In modern reconstructive surgery, polymer composite materials are increasingly used due to the combination of high biocompatibility and various functional properties; yet some properties of biomedical polymers have been insufficiently studied. The shape memory effect (SME) in such materials is particularly promising and extremely interesting for different uses. However, calculating, programming, and exploiting this effect are complex tasks that require a deep study of the molecular structure and characteristics of individual materials and their combinations [1
Within the scope of medical applications, SME is of high interest in reconstructive surgery [2
]. Recent research shows a significant step towards using polymer-based implants to replace bone tissue. Based on SME, it is possible to perform “self-fitting” of the implant to solve the problems of implant placement and its congruence [3
]. For these purposes, a polymer scaffold was compressed at a temperature above [4
], below [5
], or near the SME activation temperature and cooled without removing the load to fix the temporary shape. The activation of “self-fitting” occurs directly in the recipient’s body by one of the known methods, e.g., a direct method—heating or using additional tools—magnetic particles and fields, ultrasonic treatment [6
SME in polymer materials occurs due to conformational entropy and internal energy recovery after deformation [11
]. SME is activated at temperatures that characterize changes in the condition of the material—glass transition and melting temperatures. The deformation of an amorphous polymer at a certain temperature, which characterizes the material, leads to the polymer chains stretch into more elongated conformations. This reduces the number of available chain conformations, which is energetically unprofitable [1
]. When the load is removed, the shape is recovered based on the spatial location of the chain sections. Several parameters can describe this effect: activation temperature, activation energy, recovery stress and strain, recovery ratio, and rate. These estimated parameters can be analyzed by DSC and DMA methods [13
Polylactide (PLA) is a biocompatible, biodegradable thermoplastic polymer, one of the most widely used polymers in such areas as biodegradable packaging and disposable products, electronic devices, construction, and especially biomedicine [14
]. In addition, it has a strongly marked shape memory effect [2
], which allows it to be used as a base matrix of a composite material for “self-fitting” implants [18
]. In this material, SME is activated at the glass transition temperature (Tg
= 55–65 °C). At this temperature, the polymer passes into a viscoelastic state, which means that the polymer chains acquire greater mobility, and the energy exceeds the activation energy required for SME implementation [19
This paper aims to reduce the activation temperature of these processes for the safest use of the material as a precursor for the implant. In this case, the glass transition temperature and the threshold activation energy depend on the polymer’s molecular structure, precisely, on the molecular weight, the degree of crystallinity, and the level of chain entanglement.
SME can also be controlled by introducing various plasticizers and dispersed fillers [20
]. A decrease in the initial activation temperature of this effect may trigger an additional phase switch, such as a polymer with phase transitions occurring in other temperature ranges. The most used polymers are polyethylene glycol (PEG) [22
], thermoplastic polyurethane (TPU) [23
], polyhydroxyalkanoates (PHA) [25
], poly(ε-caprolactone) (PCL) [28
], and their combinations.
In this study, the PCL melting process as a trigger for lowering the SME activation temperature in the PLA matrix was used [9
]. The PCL melting temperature is in a range of Tm = 60–65 °C, and the glass transition temperature is below zero (Tg
= −60 °C). These two polymers are immiscible, and they do not interact with each other and rarely form any bonds between chains without copolymerization [29
]. However, PCL inclusions in the PLA matrix affect the transition temperature to the viscoelastic state of the blend.
The studied biocompatibility of PLA and PCL polymers makes them useful candidates to be used in implantology. The shape memory effect in this area is relevant for optimizing surgery in view of the phenomenon of implant self-installation [32
]. The calculation of the composition and the analysis of the composite’s structure should provide the necessary mechanical and thermal properties for use in the body.
