3.1. Chemical Structure and Intrinsic Viscosity of TPAEs.
The viscosity-average molecular weight of the TPAE and PA512 was calculated through Eq. (3), and the results are presented in Table 1. An increase in characteristic viscosity serves as a critical indicator of the successful synthesis of TPAE. The structure of the TPAEs was initially characterized using FTIR (Fig. 1). The peak observed at 1644 cm− 1 was ascribed to the C = O stretching vibration of the amide group, while the peaks at 3320 and 1530 cm− 1 were identified as the N-H stretching and bending vibrations of the amide group. The appearance of these characteristic peaks confirmed the successful synthesis of PA512.
Additionally, new characteristic peaks appeared at 1735 and 1106 cm− 1 for all TPAEs. The 1735 cm− 1 peak was attributed to the symmetric telescopic vibration of C = O in the ester moiety, while the 1106 cm− 1 peak corresponded to the anti-symmetric telescopic vibration of C-O-C in the PEG segment. These observations indicated that the esterification reaction between the PA512 prepolymer and PEG had occurred, successfully synthesizing the TPAE block copolymer.
Table 1
Intrinsic Viscosity and Feeding Values of TPAEs
sample
|
PDA/g
|
DDA/g
|
PEG/g
|
BDO/g
|
PA512[η]a
|
TPAE[η]b
|
TPAE410
|
187.22
|
456.66
|
66.67
|
14.74
|
25.62
|
37.51
|
TPAE420
|
187.22
|
456.66
|
150.00
|
9.45
|
25.62
|
36.51
|
TPAE430
|
187.22
|
456.66
|
257.14
|
2.70
|
25.62
|
43.06
|
TPAE440
|
187.22
|
456.66
|
400.00
|
0
|
25.62
|
28.61
|
TPAE330
|
187.22
|
469.70
|
266.34
|
9.32
|
20.36
|
38.27
|
TPAE230
|
187.22
|
499.07
|
287.03
|
17.22
|
15.32
|
37.46
|
a The intrinsic viscosity of PA512prepolymer.
b The intrinsic viscosity of TPAEs.
In addition, as shown in Fig. 2, the signals at δ = 1.70 (H3) and δ = 2.11 (H2) are attributed to the protons connected to the amide bond of the PA512 segments, respectively. The signals at δ = 3.19 (H1) and δ = 4.30 (H11) represent the protons connected to the − NH − and C = O of the PA512 segments, respectively. The signal at δ = 4.30 (H11) represents the protons connected to the ester bond of the PEG segments. The results of FTIR and 1H NMR analysis provide evidence for the presence of amide and ester groups, which indicates that the TPAEs were successfully synthesized.
3.3. Thermal Properties and Crystallization Behavior
TGA was conducted to evaluate the thermal stability of TPAEs and PA512 under a nitrogen atmosphere, and the corresponding curves are presented in Fig. 3 and Table 2. Figure 3 presents the TG and DTG curves for TPAEs and PA512, while Table 2 provides the corresponding thermal decomposition data. As depicted in Fig. 3. a and 3. b, for TPAEs, the values for the thermogravimetric parameters T5%, T50%, and Tmax decreased as the proportion of PEG increased in the elastomer from 413.4°C, 462.5°C, and 470.2°C to 375.1°C, 431.3°C, and 430.6°C, respectively. This observation is attributed to the increased presence of PEG groups, which disrupted the regularity of the molecular chain within the nylon crystal region[15]. This, in turn, decreases the crystal density per unit volume of TPAE and reduces the intramolecular hydrogen bonding strength, leading to decreased crystallinity and, consequently, a decreased thermal stability performance for TPAE. Figure 3.c and Fig. 3.d exhibit that when the PEG content in the elastomer is fixed, the T50% and Tmax values of TPAE show an increasing trend with the rise of the molecular weight of the hard segment, ranging from 434.2°C to 442.3°C and 430.6°C to 463.5°C. This observation can be primarily attributed to the fact that as the molecular weight of the hard segment rises, the crystalline region of the nylon phase becomes more stable, and the impact of PEG becomes relatively insignificant compared to the nylon phase. Thus, the crystal density per unit volume of TPAE rises while the crystallinity decreases, leading to a decrease in the thermal stability of TPAE. However, when the crystal density per unit volume increases, the density of intramolecular hydrogen bonding also increases, leading to an increase in the crystallinity and, consequently, an improvement in the thermal stability of TPAEs.
