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Chinese Science Bulletin 2006 Vol. 51 No. 3 293298

DOI: 10.1007/s11434-006-0293-3

The glass transition temperature and microstructure of polyurethane/epoxy resin interpenetrating polymer networks nanocomposites
JIA Qingming, ZHENG Maosheng, SHEN Renjie & CHEN Hongxiang
School of Material Science and Engineering, Xian Jiaotong University, Xian 710049, China Correspondence should be addressed to Zheng Maosheng (email: mszheng@mail.xjtu.edu.cn)

Abstract Nanocomposites with various contents of organophilic montmorillonite (oMMT) have been prepared by adding oMMT to interpenetrating polymer networks (IPNs) of polyurethane and epoxy resin (PU/EP) which had been prepared by a sequential polymeric technique. DSC experiment indicates a novel phenomenon that the glass transition temperature (Tg) of the nanocomposites increases with the oMMT content up to 3 %, then decreases with further increasing oMMT content. In order to explain this phenomenon, crosslink density, hydrogen bonding in the hard segments, crystallization of the nanocomposites and the exfoliation degree of oMMT in the nanocomposites have been investigated by swelling method, FT-IR, XRD, SEM and TEM, respectively. The results indicate that the crosslink density and the hydrogen bonding index of the nanocomposites increase, but the crystallization degree of the nanocomposites decreases with increasing oMMT content. In addition, oMMT improves the network structure of PU/EP.
Keywords: organophilic montmorillonite, interpenetrating polymer networks, nanocomposites, glass transition temperature.

immediately surrounding the particle due to the presence of the interface[1]. Polymer/layered silicate nanocomposites show dramatic improvements in mechanical properties, barrier properties, thermal resistance and flame retardant properties at lower clay loading compared with conventional composites, and offer potential access to completely new classes of materials with unique properties, which has attracted considerable concerns in many fields[2 14]. Numerous studies have shown that clay has some effect on the Tg of polymer/organic clay nanocomposites. However, no coherent conclusion has been drawn about the effect of clay on the Tg so far. Some investigators proved that the Tg of polymer/organic clay nanocomposites increased with increasing clay content[4 7]. Others found that the Tg of polymer/clay nanocomposites deceased with increasing clay content[8 13]. Moreover, Moon et al.[14] found that montmorillonite had no effect on the Tg of polyurethane/clay nanocomposite. Interpenetrating polymer networks (IPNs) are polymer alloys consisting of at least two polymers in the networks. IPNs allow mutual enhancement of the properties of polymers, and are promising to many application fields. The Tg of IPNs reflects the microstructure of polymer blends and the compatible ability of the components, so the Tg of IPNs was investigated widely[15 17]. However, study on the effects of clay on the Tg and microstructure of IPNs/organic clay nanocomposites is comparatively limited. As shown in our earlier study, the PU/EP IPNs nanocomposites exhibited excellent mechanical properties and water resistance[18]. The objective of this work is to investigate the effects of oMMT on the Tg and microstructure of the PU/EP IPNs nanocomposites and explain why the Tg of the nanocomposites changes with increasing oM MT content. 1 Experimental 1.1 Materials

Glass transition temperature (Tg) has been extensively studied for many polymers since it is one of the most fundamental features relative directly to polymer properties. In general, inorganic nanofillers do not directly contribute to the Tg of the matrix, but the interaction of the polymer chains with the surface of the particles can drastically alter the chain kinetics in the region
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The commercial 2,4-toluene diisocyanate (TDI) and Octadecylammonium were made in Shanghai Chemical Reagent Co. (China). Commercial castor oil, diglycidyl ether of biphenol A (DGEBA) and 2,4,6-tri(dimethylaminomethyl) phenol (DMP-30) were made in Tianjin Chemical Co. (China). The pristine montmorillonite was provided by South Clay Co. (China). The method for preparing organic montmorillonite was similar to Chang et al.s[19]. Castor oil and DGEBA were dried under a vacuum prior to use.
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1.2 Synthesis of the PU/EP IPNs Quantitative castor oil was placed in a roundbottomed flask, heated until 60 , and thoroughly mixed with a predetermined amount of TDI, the reaction system was stirred vigorously with a Teflon-coated magnetic stir bar, under a dry nitrogen atmosphere, for about 45 min to form a urethane prepolymer. Then a predetermined amount of the epoxy precursor (DGEBA, PU/EP=80:20) was added to the system which was stirred for a while before adding 1.5%, by weight, of DMP-30 (based on the amount of DGEBA). The mixture was degassed under a vacuum for several minutes, then poured and pressed into the preheated Teflon molds. The filled molds were heated until 120 and were cured at that temperature for several hours, then the PU/EP IPNs were synthesized, marked as PU/EP0. 1.3 Synthesis of PU/EP IPNs nanocomposites

Fig. 1. The DSC curves of PU/EP IPNs with different oMMT contents.

