production rate, continuous
process is employed. The Oaks mixer is designed to mix continu-
ously and to offer a uniform and superior mixture, variation of
foam density, and reduction in labor cost [2]. The Oaks mixer, how-
ever, is more expensive and complicated than the Hobart mixer
used in Dunlop process. This makes continuous system impractical
for small and medium enterprises (SMEs) especially in Thailand.
In our previous work [3], an alternative technique, Bubbling
process, for manufacturing NRLFs with the cellular structure simi-
lar to that of the Talalay foams without the necessary of vacuum
and freezing system, but the use of a microbubble generator, was
introduced. In this work, microbubbles were simply generated by
blowing air through a sintered porous glass and effectively foamed
⇑ Corresponding author.
E-mail address: kmatthana@eng.psu.ac.th (M. Khangkhamano).
the latex compound, instead of using a Hobert mixer in the Dunlop
or vacuum and freezing in the Talalay. The Bubbling technique
offers a number of advantages, i.e. the use of no moving parts,
low maintenance cost, and less energy consumption. In addition,
stability of the microbubbles in the presence of surfactants allows
them to be pumped without collapse [4]. In this study, microstruc-
ture and physical properties of the bubbled foams prepared at var-
ious air flow rates were highlighted in comparison with those of
the Dunlop foams.
2. Materials and methods
2.1. Materials
The formulation and materials used in this research were listed
in Table 1. High ammonia (HA) natural rubber latex was supplied
by Chalong Latex Industry Co., Ltd, Thailand. All chemicals used
were purchased from L.B. Science limited partnership, Thailand.
2.2. Preparation of NRLFs via Dunlop process
Dunlop process involves four main processing steps: compound
preparation, foaming, gelling and curing [2] as presented in Fig. 1.
Latex compound was prepared by mixing and maturing HA latex,
PO, S, ZDEC, ZMBT, and WL for 48 h. The compound (167 g) was
stirred at 1200 rpm using a Hobart mixer to attain the foam with
10 times of its original volume. DPG and ZnO were added and fol-
lowed by SSF while stirring at 500 rpm, and then molded to obtain

https://doi.org/10.1016/j.matlet.2019.126916
0167-577X/Ó 2019 Elsevier B.V. All rights reserved.
2 S. Sirikulchaikij et al. / Materials Letters 260 (2020) 126916

Table 1 a gelled foam. The gelled foam was then cured in an oven at 120 °C
Formulation for NRLF production. for 90 min and then washed with water to remove residual PO soap
Ingredients Total solid content Formulation and dried at 70 °C for 24 h.
(%) (phr)*
HA latex type 60 100
Potassium oleate (PO) 10 1.5 2.3. Preparation of NRLFs via bubbling process
Sulfur (S) 50 2
Zinc diethyldithiocarbamate 50 2 The foams were prepared similarly to the Dunlop process
(ZDEC) except the step of foaming. For foaming, an experimental appara-
Zinc 2-mercaptobenzhiolate 50 2
tus was shown in the inset (Fig. 1), the compound (167 g) was
(ZMBT)
Wingstay L (WL) 50 2 loaded into a bubble column. Air was then fed through a diffuser
Zinc oxide (ZnO) 50 5 (a pore size range of 10–16 mm) which firmly equipped inside the
Diphenyl guanidine (DPG) 33 1.4 column. The inlet air flow rate was varied at 20, 50 and
Sodium silicofluoride (SSF) 12.5 0.25
100 cm3/minute. At this stage, the compound was allowed to foam
*Amounts are given as part per hundred parts of latex (phr). and expand to 10 times of its original volume.

Fig. 1. Flow chart of NRLF preparation by Dunlop and bubbling processes. The inset demonstrates an experimental setup for bubbling process.
 S. Sirikulchaikij et al. / Materials Letters 260 (2020) 126916 3

All fabricated NRLFs were labeled differently where DF was where M and V are the mass and volume of the latex foam in g and
symbolized for the Dunlop foam, while BF20, BF50 and BF100 des- cm3, respectively.
ignated as the bubbled foams processing at air flow rates of 20, 50 Compression set was tested according to ISO1856 Method B
and 100 cm3/min, respectively. standard (Max 6%) using a compression set tester (JIS A5756,
Yasuda, Japan). The foam hardness (indentation hardness index)
3. Characterization was tested according to ISO 2439 Method A standard (Soft <100,
Medium 101–170, and Hard >170) using a foam compression tester
Morphological study was performed using a SEM (JSM-5800LV) (F0013, IDM, Australia).
and cell size was measured using ImageJ software [5]. Number of
cells per unit volume (N) and Density of the foam were determined
4. Results and discussion
using Eq. (1) [6] and Eq. (2)
!
6 qrubber 4.1. Morphological study
N¼ 1 ð1Þ
pd 3 qfoam
Fig. 2 presents cross-section photographs, microstructure, and
where, d represents the cell diameter, qrubber and qfoam are densities cell size distribution of DF and BFs produced from Dunlop and Bub-
of the solid rubber (1.09 g/cm3) and the rubber foam, respectively. bling techniques, respectively. The DF composed of non-uniform
cell size with irregular shape and heavily fractured
qfoam ¼ M=V ð2Þ
interconnective-cell structure which is in a good agreement with