Table 2
TG and DTG data of TPAEs and PA512 prepolymer
Sample
|
T5%(℃)
|
T50%(℃)
|
Tmax(℃)
|
Remant(%)
|
PA512
|
413.4
|
462.5
|
470.2
|
0.6
|
TPAE410
|
392.4
|
450.9
|
468.5
|
0.8
|
TPAE420
|
390.5
|
447.4
|
466.4
|
1.1
|
TPAE430
|
386.7
|
442.3
|
463.5
|
1.2
|
TPAE440
|
375.1
|
431.3
|
430.6
|
1.6
|
TPAE330
|
384.8
|
440.6
|
439.3
|
1.8
|
TPAE230
|
384.3
|
434.2
|
430.5
|
1.2
|
DSC curves of different TPAEs and PA512 during the first cooling and second heating scans are shown in Fig. 4, and the corresponding thermal properties are summarized in Table 3. The TPAE block copolymer is composed of PEG soft segments with lower polarity and PA512 hard segments with high polarity. The polarity mismatch between the hard and soft segments gives rise to microphase separation in the TPAEs block copolymer, resulting in two distinct melting and crystallization temperatures[16]. As illustrated in Fig. 4.a, as the PEG content increased from 0–20%, the melting and crystallization temperatures of TPAEs decreased from 203.1°C to 196.5°C and from 152.2°C to 147.8°C, respectively. This phenomenon can be attributed to the disruption of the crystalline zone structure of the PA512 phase upon the introduction of PEG, which disturbs the molecular chain arrangement within the crystalline zone of the PA512 phase, leading to a reduction in the crystallinity of the PA phase. Concurrently, the density of hydrogen bonding in the elastomer decreases, causing a weakening of the intermolecular forces and making the chain forging more susceptible to movement. This results in a further decrease in the crystalline density of the crystal zone, a reduction in crystallinity, and an increase in the degree of disorder in the elastomer's structure. The emergence of a micro-phase separation structure and a decrease in the melting temperature are also observed. When the PEG content was increased to 30%, the TPAE block copolymer still exhibited two distinct crystallization peaks and melting peaks. However, at this point, the crystallization and melting temperatures of the PA512 segment were similar to those of the PA512 prepolymer. It was presumed that this occurred due to the agglomeration of a large amount of PEG, which increased the degree of micro-phase separation[38].
Therefore, we also synthesized TPAE230 and TPAE330 for comparison with TPAE430. As shown in Figs. 4. c and 4. d, when the content of the soft segment is constant, the melting point of the PA segment in the elastomer decreases from 204.5°C to 200.1°C with a decrease in the molecular weight of the hard segment. This can be attributed to the reduction in the density of intermolecular hydrogen bonding and the weakening of the intermolecular force when the molecular weight of the hard segment decreases. As a result, the "pulling" effect of the soft segment on the hard segment becomes more pronounced, causing the PA512 phase to exist as a discrete phase within the PEG matrix, giving rise to a micro-phase separation state. This leads to a gradual decrease in the melting temperature[39].
Table 3
Thermal properties of different TPAEs and PA512.
Sample
|
Tc,s(℃)
|
Tm,s(℃)
|
Tc,h(℃)
|
Tm,h(℃)
|
ΔHc,h(J/g)
|
ΔHm,h(J/g)
|
ΔHc,s(J/g)
|
ΔHm,s(J/g)
|
PA512
|
—
|
—
|
152.2
|
203.1
|
59.1
|
62.3
|
—
|
—
|
TPAE410
|
12.7
|
37.2
|
150.5
|
198.5
|
45.5
|
58.9
|
7.4
|
4.6
|
TPAE420
|
16.2
|
38.5
|
147.8
|
196.5
|
38.5
|
56.1
|
9.8
|
9.5
|
TPAE430
|
39.2
|
53.5
|
155.7
|
204.9
|
36.4
|
35.6
|
36.0
|
34.1
|
TPAE440
|
32.8
|
50.5
|
154.3
|
204.5
|
33.3
|
35.6
|
52.8
|
53.3
|
TPAE330
|
23.17
|
40.7
|
168.2
|
205.5
|
27.1
|
28.2
|
15.4
|
15.1
|
TPAE230
|
25.33
|
41.8
|
165.3
|
200.1
|
38.2
|
45.1
|
24.7
|
30.4
|
Since block copolymers usually have two or more components, the molar weight and crystallizability of different components can affect the crystallinity of different domains in the block copolymer[40]. WAXD analysis at 25 ℃ was performed to study the crystal structure of TPAEs (Fig. 5). The XRD pattern of PA512 exhibits a single diffraction peak at 2θ = 20.9 °, which is attributed to the α-crystalline structure. When the molecular weight of the hard segment is held constant, the addition of soft segment mass results in the appearance of new diffraction peaks at 2θ = 19.1 ° and 2θ = 23.2 ° for TPAE, which are attributed to the α-crystalline structure. TPAE410 and TPAE420 do not exhibit obvious crystallization peaks at these two positions at this time. This is because the crystallization temperatures of the soft segments are 12.7°C and 16.2°C, respectively, so the soft segments of TPAE410 and TPAE420 are only partially crystallized or amorphous at 25°C, which explains why no obvious diffraction peaks were observed on the XRD pattern. For TPAE430 and TPAE420, both the γ and α crystalline forms are present. This is because the addition of PEG leads to a more flexible elastomer with a higher molecular weight, allowing the chain segments to move more freely and facilitating crystallization, resulting in the formation of both γ and α crystals.