Castor oil and different amounts of oMMT (1%, 3%, 5%, by weight, based on the amount of castor oil and TDI) were placed in a round-bottomed flask, heated and stirred vigorously with a Teflon-coated magnetic stir bar, for about 4 h, then the temperature of the mixed system was reduced to room temperature, and quantitative TDI was added to the system. The following steps were the same as those of synthesis of PU/EP IPNs. The PU/EP IPNs nanocomposites with different oMMT contents were prepared, marked as PU/EP1, PU/EP3 and PU/EP5, respectively. 1.4 Characterization

Differential scanning calorimetry (DSC) tests were carried out on the DSC 822e (METTLER TOLEDO) to measure the glass transition temperature. Temperature and energy calibration were carried out with indium. The scan rate was 10 /min within the temperature range of 70100. Fig. 1 plots the DSC results of samples upon heating with the glass transition temperature being marked and the glass transition temperature is taken at the median point in the range of glass transition. Crosslink density of the PU/EP IPNs nanocomposites with different oMMT contents was tested by swelling method. The test method and steps are similar to that of Lu et al.[20]. Fourier transform infrared spectra (FTIR) of oMMT, PU/EP IPNs and PU/EP IPNs nanocomposites were
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conducted on an IRprestige-21 spectrometer in the wave number range of 4000400 cm1. X-ray diffraction (XRD) was used to determine the basal spacing in the nanocomposites, and the test was performed at room temperature with a Rigaku X-ray diffractometer with a CuK radiation source (=0.154 nm), which was operated at 40 kV and 30 mA. The samples were snapped under the same tensile test condition, and then fractured surface was coated with gold (100 A) using an Edwards S 150 A sputter coater. The fractured surface structure of the nanocomposites was observed by a JEOL JSM-6400 scanning electron microscope (SEM) operated at 20 kV. Samples were prepared by an LKB Bromma 2088 Ultrotome at 50, giving sections of nearly 100 nm in thickness. Subsequently, one layer of carbon of about 10 nm in thickness was deposited on these slices on mesh 300 copper nets for TEM observations on a Hitachi H-600 electron microscope with an acceleration voltage of 120 kV. 2 2.1 Results and discussion DSC analysis

The changes of the Tg for the pure PU/EP IPNs (PU/EP0) and the PU/EP IPNs nanocomposites with different oMMT contents are presented in Fig. 1. The primary relaxation observed at 30 to 30 in Fig. 1 is regarded as the -relaxation, and has been designated to the glass transition of PU soft segment. PU/EP0 and the PU/EP IPNs nanocomposites with different oMMT contents have a single Tg within the temperature range of 70100, which reveals that PU is compatible with EP and oMMT does not cause the phase separation between PU and EP. But the Tg of the
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PU/EP IPNs nanocomposites increases with oMMT content up to 3%, and reaches a maximal value, 9.8, which is 7.8 higher than that of PU/EP0. Then the Tg deceases with further increasing oMMT content. The changes in the Tg of these nanocomposites with different oMMT contents suggest that certain interactions between oMMT and the PU/EP IPNs improve microstructure and morphology of these nanocomposites. 2.2 Crosslink density test bonding of PU/EP IPNs, the carbonyl region in the FT-IR spectra for the PU/EP IPNs nanocomposites with different oMMT content is used to analyze the hydrogen bonding properties. The stretching vibration mode of the carbonyl group in the PU/EP IPNs nanocomposites can be observed from 1770 to 1700 cm1. The peak at 1740 cm1 is associated with the free carbonyl of the urethane group, and the peak at 1712 cm1 is caused by the hydrogen-bonded carbonyl of the urethane group. By measuring the peak intensity ratio of these two carbonyl groups, it is possible to give an estimate of the degree of hydrogen bonding. The hydrogen bonding index (R) may be defined as the ratio of the absorbance A1712/A1740. With the approximation of the baseline method, the hydrogen bond index may be expressed as (1) R = Cbondedbonded/Cfreefree =A1712/A1740, where A is the absorbance of characteristic band, C is the concentration, and is the extinction coefficient of bonded and free carbonyl groups[5]. The value of bonded/free is 1.01.2. Here 1.0 is taken as the value of bonded/free. The hydrogen bonding changes of carbonyl are presented in Fig. 3. R of PU/EP0 and PU/EP IPNs nacocomposites with different oMMT contents is shown in Table 1 according to eq. (1). It can be seen from Table 1 that the degree of hydrogen bonding of carbonyl increases with increasing oMMT content. PU/EP3 has the maximal R value, which corresponds to the maximal Tg. These results from FT-IR analysis indicate that oMMT has an obvious effect on hydrogen bonding of carbonyl in PU/EP IPNs, which causes the change of he Tg of PU/EP IPNs. 2.4 XRD analysis In order to study the relations between hydrogen bonding and the dispersion and exfoliated degree of oMMT, the XRD patterns of the PU/EP IPNs nanocomposites with different oMMT contents are shown in Fig. 4. The d-spacing value of clay in the PU/EP5 is calculated to be 4.2 nm, according to Bragg formula[21]. However, there are still some clay layers assembled together, which can be seen from Fig. 5. A complete and effective entry of monomers into the oMMT layers is very difficult when oMMT content is higher. Because the entropy gained by desorption of solvent molecules is not enough for all monomers to intercalate[5]. No characteristic diffraction peaks appear in the range of 2 from 1.5 to 15 in PU/EP1 and PU/EP3, implying that the d-spacing values of clay in PU/EP1 and
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Crosslink density of polymer has prominent effects on Tg. With the increase of crosslink density of a polymer, the free volume of the polymer reduces, the motions of the molecular chains are restricted, and the Tg will increase, vice versa. Crosslink density of the PU/EP IPNs nanocomposites with different oMMT contents was measured using the swelling method and the results are presented in Table 1. The balance swelling volume percent (Vr) and crosslink density (K) of the PU/EP IPNs nanocomposites increase with increasing oMMT content and reach a maximal value when oMMT content is 3%. The corresponding Tg also increases and reaches a maximal value. However, with a continuous increase of oMMT content, the Vr and K of PU/EP5 reduce, and the corresponding Tg decreases. This is because oMMT, as a catalyst, retards the curing rate of PU and accelerates the curing rate of EP, which results in complete cure of PU and EP, and promotes K of the PU/EP IPNs. Other causes can result from the confinement of the segmental motions of intermolecular chains of the nanocomposites within the clay galleries and the increase of hydrogen bonding of these nanocomposites with increase of oMMT content, which can also be proved by FT-IR analysis.
Table 1 Tg, Vr , K and R of PU/EP IPNs with different oMMT contents Tg () Vr K R PU/EP0 2.0 0.82 0.72 0.812 PU/EP1 7.7 0.89 0.81 0.870 PU/EP3 9.8 0.92 0.86 0.961 PU/EP5 7.1 0.85 0.78 0.885

