Polymer Testing 65 (2018) 352–359

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Polymer Testing
journal homepage: www.elsevier.com/locate/polytest

Material Properties

The preparation of calcium pimelate modified OMMT from natural Ca- T

montmorillonite and its application as β-nucleating agent for polypropylene
Jing Cao, Na Wen, Yuying Zheng∗
College of Materials Science and Engineering, Fuzhou University, Fuzhou 350108, Fujian, People's Republic of China

A R T I C L E I N F O A B S T R A C T

Keywords: Ca-montmorillonite (Ca-MMT) was first modified with different amount of two different kinds of surfactants to
Ca-montmorillonite obtain organo-montmorillonites (OMMTs) directly via ion exchange between Ca2+ and alkyl ammonium cations.
Calcium pimelate Then remained Ca2+ in OMMTs was reacted with pimelic acid (HA) to obtain CaHA-OMMTs. PP/CaHA-OMMT
Polypropylene composites were prepared. Results of FT-IR demonstrate the existence of long-chain alkyl in OMMTs, and CaHA
β-nucleating agent
in CaHA-OMMTs. The reaction between HA and OMMT could lead to an increase in d-spacing value of clay.
CaHA-OMMTs with high CaHA contents and obviously increased d-spacing values were obtained. Results of
WAXD and TEM show exfoliated clay platelets in PP/CaHA-OMMT composites. The obviously increased Tc, and
the high β-phase content in PP/CaHA-OMMT composites demonstrate the high β-nucleation efficiency of CaHA-
OMMTs. Composites with higher content of β-phase epitaxial crystallized on exfoliated clay platelets display
largely improved impact strength.

1. Introduction transition of exchangeable metal ion type from Ca-MMT to Na-MMT by

Polymer-layered silicate nanocomposites (PLAN) have become an
important area of polymer composites research because of its unique
physical and chemical properties, such as high mechanical strength,
modulus, thermal stability, and low gas permeability [1–3]. Mon-
tmorillonite (MMT) is one of the most commonly used 2:1 layered clay
minerals in which the negative layer charge is electrically balanced by
the equal charge of exchangeable cations, such as Na, Ca, or K [4]. Due
to the abundance of MMT as a natural mineral, the physico-chemical
properties, high cation exchange capacity and high surface areas of
MMT, it has been widely used in industrial applications and researches
as reinforcing filler [5–7], catalysts [8,9], rheology control reagents
[10,11], waterproof and adsorbents [12–14].
Pristine MMT can only compatible with hydrophilic polymers, such
as poly (ethylene oxide) (PEO) [15], or poly (vinyl alcohol) (PVA) [16].
To make MMT compatible with other polymers such as polypropylene,
it is necessary to prepare organo-montmorillonites (OMMT) by convert
the normally hydrophilic surface to an organophilic one, making the
intercalation of many engineering polymers possible. The quaternary
alkyl ammonium salts with the alkyl chain of 12–18 carbon atoms are
the most commonly used organic source for preparing OMMT. How-
ever, most previous research focused on the synthesis of organoclays
using Na-montmorillonites (Na-MMT) [17–20]. The organic modifica-
tion of Ca-montmorillonites (Ca-MMT) was usually realized by the
an ion exchange reaction between Na+ and Ca2+ cations in an aqueous
system and then quaternary ammonium cations were intercalated into
the interlayer spaces of Na-MMT through a second ion exchange reac-
tion. There were also several reports about the organic modification of
Ca-montmorillonites directly [21–23].
In addition to the organic modification of Ca-MMT through ion
exchange reaction, the interlayer Ca2+ ion make it possible to introduce
some functional compounds to MMT. Dai X et al. [24] reported the
preparation of calcium pimelate (CaHA) supported MMT through the
chemical reaction between pimelic acid (HA) and Ca2+ ion on the
surface of OMMT, which provides heterogeneous β-nucleation effect for
isotactic polypropylene (iPP). Moreover, CaHA has been widely used to
improve the β-nucleating efficiency of the inorganic fillers including
aluminum hydroxide [25], TiO2 [26], CaCO3 [27,28], carbon nano-
tubes [29], zeolite [30], etc. The results show that using CaHA sup-
ported β nucleating agent is an effective way to enhance the β-crys-
tallization of PP and PPR.
However, it is with regret that the dispersion condition of OMMT
layers in polypropylene matrix was not involved in Dai X's research. For
example, were they intercalated or exfoliated in the matrix? How the
reaction between OMMT and HA affects the interlayer distance of
OMMT? These are very important because the dispersion condition of
clay platelets in nanocomposites are shown to be closely related to the
final properties of the nanocomposites. The large aspect ratio of silicate