3.3. Phase Morphology
SEM analysis was performed to ascertain the surface morphologies of the TPAEs and PA512, by which the phase structure of the polymer, especially the microphase separation structure, can be observed. In the present work, we can observe the distribution of the microphase domains of TPAE330 and TPAE430 using an SEM microscope (Fig. 6). It can be observed from Fig. 6.a that PA512 possesses a continuous phase with a relatively flat and smooth overall morphology. However, the introduction of PEG leads to the elastomer's interface becoming rough. When the polarity difference between the hard and soft segments is significant enough, the elastomer exhibits a micro-phase separation structure, as seen in TPAE420, TPAE430, and TPAE330, which show the micro-phase separation. TPAE330 exhibits the most prominent micro-separation, contributing to its largest elongation at break.
The DMA analysis serves as additional validation of the microphase separation structure in the polymer, corroborating the trends observed in DSC. Examining the tan δ-temperature curves (Fig. 7. b and Fig. 7. d), it is evident that TPAE exhibits two transition peaks, which correspond to the α and β transitions, respectively, transitioning from higher to lower temperatures[41]. The α transition signifies the commencement of movement within the PA512 hard segments in the amorphous region, triggered by the dissociation of hydrogen bonds among PA512 molecular chains. The temperature of this α transition corresponds to the Tg of the PA512 amorphous phase, which can serve as an additional switching temperature to enable a multi-shape memory effect. On the other hand, the β transition is associated with the synergistic effect of two distinct relaxations: one originating from the relaxation of the amorphous PEG soft segments, and the other attributed to the local chain mobility of amide groups within the amorphous PA512 hard domains that do not participate in hydrogen bonding with each other. These findings are in agreement with the observations made in Fig. 7.
Indeed, Fig. 7. d presents a clear visualization of this trend: when the molecular weight of the soft segment remains constant, the α transition temperature gradually shifts towards lower temperatures and converges towards the β peak as the molecular weight of the PA512 hard segment decreases. This observation suggests improved compatibility between the PA512 hard segments and the PEG soft segments, thus confirming the presence of microphase separation. When the content of PEG was increased to 20 wt%, the α transition temperature shifted towards lower temperatures and moved closer to the β peak. This suggested that as the molecular weight of PEG increased, the molecular polarity difference between PA512 and PEG segments became greater, resulting in inhomogeneous dispersion of the bi-continuous structure, leading to a reduction in microphase separation. However, when the PEG content was increased to 30 wt%, the α transition temperature inclined towards the temperature of nylon, and the degree of microphase separation increased, as can be seen in the SEM image. This indicated that a higher content of PEG could lead to more significant microphase separation.
Figure 7. a and Fig. 7. c display the storage modulus as a function of temperature. Below the Tg, the storage modulus remains relatively constant with increasing temperature due to the freezing of chain segments. As depicted in Fig. 7. a, the E′ value decreases continuously with an increase in PEG content. Particularly around − 30°C, the E′ begins to decrease sharply, attributable to the glass transition of PEG. Above Tg, the storage modulus decreases dramatically due to the mobilization of chain segments. At approximately 55°C, a relatively stable rubbery plateau region becomes evident in all samples, indicating a highly elastic state that is characteristic of thermoplastic elastomers and block copolymers with uniform PA512 segments.