3. Results and Discussion
3.1. Analysis of Material Composition and Structure
The FTIR spectrum of the composite blend of PLA and PCL is shown in Figure 1
. The region of 2850–3000 cm−1
includes three bands of 2998, 2946, and 2854 cm−1
, which relate to symmetric/asymmetric bending of groups −C−H in PLA and to −CH3
stretching. At the same time, these spectrum peaks characterize asymmetric and symmetric −CH2
stretching in PCL at 2946 and 2865 cm−1
, respectively. In the other part of the spectrum, the peaks can be attributed to the following vibrations: −C=O stretching (1751 cm−1
bending (1360 and 1454 cm−1
), −CH3 bending, and −C−COO stretching (1081 and 1266 cm−1
) for PLA. The following bands belong to PCL: C=O stretching (1724, 1182 cm−1
), valence vibrations C−O−C (869, 1043, and 1109 cm−1
), C=C stretching (1286 cm−1
The microphotographs of the quasi-brittle fracture surface of a PLA/PCL polymer blend were obtained using scanning electron microscopy (Figure 2
). Cavities and spherical inclusions of less than 5 microns were found on the fracture surface. This surface relief is most likely due to the fact that PCL coalesces into small droplets and appears as an inclusion in the PLA matrix [28
]. Due to the mechanical action, cavities where these droplets were located can be observed at the fracture surface, and in some places, inclusions are visible. Their formation proves the immiscibility of the two polymers.
The DSC method was used to evaluate thermal transitions in the polymer blend. The method was performed in three stages: first heating, cooling, and second heating. The study results are shown in Figure 3
The first heating eliminates the sample’s thermal history. The melting peaks of PCL and PLA are found at 57.5 and 152.3 °C, respectively [9
]. At 98.4 °C, an exothermic effect of cold crystallization of PLA is observed, which indicates that PLA does not completely crystallize when the samples are obtained at temperature treatment.
During the first heating, the melting peak of PCL and the glass transition of PLA overlap in a temperature range of about 45–62 °C, so it is impossible to determine the values accurately. When reheated, two peaks of 55.5 and 60.5 °C are visible due to the changes in the crystal structure of polymers due to cooling at a sufficiently high speed [30
]. At cooling, PCL manages to completely crystallize so that its melting peak shifts towards higher temperatures when reheated. In the case of PLA, the inflection that characterizes the transition to the viscoelastic state is shifted towards lower temperatures. In addition, during further heating, cold crystallization is not explicitly expressed.
3.2. Mechanical Properties
The compression test results (Figure 4
) show that PCL inclusion in the PLA matrix reduces mechanical characteristics, such as Young’s modulus (E
) and yield strength, as also shown in Table 1
. These values are directly related to the possibility of using this composite material for self-fitting implants, as before installing an implant, for instance, a preliminary load is required to fix the temporary shape. In this case, the stress value should not exceed 80 MPa to avoid irreversible deformations of the material.
3.3. Shape Memory Effect
The dynamic mechanical analysis of the samples was performed to determine the temperature phase transitions of a composite blend containing 10 wt.% PCL. Figure 5
shows the graphs of the dynamic elastic modulus, loss modulus, and tan δ
as a temperature function.
To evaluate SME, the DMA was used to determine the transition temperature that corresponds to the temperature of SME activation. It is characterized by a drop in the elastic modulus at the transition temperature. In this case, there is a peak on the elastic modulus curve, the maximum of which is reached at 45.6 °C. Above this temperature, there is a dramatic fall in the modulus of elasticity. Accordingly, the transition of the PLA/PCL blend to the viscoelasticity starts at a temperature of about 46 °C, which is almost 10 °C lower than for pure PLA.
The peak on the tan δ curve indicates an abrupt shift in the strain. In comparison with the pure PLA, this peak is shifted towards lower temperatures. This is probably due to the melting of one of the phases. The PCL melting point varies between 59 and 64 °C, which is shown on the curve.
When studying SME by various methods, such as DSC, where the focus is on thermal transitions in the material, and DMA, where the mechanical characteristics are studied as a function of temperature, there is a discrepancy in temperatures characterizing the same processes in terms of SME. The trigger for starting the SME activation in the PLA/PCL blend is the beginning of the melting process in PCL. At first heating of the DSC, the values in the melting region of PCL and the glass transition of DSC are unclear. This and the apparent peak of 45.6 °C of the storage modulus can be explained by the fact that PCL softens and melts at this set temperature, providing greater mobility of molecular chains. Therefore, the pronounced SME occurs below the glass transition temperature of the PLA matrix.
To study the SME parameters, such as recovery stress and recovery strain, the 3.5 cm long samples were deformed at 100%. Figure 6
shows the recovery strain curve as a function of temperature. For this test, the samples with a fixed temporary shape were placed in grips, one of which was not fixed, and heated from 26 to 70 °C at a rate of 2 °C/min. When the temperature reached 53.3 °C, the samples’ length began to decrease, and the samples returned to the permanent shape.