Fig. 2. Macroscopic cross-section view, SEM images, and cell size distribution of the Dunlop and the Bubbled foam.
4 S. Sirikulchaikij et al. / Materials Letters 260 (2020) 126916
Fig. 3. Density, indentation hardness index, compression set, and recovery percentage of the DF and BFs.
the previous study [7]. Its average cell size was 378 mm. In contrast,
the BFs exhibited spherical cell shape, crack-free and flawless
interconnected foam network which such structure is normally
achieved by Talalay process [8]. Such cellular structure produced
by Bubbling and Talalay processes enhances compression set,
durability, and breathability and permeability of the foams [9].
Furthermore, the cell sizes for each BF were similar throughout
the specimen, suggesting its homogeneous density and hardness
throughout the specimen. The average cell sizes gained from the
BF20, BF50, and BF100 were 415, 496, and 727 mm, respectively,
which increased with the flow rate.
The number of cells per unit volume (N) for the DF, BF20, BF50,
and BF100 were 2.39  105, 2.16  105, 1.73  105, and
0.72  105 cells/cm3, respectively. The cell size is proportional to
the flow rate but inversely proportional to N. This is because larger
bubble size is formed when higher air flow rate (or larger pore size
of the diffuser) is applied [10]. It is worth to note that, either
reduced air flow rate or pore size of the diffuser, the foam with
smaller cell size than that of the BF20 can be fabricated. The differ-
ence in cell size when the flow rate was adjusted suggests an
advantage of this technique that cell size can be adjustable, and
hence the physical and mechanical properties can also be altered.
4.2. Physical properties
Density, compression set, and indentation hardness index were
presented in Fig. 3. All the BFs possessed lower density than the DF.
Among the BFs, the density decreased with the increased flow rate
(Fig. 3a). Cellular structure and density are closely related to each
other. When the cell size increases, it also causes the expansion
ratio of the foam [11]. As a result, reduced number of cells per unit
volume and hence lower density of the foam [11]. For compression
set (Fig. 3c), the value declined with the decreased flow rate. As
compared to the DF, less value of compression set was achieved
from the BF20 and BF50. According to Ariff and co-workers [12],
cell size plays a major role in compression set measurement. Sup-
posedly, the larger cells are prone to collapse first rather than the
smaller ones due to microscopic deformation at the cell wall. How-
ever, in this event, it is possible that, during the deformation, the
smaller cells in between the cell wall along with spherical cell
shape and good interconnected cell network were not damaged
or ruptured leading to a better compression set and recovery of
the foam. The highest recovery percentage of 97% was found on
the BF20 and BF50 (Fig. 3d). The DF showed poorer ability to
recover even though it possessed smaller cell size than the BFs.
This phenomenon is attributed to the distinction in cellular struc-
ture of the two foam types. In addition, the hardness index values
(Fig. 3b) of all foams were less than 100 N which are classified as
soft foams. The index values of the BFs were proportional to the
cell size; the value increases linearly with the cell size [8]. There-
fore, hardness level of the BFs can also be altered by controlling
the air flow rate.
5. Conclusions
Bubbling process was used as an alternative low-cost technique
for NRLF production. The bubbled foams possessed spherical cell
structure with flawless interconnected foam network. By using this
method, cell size and physical properties of the foams can be
altered by varying air flow rate.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
This research was supported by the Faculty of Engineering
(grant number ENG6027010222S) Prince of Songkla University.
 S. Sirikulchaikij et al. / Materials Letters 260 (2020) 126916 5

References Polym. Sci. 62 (1) (1996) 117–127, https://doi.org/10.1002/(SICI)1097-4628

(19961003)62:1.
[7] A.F.A. Karim, H. Ismail, Z.M. Ariff, Mechanical and morphological properties of
[1] A.S.M. Bashir et al., Mechanical, thermal, and morphological properties of
kenaf powder filled natural rubber latex foam, AIP Conf. Proc., 2015, DOI:
(eggshell powder)-filled natural rubber latex foam, J. Vinyl Add. Tech. 23 (1)
10.1063/1.4919166.
(2017) 3–12, https://doi.org/10.1002/vnl.21458.
[8] D.C. Blackley, Polymer Latices: Science and Technology Volume 3: Applications
[2] D. Eaves, Handbook of Polymer Foams, Rapra Technology Limited, Shrewsbury,
of Latices, 2nd ed., Springer, Netherlands, 1997.
UK, 2004.
[9] S.K. Luo et al., Study on the cell structure and mechanical properties of methyl
[3] S. Sirikulchaikij et al., Rubber foam processing via bubbling technique, Mater.
vinyl silicone rubber foam materials, Adv. Mater. Res. 1004–1005 (2014) 297–
Sci. Forum 962 (2019) 96–100, https://doi.org/10.4028/www.scientific.net/
306, https://doi.org/10.4028/www.scientific.net/AMR.1004-1005.297.
MSF.962.96.
[10] D. Ma et al., Two-dimensional volume of fluid simulation studies on single
[4] S. Khuntia, S.K. Majumder, P. Ghosh, Microbubble-aided water and wastewater
bubble formation and dynamics in bubble columns, Chem. Eng. Sci. 72 (2012)
purification: a review, Rev. Chem. Eng. 28 (4–6) (2012) 191–221, https://doi.
61–77, https://doi.org/10.1016/j.ces.2012.01.013.
org/10.1515/revce-2012-0007.
[11] G. Wypych, Handbook of Foaming and Blowing Agents Toronto, ChemTec
[5] V. Amandine et al., An ImageJ tool for simplified post-treatment of TEM phase
Publishing, Canada, 2017.
contrast images (SPCI), Micron 121 (2019) 90–98, https://doi.org/10.1016/j.
[12] Z.M. Ariff et al., Effect of foaming temperature and rubber grades on properties
micron.2019.01.006.
of natural rubber foams, J. Appl. Polym. Sci. 107 (4) (2008) 2531–2538, https://
[6] K.C. Guriya, D.K. Tripathy, Morphology and physical properties of closed-cell
doi.org/10.1002/app.27375.
microcellular ethylene–propylene–diene terpolymer (EPDM) rubber
vulcanizates: effect of blowing agent and carbon black loading, J. Appl.