3.4. Tensile properties analysis
The tensile properties of TPAE block copolymers were measured at room temperature using a SANS-CMT6104 tensile testing machine. All samples exhibit a typical stress-strain curve of a thermoplastic elastomer, further confirming that the introduction of PEG transforms the PA512 into an elastomer. All the samples present a yield behavior during the stretching process, which means polymer chain slipping occurs, resulting in plastic deformation when the external force exceeds the elastic limitation of the material.
As shown in Fig. 8. a, when the molecular weights of PEG and PA512 are kept constant, the yield strength (σy) is 42.3 MPa, 29.2 MPa, 24.0 MPa, and 31.0 MPa, respectively, while the elongation at break (εb) increases as the proportion of PEG increases. This can be attributed to the fact that as the content of PEG segments in the elastomers grows, the PEG segments reduce crystallinity and the force between the molecular chains of the hard segments, resulting in a decreased rigidity of the elastomers and allowing for greater elongation. Therefore, the tensile strength decreased. Concurrently, the elongation at the break of the elastomer increased significantly, showcasing favorable toughness, which is attributable to the integration of polyethylene glycol. The latter enhances the randomness of the molecular chain, decreases intermolecular polarity, and notably enhances the flexibility of the molecular chain. However, the TPAE440's injection-molded samples displayed a skin-core separation structure. Under tensile force, the samples were pulled apart directly at the narrow neck following the yield point, potentially due to the high PEG content causing part of the PEG to agglomerate. The tensile strength of TPAE430 is indeed higher than that of TPAE420, which seemingly contradicts the general understanding that the tensile strength of elastomers decreases when the content of soft segments increases. One possible explanation for this phenomenon could be the presence of butanediol in TPAE420, which introduces more low molecular chain segments and disrupts structural regularity. Conversely, TPAE430 has a greater density of hydrogen bonding, resulting in stronger intermolecular forces and, therefore, a macroscopically superior tensile strength[42]. As for TPAE440, the decrease in its tensile strength can be attributed to the use of PEG as the soft segment without incorporating BDO groups. Thus, the molecular chain is more rigid and regular, with increased chain flexibility leading to decreased macroscopic tensile strength. Furthermore, the integration of PEG into the PA512 phase renders it more susceptible to stress concentration phenomena, leading to the development and enlargement of microcracks. As stretching persists, these microcracks continue to expand until the sample fails macroscopically, leading to a decrease in elongation at break.
Figure 8. b shows the yield strength (σy) increases and elongation at break (εb) decreases with the molecular weight of PA512 increasing when the molecular weight of PEG remains the same. This phenomenon occurs because as the molecular weight of the hard segments decreases, the hydrogen bonding density of TPAE reduces, leading to weaker intermolecular forces and a lower σy.
3.5. Rheological properties
The unique dynamic fluidity of the polymer melt is due to its chain-like development structure, and understanding this fluidity is crucial for analyzing the polymer structure and compatibility[43]. As shown in Figs. 9. a and 9. b, the storage modulus (G') of TPAE increases significantly with increasing frequency. This is because, in the low-frequency region, the deformation of the molecular chain can keep up with the changes in the external force, resulting in a lower storage modulus (G'). However, as the frequency increases, the acting time of the shear force becomes shorter, which means the deformation time of the macromolecular chain also becomes shorter, far less than the relaxation time of the molecular chain. This leads to the deformation of the macromolecular chains not being able to keep up with the changes in external forces, resulting in the system's elastic properties becoming dominant, causing G' to increase significantly.
As shown in Figs. 9. a and 9. d, the storage modulus (G') gradually increases with the increase in PEG content. The addition of PEG enhances the interaction between TPAE, hindering the movement of molecular chains and making the conformational change more complex. Under the action of external forces, more energy can be absorbed, leading to an increase in the storage modulus (G'). Figure 4(c) presents the curve of complex viscosity (η*) of TPAE as a function of angular frequency at 210.0°C. It can be observed that the complex viscosity of the polymer decreases with the increase in angular frequency, which is a typical shear thinning phenomenon. Under the action of high shear frequency, the disentanglement is greater than the entanglement, leading to the destruction of the internal network structure of the system, a decrease in viscosity, and the occurrence of shear thinning. Additionally, as the content of PEG increases, the complex viscosity of the elastomer gradually trends towards that of pure nylon. This can be attributed to the introduction of PEG, which leads to the originally stable system becoming more chaotic with increased molecular chain entanglement, resulting in increased polymer viscosity. Therefore, the complex viscosity gradually increases and ultimately converges to a point.