∗
Corresponding author.
E-mail address: yyzheng@fzu.edu.cn (Y. Zheng).

https://doi.org/10.1016/j.polymertesting.2017.11.031
Received 19 October 2017; Received in revised form 28 November 2017; Accepted 29 November 2017
Available online 01 December 2017
0142-9418/ © 2017 Elsevier Ltd. All rights reserved.
J. Cao et al.
can fully contribute to the nanocomposites property under the condi-
tion that large stacks of silicate exfoliate or delaminate into individual
layers. On the other hand, the raw material used in Dai X's research is
commercial OMMT, which was prepared from Ca-MMT by the ion ex-
change of Ca2+ and Na+, and then the intercalation of quaternary
ammonium cations into the interlayer spaces of Na-MMT. Therefore,
the concentration of Ca2+ ions remained in the interlayer could be very
low and is unknown for the users.
In this paper, OMMTs with β-nucleation surface was prepared from
natural Ca-MMT. Two kinds of quaternary alkyl ammonium salts were
used for the preparation of OMMTs respectively. This was done directly
without the exchange of Ca2+ and Na+. The as prepared OMMTs were
then reacted with HA to obtain OMMTs with CaHA surface. The in-
fluence of alkyl ammonium salts loading on the interlayer distances of
OMMTs and OMMTs with CaHA was studied. The OMMTs with CaHA
were then used to prepare PP nanocomposites. The dispersion condi-
tions of clay platelets, β-phase content, crystallization behavior, and
mechanical properties of the nanocomposites were discussed.
2. Experimental
2.1. Materials
The Ca-MMT used in this study was supplied by Shijiazhuang
Changli Minerals Co., LTD. The CEC of the Ca-MMT is 80 meq/100 g.
The cationic surfactants octadecyltrimethylammonium (ODTMA, 98%)
and dihexadecyldimethylammonium bromide (DHAB, 97%) for the
preparation of organoclay, and the chemical grade pimelic acid (HA)
were supplied by Shanghai Aladdin Bio-Chem Technology Co., LTD.
CaHA was prepared by pimelic acid/calcium hydroxide in our labora-
tory. The polypropylene (PP) used in this study was k8050
(MFR = 50 g/10 min) provided by Formosa Chemicals & Fiber
Corporation. Polypropylene-graft-maleic anhydride (PP-g-MA, Dow
chemical Inc., USA) with a MA content of 1.0% and a MFI of 100 g/
10 min was used as compatibilizer.
2.2. Synthesis of the organo-montmorillonites (OMMTs) and CaHA-
OMMTs
The synthesis of OMMTs were performed using the following pro-
cedure: 10 g of Ca-MMT was dispersed in 300 mL of deionised water
gradually then magnetic stirred for 30 min. A predissolved stoichio-
metric amount of surfactant was firstly dissolved in 100 mL of deionised
water and was then stirred for a further 30 min. The dissolved surfac-
tant was slowly added to the clay suspension at room temperature. The
CEC of the Ca-MMT is 80 meq/100 g, which represents a measure of the
loading of the clay with the cationic surfactant. During the synthesis,
the surfactant concentrations in terms of the CEC value were 0.4 CEC,
0.7 CEC and 1.0 CEC, respectively. The OMMTs modified by ODTMA
were denoted as ODTMA-04, ODTMA-07 and ODTMA-10, and those
modified by DHAB were denoted as DHAB-04, DHAB-07 and DHAB-10,
respectively. The mixtures were then stirred for 3 h at room tempera-
ture under ultrasonication. After reaction, the white precipitate was
isolated by filtration and the excess of bromide and organic ions was
removed by repeated washing with deionized water until a negative
result of the AgNO3 test was obtained. The samples were dried at room
temperature, and then at 65 °C in a vacuum oven overnight. The dried
OMMT were ground in an agate mortar.
The dried OMMT and HA were firstly mixed and ground at room
temperature and then placed in a vacuum oven to react at 120 °C for
1 h. The mass ratio of OMMT to PA was fixed at 10. The CaHA -OMMTs
prepared from OMMTs modified by ODTMA were denoted as ODTMA-
04-HA, ODTMA-07-HA and ODTMA-10-HA, and DHAB-04-HA, DHAB-
07-HA and DHAB-10-HA for those modified by DHAB.
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Polymer Testing 65 (2018) 352–359
2.3. Preparation of PP/CaHA-OMMT nanocomposites
The CaHA-OMMTs were dried in a vacuum oven and then mixed
with PP-g-MA and PP by a mini-extruder (WLG10G, Shanghai Xinshuo
Precision Mechanics Co., LTD) and injection molded by a mini-injection
molding machine (WZS10G, Shanghai Xinshuo Precision Mechanics
Co., LTD) to form rectangular bars with a dimension of
80 × 10 × 4 mm3. Both the content of OMMT and PP-g-MA was fixed
at 5 wt %. For comparison, PP/Ca-MMT composite was also prepared