The same heating parameters were provided for the study of the recovery stress. The samples deformed to the temporary stretched shape were placed in fixed grips. When heated to 40 °C, relaxation occurred within the material. After that, the stress increased up to 1 MPa. When compared with the previous work on SME in PLA composites, it can be seen that recovery stresses increased from 1.5 MPa for neat PLA to 3 MPa in the case of dispersedly filled PLA [19
], which was associated with the appearance of an additional rigid “fixed” phase and increased crystallinity. On the contrary, in the current study, the decrease in recovery stresses is associated with the presence of an additional soft phase—PCL.
A significant characteristic of the polymer shape memory effect is the apparent activation energy. It determines the height of the energy barrier that must be overcome to achieve shape recovery. The DMA results were used to determine this characteristic for pure PLA, polymer blend PLA + 10%PCL, and pure PCL. Figure 7
presents the Arrhenius plots of the specific rate constant to determine the activation energy. Table 2
shows the apparent activation energy values. For the glass transition activation of the studied polymer blend PLA + 10%PCL, this value was approximately 186 kJ/mol, 85 kJ/mol less than for pure PLA. As previously assumed, the transition to the viscoelastic state of the polymer blend requires less energy, which means less energy is needed to activate shape memory. The activation energy of the melting processes of pure PCL has a significantly higher energy barrier.
To demonstrate the shape memory effect, a plate was fixed in a temporary shape in the form of a rolled tube (Figure 8
A). The plate was heated in a metal container in the air at a temperature of 50 °C. The plate recovered a shape close to the permanent one in 2.5 min, but it did not fully restore its shape due to a lower recovery stress than in the pure PLA. Figure 8
B shows the shape memory effect in the PLA/PCL blend.
3.4. Biological Compatibility Test
The separately considered polymers of PLA and PCL are biocompatible and are widely used as medical devices, such as fixing rods, plates, pins, screws, and suture materials [15
To assess the biocompatibility of the polymer composite, the SC1 cell line (7000 cells) was plated in the wells of a 96-cell well. After 48 h of incubation cell cultivation with the samples, a cell viability analysis was performed using spectrophotometry (Figure 9
Based on the results, it could be determined that the polymer composite material PLA + 10%PCL had no acute toxic effect on the cells. At the same time, there was a slight decrease in the percentage of cell viability compared to the control. This may be due to mechanical damage to the cells when organizing the experiment or to the fact that the cells were deposited in higher numbers at the bottom of the plate than on the surface of the sample.
The modification of the material composition in this study made it possible to adapt the shape memory effect for medical applications, such as self-fitting implants. However, several biological and clinical studies in vitro and in vivo are necessary to fully approve the possibility of using this material. In addition, the reduction of mechanical properties also implies further work with the composition. The incorporation of bioactive ceramic particles into the composition [19
] or the creation of block copolymers [36
] can positively affect the amount of the rigid phase, improving the mechanical characteristics and the characteristics of the SME.
To reduce the SME activation temperature, a polymer blend based on polylactide and polycaprolactone has been suggested.
The droplet-shaped particles of PCL are distributed in the PLA matrix, which occurs due to their immiscibility. In this case, the inclusions act as a trigger for SME activation due to their melting, making it possible to achieve this temperature.
The introduction of PCL in the PLA matrix leads to a reduction of mechanical characteristics. Notably, Young’s modulus decreased by almost 200 MPa, which can be related to the efficiency of the SME use.
The transition temperature of 45.6 °C was determined by the DMA method. This temperature corresponds to the temperature of the SME activation. Finally, for the glass transition activation of the investigated polymer blend PLA + 10%PCL, this value was 85 kJ/mol less than for the pure PLA. As previously assumed, the transition to the viscoelastic state of the polymer blend requires less energy, which means less energy is needed to activate shape memory.
The composite material was also examined for biological compatibility. No acute toxic effects on the cells were detected.
By reducing the activation temperature of the shape memory effect to an acceptable use in the body and by reducing the energy barrier of the activation process, the composite material PLA + 10%PCL is a promising material for self-fitting bone implants and other biomedical applications.