As shown in Figs. 9. d and 9. f, when the molecular weight of the hard section increases, both G' and G'' exhibit an increasing trend at low frequencies, while converging to one value at high frequencies. The storage modulus of the polymer is influenced by the molecular weight distribution at high frequencies while the change in storage modulus at low frequencies is dictated by the molecular structure. As the molecular weight of the hard segments grows, the hydrogen bonding density within the elastomer increases, resulting in enhanced intermolecular forces. This leads to an increase in the energy G' and a decrease in η* at low frequencies.
3.6. Shape memory performance and Temperature sensing device
There are several key elements that SMPs must possess to exhibit the shape memory effect [44], [45], [46], [47]: First, the soft and hard segments must undergo adequate phase separation to achieve an optimal SME. Secondly, cross-linking points must be formed through chemical or physical interactions between the hard segments, allowing the polymer to maintain its original macroscopic shape while preventing chain slipping and breaking and providing resilience through an entropy-increasing process during deformation. Lastly, the crystallization of soft segments immobilizes the polymer chains, fixing the temporary shape when the temperature falls below the soft domains' crystallization temperature. In the present study, the highly polar PA512 hard segments and nonpolar PEG soft segments underwent microphase separation due to thermodynamic incompatibility. Moreover, the PA512 hard segments formed crystals acting as physical cross-linking points through hydrogen bonding, driving the material to recover its shape above the Tm of PEG. The PEG soft segments, on the other hand, provided a fixed force for deformation through crystallization below the Tc of PEG. Therefore, the TPAE block copolymer demonstrated an outstanding SME.
The heat-triggered shape memory behavior of TPAE block copolymers was investigated, and the results are presented in Figs. 10. a-c. Figure 10.a illustrates the complete shape recovery process of TPAE420 at 60°C, where the sample transitions from the temporary "U" shape to its permanent "bar" shape within 210 s. Figure 10.b depicts the impact of PEG content on the recovery ratio of the composites. It was observed that as the amount of PEG increased, the recovery ratio of the composites also improved, reaching 69.4% and 73.3% for PEG contents of 20 wt% and 30 wt%, respectively. This can be attributed to the increase in the proportion of PEG soft segments acting as reversible microdomains within the TPAE matrix, which provides a larger restraining force for deformation, ultimately leading to enhanced shape memory effects in the TPAE system. Figure 10.c reflects the effect of the PA512 prepolymer molecular weight on the recovery ratio of the TPAE. The increasing molecular weight of PA512 prepolymer leads to an increase in cross-linking points, which results in a gradual increase in the recovery ratio of up to 94.4%, 90.1%, and 73.3%. However, this also causes the TPAE restitution rate to decrease as the higher molecular weight produces more cross-linking points within the TPAE block copolymers. Additionally, irreversible plastic deformation occurs more readily, contributing to the improved shape-memory effect. The insufficient fixing force during the shape programming step, which is attributed to the crystallization of PEG domains, is unable to counteract the elasticity of the PA512 crystalline network, failing shape fixation. The Rf and Rr were recorded in Table 4.
Table 4
The shape fixity ratio (Rf) and shape recovery ratio (Rr) of TPAEs
Sample
|
Rf (%)
|
Rr (%)
|
TPAE420
|
79.5
|
69.4
|
TPAE430
|
62.4
|
73.3
|
TPAE330
|
90.7
|
90.1
|
TPAE230
|
91.2
|
94.4
|
The TPAE420 and TPAE330 samples demonstrated macroscopic shape memory behavior (Fig. 11). Both samples were twisted after being heated to 60 °C and then placed in a -30 °C refrigerator for 5 min to fix the helical shape. Upon reheating to 60 °C, the sample almost completely recovered to their original shapes, showcasing their excellent shape memory performance. It is worth highlighting that the choice of -30 °C for shape fixing and 60 °C for shape recovery was made to facilitate rapid and complete crystallization and melting of the PEG domains, respectively, thereby ensuring fast shape fixation and recovery. The switching temperature of TPAE can be further tuned over a wide range by adjusting the ratio and type of soft and hard segments, which holds significant potential for various practical applications.
The Figs. 12. a-c illustrate the temperature memory effect of the TPAE, we have developed a force-induced temperature device. When the TPAE330 is bent and secured on a heating table set at 60°C, a small ball placed in proximity to the TPAE330 will cause the sample to visibly alter its shape after 25 s. At the 50s mark, the TPAE330 will propel the small ball away.