with the same conditions.
2.4. Characterization of OMMTs and CaHA-OMMTs
OMMTs and CaHA-OMMTs were characterized by fourier-transform
infrared spectrum (FT-IR), wide-angle X-ray diffraction (WAXD) and
thermogravimetric analysis (TGA). The FT-IR measurements were car-
ried out on a Nicolet 5700 fourier-transform IR spectrometer. The
WAXD tests of were carried out on an Ultima III instrument with a
conventional CuKa X-ray tube at a voltage of 40 kV and a filament
current of 40 mA. The scanning 2θ range was between 2° and 12° to
characterize the interlayer distance of clay. The scanning rate was 2°/
min. TGA was carried out under nitrogen with a TA Instrument TGA
Q600 thermogravimetric analyzer at a heating rate of 20 °C/min from
35 °C to 900 °C.
2.5. Characterization of PP/CaHA-OMMT composites
The morphologies of clay platelets in PP/CaHA-OMMT composites
were characterized by WAXD and transmission electron microscopy
(TEM). The crystallization behaviors were investigated by differential
scanning calorimetry (DSC), and mechanical properties were obtained
by Charpy impact tester. The WAXD was characterized between 10° and
35° to investigate the crystalline morphology of PP. The content of β-
phase was calculated by the Turner-Jones equation [31].
Iβ (300)
Kβ =
Iβ (300) + Iα (110) + Iα (040) + Iα (130) (1)
where Kβ is the relative β-form content, and
Iβ (300), Iα (110), Iα (040) and Iα (130) are the diffraction peak intensity of the
(300) crystal plane of the β-form, the peak intensities of the (110),
(040) and (130) crystal planes of the α-form, respectively. TEM was
operated with Philips CM200 at an acceleration voltage of 200 kV.
Ultrathin sections of 100 nm were prepared on a Leica Ultracut FC
microtome at cryogenic temperature using a diamond knife. DSC was
carried on with a Netzch DSC 214 DSC under nitrogen atmosphere.
About 5 mg of sample was heated from ambient temperature to 210 °C
at a heating rate of 20 °C/min and held at this temperature for 5 min to
eliminate the thermal history. Then samples were cooled to room
temperature at a cooling rate of 10 °C/min, and re-heated to 200 °C at a
heating rate of 20 °C/min. β-fraction (βC) was estimated from DSC by
equation (2) [32].
(1 − λ ) β
βC =
(1 − λ ) β + (1 − λ )α (2)
where (1-λ) is the degree of crystallinity associated with each phase. It
can be calculated from the ratio ΔHa/ΔHf, where ΔHa and ΔHf are the
apparent and completely crystalline heats of fusion, respectively. The
values 177.0 and 168.5 J/g were used for the ΔHf for 100% crystalline
α-iPP and 100% crystalline β-iPP, respectively [33].
Charpy impact tests were performed following ISO 179-1:2000.
Injection-molded rectangular samples with dimensions of
80 mm × 10 mm × 4 mm and a single-edge 45° notch were tested
using a Charpy impact tester (XJJ-5, Chengde Jiande Testing
Equipments Co., Ltd, China).
J. Cao et al.
Fig. 1. FT-IR spectra of original Ca-MMT and OMMT modified by ODTMA and DHAB.
3. Results and discussion
3.1. Characterization of OMMTs and CaHA-OMMTs by FT-IR, WAXD and
TGA
FT-IR spectra provide information on the minerals present in the
samples and the chemical composition of the dominant minerals. Fig. 1
displays the FT-IR spectra of Ca-MMT and OMMTs. The Ca-MMT ex-
hibits an absorption band near 3625 cm−1 corresponding to the OH
stretching vibration, which is typical for MMT of high octahedral alu-
minum content. The broad band at 3436 cm−1 is caused by the OH of
water present in the minerals and in KBr. The broad band near
1035 cm−1 is caused by the complex Si-O stretching, and the 796 cm−1
proves the occurrence of microcrystalline SiO2 admixture. Compared to
Ca-MMT, OMMTs modified by ODTMA or DHAB show absorption
bands at around 2925 cm−1, 2852 cm−1 and 1470 cm−1. The narrow
bands at 2925 and 2852 cm−1 correspond to the asymmetric and
symmetric CH stretching vibrations of alkyl chains, and the 1470 cm−1
attributed to the asymmetric (C-H) bending vibration of CH3 and CH2
groups. Moreover, the intensity of the above bands increases with the
amount of ODTMA or DHAB increasing. These results demonstrate the
long-chain alkyl chains have been successfully introduced onto Ca-
MMT through the ion exchange between Ca2+ and alkyl ammonium
cations. Fig. 2 shows the IR spectra of HA, CaHA and CaHA-OMMTs.
Compared to the spectra of OMMT, the CaHA-OMMTs show char-
acteristic bands at 1580 cm−1 and 1540 cm−1, corresponding to the
Fig. 2. FT-IR spectra of HA, CaHA and CaHA modified OMMT.