2.3

FT-IR analysis

The degree of phase separation plays a key role in glass transition temperature of IPNs, and hydrogen bonding between functional groups is closely related to the phase separation. The hydrogen bonding in the PU/EP IPNs nanocomposites is very complex, which is shown in Fig. 2. In order to prove the effect of oMMT on hydrogen
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Fig. 2. Hydrogen-bonding interactions in PU, EP, DMP-30 and clay layers.

Fig. 3. FTIR spectra of PU/EP IPNs with different oMMT contents.

Fig. 4. The XRD patterns of the PU/EP IPNs nanocomposites with different oMMT contents.

PU/EP3 are higher than 4.2 nm. It can be proved further by Fig. 5. It can also be seen from Fig. 4 that PU/EP0 exhibits a diffraction peak at about 20o, which is regarded as crystallization of PU hard segments[6, 22] and is found at the same location for all of the PU/EP IPNs nanocomposites. These diffraction peaks become broader and the in
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tensity becomes weaker with increasing oMMT content, which indicates that oMMT reduces the crystallization degree of the PU/EP IPNs[13,23]. Reducing the crystallization degree can result in decrease of the Tg. 2.5 SEM and TEM analysis Fig. 5 presents the morphology of the frozen fractured surfaces of the PU/EP IPNs nanocomposites with
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Fig. 5. The SEM patterns of (a) PU/EP0; (b) PU/EP1; (c) PU/EP3 and (d) PU/EP5.

different oMMT contents, and shows one continuous phase morphology without manifest dispersed microdomains. However, when oMMT was added to PU/EP IPNs, the PU/EP IPNs nanocomposites have a distinct net fracture structure, which means that proper oMMT content improves phase morphology of the PU/EP IPNs nanocomposites. TEM further provides more direct information on morphology in real space. The TEM images of PU/EP IPNs nanocomposites with different oMMT are presented at the lower left parts of Fig. 5(b), (c) and (d), respectively. Every TEM image was magnified by 5 ten thousand times. Fig. 5(b) and (c) show that the oMMT layers are disordered and dispersed relatively homogeneously in PU/EP IPNs matrix when oMMT content is 1% or 3 %. But Fig. 5(d) shows an intercalated structure and about 4 nm of distance among oMMT layers. Moreover, when oMMT content is 1% or 3%, interface interaction between oMMT and PU/EP IPNs matrix is better than that when oMMT cotent is 5%. It can be judged from the above FT-IR, XRD, SEM and TEM analysis that the higher the dispersion and exfoliation degree of oMMT, the bigger the crosslink density of the PU/EP IPN nanocomposites, and the higher the corresponding Tg. 3 Conclusions

SEM and TEM analysis prove further that effects of oMMT on the Tg are closely relative to crystallization degree, the dispersion and exfoliated degree of oMMT in PU/EP matrix. The changes of crosslink density, hydrogen bonding and crystallization degree with increasing oMMT content are the main reasons for influencing the Tg of the PU/EP IPNs nanocomposites. Proper oMMT content can change the network structure between polyurethane and epoxy resin.
Acknowledgements This work was supported by the Doctoral Foundation of Xian Jiaotong University and Tackling Key Problem Program of Shaanxi Science and Technology Bureau (Grant No. 2004K07-G12).

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