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Polymer Testing 65 (2018) 352–359
stretching vibration of C-O and C=O of CaHA, respectively. This is
resulted from the reaction between the Ca2+ of Ca-MMT and the
–COOH of HA adhered on the surface of Ca-MMT.
WAXD could provide information of the basal spacing of clays di-
rectly. Changes in basal spacings are often an indication that organic
surfactant has been intercalated within the interlayers of clay. Fig. 3(a)
and Fig. 3(b) display WAXD patterns of Ca-MMT, OMMTs and CaHA-
OMMTs modified using DHAB and ODTMA, respectively. Original Ca-
MMT displays characteristic (001) diffraction corresponding to a d-
spacing of 1.48 nm, which is typical for Ca-MMT containing Ca2+
surrounded by two layers of water molecules [34]. The dominant d-
spacing of OMMTs modified by DHAB increases to 3.01 nm, 3.65 nm
and 3.71 nm with DHAB loading of 0.4 CEC, 0.7 CEC and 1.0 CEC,
respectively. The value increases further to 3.37 nm, 3.72 nm and
3.77 nm, respectively after the reaction between Ca2+ and HA. At a low
dosage (0.4 CEC) of ODTMA, the dominant d-spacing value of OMMT
modified by ODTMA remains almost the same with original Ca-MMT.
And the subsequent reaction between HA and Ca2+ has little effect on
the d-spacing value. With the ODTMA concentration increases to 0.7
CEC and 1.0 CEC, the dominant d-spacing value reaches 2.57 nm and
2.54 nm, and further increases to 3.21 and 3.19 nm, respectively after
the reaction between Ca2+ and HA. Moreover, the relative peak in-
tensities of both OMMT and CaHA-OMMT become higher with the in-
crease of ODTMA or DHAB loading, while the widths at half-peak
height are smaller, suggesting a narrower interlayer d-spacing dis-
tribution of the OMMTs and CaHA-OMMTs at a higher surfactants level.
The expansion of interlayer spacing of OMMTs demonstrates the
successful intercalation of long-chain alkyl ammonium cations into the
interlayers of Ca-MMT, resulting from the exchange of Ca2+ in the Ca-
MMT by organic ODTMA+ or DHAB+ cations. With the same con-
centrations of surfactants, the OMMTs modified by DHAB exhibit larger
d-spacing values than those modified by ODTMA. This is reasonable
because the double long-chain alkyl of DHAB gives rise to lager volume
in the interlayer of OMMTs than ODTMA. The further increased d-
spacing values of CaHA-OMMTs except ODTMA-04-HA compared to
their precursor OMMTs implies the reaction between Ca2+ and HA
occurs in the interlayer of OMMT. The expansion of interlayer spacing
and the higher hydrophobicity of OMMT would make it more compa-
tible with polymer molecules and the intercalation of polymer mole-
cules into the interlayer of OMMT more easily. The d-spacing value of
ODTMA-04-HA, as well as those corresponding to the weak peaks in
other CaHA-OMMTs remains almost the same with their precursor
OMMTs. Considering the d-spacing value is large enough for HA to
intercalate into the interlayer, and the amount of Ca2+ in the interlayer
is sufficient in this case, this result is probably because the intercalation
of HA could not resist the strong interaction between clay platelets. The
reaction induced expansion occurs only when the d-spacing is larger
than a critical value (dc). Based on the WAXD results in Figs. 3 and 4, it
is concluded that dc is larger than 1.85 nm.
TG and DTG curves of Ca-MMT, HA, CaHA, OMMT and CaHA-
OMMT prepared with DHAB at 0.4 CEC are shown in Fig. 4(a) and (b),
respectively. The calculated TGA data are listed in Table 1. Two main
mass loss steps are observed for Ca-MMT. The first mass loss between
35 °C and 160 °C is attributed to the dehydration of water absorbed on
the surface and in the interlayers of Ca-MMT. The last mass loss step at
500–750 °C is assigned to the decomposition of OH groups on the Ca-
MMT. The dehydration caused a 12.3% mass loss, while 3.8% were
caused by the dehydroxylation. The HA degrades completely between
130 and 350 °C, while three degradation processes are observed for
CaHA. The mass loss of 7.6% at 155–215 °C is attibuted to the eva-
poration of crystalline bonded water. The mass loss of 40.9% in the
temperature range of 385–480 °C is corresponding to the evaporation of
organic substances, cyclohexanone produced by decomposition of
CaHA. The mass loss of 15.9% at temperature between 630 °C and
730 °C is the evaporation of CO2 produced by decarboxilation process of
CaCO3 formed in heating decomposition process.
J. Cao et al. Polymer Testing 65 (2018) 352–359

Fig. 3. WAXD patterns of Ca-MMT, OMMTs and CaHA-

OMMTs modified by DHAB (a) and ODTMA (b).

The overall mass loss of DHAB-04 is higher than that of Ca-MMT Table 1
due to the decomposition of DHAB+ cations upon heating. The de- Thermal degradation data of CaHA, HA, Ca-MMT, DHAB-04 and DHAB-04-HA.
gradation at temperature between 220 °C and 500 °C with a mass loss of
Sample Degradation stage Temperature range Mass loss (%)
14.2% is attributed to the degradation of DHAB. For DHAB-04-HA, the
mass loss of 22.4% between 150 °C and 500 °C is attibuted to the de- CaHA Ⅰ 155–215 7.6
gradation of reacted HA and the degradation of DHAB. The mass loss in Ⅱ 385–480 40.9
the temperature range of 550–750 °C for DHAB-04 and DHAB-04-HA is Ⅲ 630–730 15.9
HA Ⅰ 130–350 97.1
2.9% and 2.5%, respectively, which is related to the dehydration of the Ca-MMT Ⅰ 35–160 12.3
hydroxyl groups on the silicate crystal. Ⅱ 500–750 3.8
Effect of the loadings of DHAB and ODTMA on the TG curves of DHAB-04 Ⅰ 220–500 14.2
OMMTs and CaHA-OMMTs modified by DHAB and ODTMA are shown Ⅱ 550–750 2.9
DHAB-04-HA Ⅰ 150–500 22.4
in Fig. 5 (a) and (b), respectively. The calculated data of TG curves were
Ⅱ 550–750 2.5
listed in Table 2 and Table 3. TG curves of OMMTs are similar with that
of DHAB-04. All display two main degradation stages in the tempera-
ture range of around 220–500 °C and 550–750 °C, respectively. It is between HA and Ca2+ in the interlayer of the platelets, allowing more
observed in Table 2 that with the increase of surfactant loading, both Ca2+ to react with HA.
the total mass loss and the mass loss in the temperature range of
220–500 °C increases linearly, implying the content of surfactant mo-
lecules bonded to the Ca-MMT siloxane layer increases gradually. The 3.2. Characterization of CaHA-OMMTs in PP/CaHA-OMMT composties
TG curves of CaHA-OMMTs are similar with that of DHAB-04-HA. All
display two main degradation stages in the temperature range of It is well known that the significant property improvement of
150–500 °C and 550–750 °C, respectively. The content of CaHA sup- polymer occurs only for exfoliated composites resulted from the inter-
ported on OMMTs were calculated by equation (3). action of clay platelets with polymer matrix. The dispersibility assess-
ΔWCaHA − OMMT − ΔWOMMT ment of Ca-MMT and CaHA-OMMTs with different surfactant loading in
ΔWCaHA % = PP nanocomposites was carried out by WAXD and the results are shown
ΔW0 (3)
in Fig. 6. The diffraction patterns of PP/Ca-MMT composite and PP/
where ΔWCaHA is the content of CaHA in CaHA-OMMT, ΔWCaHA − OMMT is ODTMA-04-HA shows a broad diffraction peak at 2θ = 6.01° and 5.89°,
the mass loss of CaHA-OMMT between 385 and 480 °C, ΔWOMMT is the corresponding to the d-spacing of 1.47 nm and 1.50 nm, respectively,
mass loss of OMMT at 385–480 °C, ΔW0 is the mass loss of CaHA at which maintain the value of neat Ca-MMT. However, no obvious dif-
385–480 °C and the value is 40.9%. The calculated content of CaHA are fraction peak was seen in the XRD patterns of other nanocomposites,
listed in Table 3. As expected, the content of CaHA decreases with the suggesting the predominant existence of exfoliated clay platelets. In
loading of DHAB or ODTMA increasing, because the content of Ca2+ in order to support the XRD results, TEM micrograph was investigated and
OMMTs decreases with the loading of DHAB or ODTMA. The contents the results shown in Fig. 7 also demonstrates that multilayered struc-
of CaHA in CaHA-OMMTs modified by DHAB are higher than those ture is dominant in PP/ODTMA-04-HA, while the clay platelets are
modified by ODTMA, which may be attributed to the larger interlayer exfoliated in PP/ODTMA-07-HA. The exfoliation of clay platelets is
spacing of the former facilitates the intercalation of HA and the reaction attributed to the intercalation of long-chain alkyl ammonium cations

Fig. 4. TG (a) and DTG (b) curves of Ca-MMT, HA,

CaHA, DHAB-04 and DHAB-04-HA.

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J. Cao et al. Polymer Testing 65 (2018) 352–359

Fig. 5. TG curves OMMTs and CaHA-OMMTs modified

by DHAB (a) and ODTMA (b).

Table 2
Thermal degradation data of OMMTs modified by DHAB and ODTMA.

Sample Mass loss of surfactant (%) Total mass loss (%)

DHAB-04 14.2 19.0

DHAB-07 20.4 25.9
DHAB-10 27.5 31.2
ODTMA-04 9.6 15.5
ODTMA-07 16.1 24.0
ODTMA-10 21.3 26.7

Fig. 7. TEM images of PP/ODTMA-04-HA composite (a) and PP/ODTMA-07-HA com-

Table 3 posite (b).
The calculated data of TG curves and the content of CaHA.

Surfactant Content of Mass loss of Mass loss of CaHA CaHA

furfactant OMMTs at –OMMTs at content
(CEC) 385–480 °C (%) 385–480 °C (%) (%)

DHAB 0.4 6.04 12.24 15.2

0.7 8.13 12.10 9.7
1.0 7.78 10.64 7.0
ODTMA 0.4 6.24 8.83 6.3 PP/ODTMA-10-HA
Intensity

0.7 7.01 8.11 2.7

PP/ODTMA-07-HA
1.0 7.76 8.02 0.7
PP/ODTMA-04-HA
PP/DHAB-10-HA
PP/DHAB-07-HA
PP/ODTMA-10-HA
PP/DHAB-04-HA
PP/Ca-MMT
PP/ODTMA-07-HA
PP

1.50 10 15 20 25 30 35
PP/ODTMA-04-HA
2θ (degree)
PP/DHAB-10-HA
Intensity

Fig. 8. WAXD patterns at 2θ range of 10–35° for PP and PP composites with Ca-MMT and
PP/DHAB-07-HA CaHA-OMMTs.

PP/DHAB-04-HA
3.3. Crystallization structure of the composites
1.47
PP/Ca-MMT WAXD patterns concerning the crystal morphology of PP and PP
composites with Ca-MMT or CaHA-OMMTs are displayed in Fig. 8. The
tested samples are rectangular bars obtained by injection molding. It is
2 4 6 8 10 12 14
obvious that PP and PP/Ca-MMT composite display diffraction peaks at
2θ (degree) 2θ = 14.1°, 16.9° and 18.8°, corresponding to the primary reflection of
Fig. 6. WAXD patterns at 2θ range of 2–12° for PP composites with Ca-MMT and CaHA- the (110), (040) and (130) planes of α-phase PP crystals, respectively.
OMMTs. While all the composites with CaHA-OMMTs exhibit the characteristic
diffraction peak at 2θ = 16.0° and 21.1°, which corresponded to the
into the interlayer spacing of Ca-MMT, which increases the interlayer primary reflection of the (300) and (301) planes of β-phase, respec-
distance and improves the compatibility between MMTs and PP, as well tively. A higher relative intensity of (300) peak reflects a higher content
as the further expansion of interlay spacing induced by the CaHA fa- of β-phase. The Kβ values calculated by equation (1) are listed in
cilitate the intercalation of PP chains into the interlayer of clay platelets Table 4. The Kβ values vary from 0.60 to 0.71 for all PP/CaHA-OMMT
and hence the exfoliation of platelets under shear. composites. Composites modified by DHAB show higher Kβ values than
those modified by ODTMA, which is probably due to the higher content
of CaHA of the former. Moreover, it seems that the Kβ values increase

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J. Cao et al. Polymer Testing 65 (2018) 352–359

Table 4
Thermal parameters of various samples calculated from DSC.

Tc (oC) Tmβ (oC) Tmα (oC) βc Kβ

PP 116.5 – 163 0.00 0.00

PP/Ca MMT 117.7 – 163.6 0.00 0.01
PP/DHAB-04-HA 125.2 152.5 164.2 0.93 0.67
PP/DHAB-07-HA 124.3 153.4 164.3 0.92 0.65
PP/DHAB-10-HA 124.3 153.4 164.2 0.95 0.71
PP/ODTMA-04-HA 125.2 153.5 163.9 0.92 0.60
PP/ODTMA-07-HA 125.8 152.2 163.6 0.91 0.62
PP/ODTMA-10-HA 125.2 153.7 164.5 0.94 0.69

slightly, although the content of CaHA decreases with surfactant

loading increasing, indicating the high β-nucleation efficiency of CaHA
supported by OMMTs especially those with exfoliated clay platelets
resulted from larger interlayer distance. This is reasonable because the Fig. 10. Charpy impact strengths of the composites.
larger interlayer spacing results in higher portion of exfoliated platelets,
thus provides more surface area for the crystallization of β-crystal.
The results suggest that the dispersion condition of clay platelets is
more important than the content of CaHA in CaHA-OMMTs to the
3.4. Melting and crystallization behaviors of the composites formation of high content β-crystal in our researched range.

Considering the strong shear during processing impeding the for-

3.5. Mechanical properties of the composites
mation of β-crystal, the Kβ values of the injection molded bars are re-
latively slow and influenced by the processing conditions. To demon-
Charpy impact strengths of the injection molded bars of PP/CaHA-
strate the β-nucleation ability of the prepared CaHA-OMMTs further,
OMMTs composites were tested to investigate their final properties. The
DSC cooling curves at a rate of 10 °C/min and the subsequent heating
results are displayed in Fig. 10. PP exhibits impact strength of 1.7 kJ/
curves were recorded. DSC cooling and heating curves are shown in
m2. With the addition of Ca-MMT, the impact strength shows no ob-
Fig. 9(a) and Fig. 9(b), respectively. The data obtained from DSC curves
vious change. The addition of CaHA-OMMT modified by 0.4 CEC
and βc values calculated from equation (2) are listed in Table 4. From
ODTMA gives rise to a slight increase of impact strength, while the
Fig. 9(a), one observes a crystallization temperature (Tc) of 116.5 °C for
addition of others lead to obviously improved impact strength, espe-
PP and a slightly increased Tc of 117.7 °C for PP/Ca-MMT composite.
cially those with exfoliated platelets. The maximum value reaches
For PP/CaHA-OMMTs composites, the Tc values increase to 124–126 °C,
3.25 kJ/m2 for PP/DHAB-10-HA. In addition, composites with DHAB
regardless of the kind of surfactants or their loadings, suggesting the
modified CaHA-OMMTs show slightly higher impact strength than
strong nucleation effect of CaHA-OMMTs on PP. The DSC heating
those with ODTMA modified CaHA-OMMTs. These results reveal both
curves of PP and PP/Ca-MMT composite exhibit only one melting peak
the content of β-crystal and the dispersion condition of clay in the
of α-crystal at around 163 °C. Combined with the cooling curve of PP/
composites plays an important role in the final performance of the
Ca-MMT composite, it is concluded that original Ca-MMT shows weak
composites. Composites with high content of β-crystal supported by
α-nucleation effect on PP. The PP/CaHA-OMMT composites modified
exfoliated CaHA-OMMTs platelets, especially those whose precursor
using either ODTMA or DHAB exhibited two melting peaks at about
CaHA-OMMTs with larger d-spacing values, exhibit largely improved
152–154 °C and 163–165 °C, corresponding to the melting of β- and α-
toughness.
crystal, respectively. Additionally, melting peak corresponding to β-
crystal is much higher than that of α-crystal for all PP/CaHA-OMMT
composites, indicating the predominant existence of β-crystal in PP. All 3.6. Toughening mechanism in PP/CaHA-OMMT composites
PP/CaHA-OMMT composites exhibit a value higher than 0.9, regardless
of the loading of surfactants or the content of CaHA in the CaHA- Based on the above results, schematic diagrams of the preparation
OMMTs. Moreover, PP/DHAB-10-HA and PP/ODTMA-10-HA exhibit of PP/CaHA-OMMT composites from well intercalated and non-inter-
slightly higher values than other composites in their same group, which calated CaHA-OMMTs are illustrated in Fig. 11. For well intercalated
is in accordance with the DSC results. This is due to the strong β-nu- CaHA-OMMTs (Fig. 11(a)), the clay platelets are easily exfoliated under
cleation effect of CaHA supported by OMMTs platelets, especially the shear when compounded with polymer melt. Then the CaHA supported
well exfoliated ones, which supply more nucleating surface for PP [24]. by exfoliated clay platelets exhibits high β-nucleation efficiency and

Fig. 9. DSC cooling (a) and heating (b) curves of

OMMTs and CaHA-OMMTs.

357
J. Cao et al.
Fig. 11. Schematic diagrams of the preparation of PP/CaHA-OMMT composites with well intercalated (a) and non-intercalated (b) OMMTs.
lead to high content of β-crystal epitaxial crystallized on the surface of
clay platelets. This exfoliated platelets supported β-crystal could fully
contribute the nanocomposites property and the toughening effect of β-
crystal. When the non-intercalated CaHA-OMMTs are compounded
with polymer (Fig. 11(b)), it is difficult for polymer chains to inter-
calate into the interlayer spacing, thus the multilayered structure are
predominant in the composite. Under cooling, the CaHA induced β-
crystallizaiton occurs on the surface of stacked clay platelets. Although
the content of CaHA is higher in this case, the lower surface area sup-
plied by stacked clay platelets limits the β-nucleation sites density and
results in the formation of microcomposite rather than nanocomposite.
Thus the mechanical performance of the composite is relatively lower.
4. Conclusions
In this paper, a two-step method was used to prepare CaHA-OMMTs
from Ca-MMT. Firstly, DHAB and ODTMA were used respectively to
modify Ca-MMT and prepare OMMTs directly. Then HA was added to
react with Ca2+ in the OMMTs to obtain CaHA-OMMTs. Both the in-
troduction of surfactant and the reaction between HA and Ca2+ results
in an increased d-spacing value of clay except the OMMT and CaHA-
OMMT modified with 0.4 CEC ODTMA. OMMTs and CaHA-OMMTs
prepared with DHAB shows larger d-spacing values than those modified
by ODTMA. The reaction between OMMT and HA leads to an increase
of d-spacing when the d-spacing value of OMMT is larger than 1.85 nm.
The content of CaHA in the CaHA-OMMTs modified by DHAB is higher
than those modified by ODTMA. However, the content of CaHA in
CaHA-OMMTs modified by both surfactants decreases with the increase
of surfactant loading, which is determined by the concentration of re-
mained Ca2+ in their precursor OMMTs. Most of the clay platelets are
exfoliated in PP/CaHA-OMMTs composites except for PP/ODTMA-04-
HA. PP/CaHA-OMMT composites show obviously increased Tc com-
pared to PP. In our researched range, CaHA-OMMTs with lower CaHA
content but larger interlayer spacing could induce higher content of β-
crystal. Both the dispersion condition of clay platelets and the β-phase
content in the composites contributes the toughness of the composites.
The β-crystal epitaxial crystallized on the surface of exfoliated clay
platelets could fully contribute to the nanocomposites property and the
toughening effect of β-phase simultaneously.
This paper shed light on the preparation of OMMT supported β-
nucleating agent for PP with well intercalated clay platelets and high β-
nucleation efficiency from natural Ca-MMT by a simple, effective and
358
Polymer Testing 65 (2018) 352–359
low-cost method.
Acknowledgements
This work was supported by the Guidance Project of Science and
Technology Agency of Fujian province (Grant No. 2015H0016).
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://dx.
doi.org/10.1016/j.polymertesting.2017.11.031.
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