3.1 Interactions of PLA / CA blends
Fig. 1c- 1d shows the FT-IR spectra of PLA / CA blends with different content of PAMAM and the wavenumbers of the characteristic peaks are listed in Tab. S1. It can be observed that PLA exhibited typical vibration absorption of -CH2- at 2947 cm-1, the stretching vibration absorption peak of ester carbonyl C=O at 1747 cm-1 and the stretching vibration absorption peak of C-O-C at 1180 cm-1, 1128 cm-1,1078 cm-1 and 1041cm-1, respectively. When CA was added to PLA (Fig. 1d), the vibration absorption peak of -CH2- decreased from 2944 cm-1 to 2918 cm-1, while other peaks remained almost unchanged, indicating that there might be hydrogen bond between -OH of CA and -C=O of PLA[28].
When PAMAM was added (see Fig. 1d), the vibration absorption peaks of -CH2- group, C=O group and C-O-C were blue shifted, indicating the hydrogen bond interaction in the blends. At the same time, compared with the spectra of PAMAM in Fig. 1c, there was no obvious N-H peak of amide bond in PLA / CA blends with PAMAM, which proved that the amino group of PAMAM formed hydrogen bond with PLA and CA. The schematic diagram of hydrogen bonding between PAMAM and PLA / CA blends and intermolecular interaction between PLA and CA were shown in Fig. 1e. PAMAM could form hydrogen bonds with both PAMAM and PLA, leading to the improved compatibility between the two moieties.
3.2 Morphology characterization
Fig. 2 shows the SEM images of the fracture surface of the PLA / CA blends with different PAMAM contents. As shown in Fig. 2a, CA exhibited a spherical shape in the PLA matrix, showing an obvious sea-island structure. The smooth surface, clear phase interface and ununiform distribution of CA spherical particles indicated limited compatibility between the two moieties. [29]. Upon addition of PAMAM (Fig.2(b)-(d)), it was obvious that the dispersion of CA in the PLA matrix became more uniform, the particle size decreased and the distribution became narrower (Supplementary Material Fig. S1). In addition, the increase of surface roughness CA indicated the improved compatibility. The blend exhibited obvious ductile fracture characteristics, which indicated that PAMAM could improve the toughness of PLA / CA blends. The addition of PAMAM destroyed the original hydrogen bond between the two phases, and produced new hydrogen bond, which improved the compatibility of CA in PLA. By reducing the diameter of dispersed particles, the interfacial adhesion was improved [30].
As shown in Fig. 2e- 2f, when the content of PAMAM was greater than 3 phr, the particle size of CA particles increased and the particle size distribution was wider (Fig. S1), indicating the decreased dispersion effect of CA in PLA matrix. The surface roughness and voids number of PLA matrix decreased, while that of CA increased. Due to the strong intermolecular hydrogen bond between PAMAM and PLA / CA blends, the high content of PAMAM was tended to accumulate on the surface of CA, which aggravated the agglomeration of CA and increased the particle size. At the same time, the interaction between PAMAM and PLA was weakened, but the interaction with CA was enhanced, resulting in the descending compatibilization effect of PAMAM on PLA / CA blends.
3.3 Crystalline Properties
Fig. 3 shows the POM images of PLA / CA blends isothermal crystallized at 120 °C for 30 minutes. In PLA / CA blends, CA could promote the crystallization rate of PLA as a nucleating agent, but the agglomeration phenomenon inhibited the nucleation effect of CA [31]. From Fig. 3a, the crystal of PLA was spherulite, with a large number of nuclei generated, but the crystal size was small and most of the crystals were imperfect due to the poor crystallinity of PLA and the imperfect crystal growth. When PAMAM was added, as shown in Fig. 3(b) - (d), the spherulite size tended to increase, and the dispersion state was more uniform than that without PAMAM. With 5 phr PAMAM, the number of nuclei of PLA decreased greatly and the grain size became larger. As can be seen from Fig. S2, the average spherulite size of PLA was 147.66 μm in PLA / CA blends. With the addition of PAMAM, the spherulite size of PLA increased gradually, the average spherulite size of PLA with 5 phr PAMAM was 553.04 μm. With the addition of PAMAM, the number of nuclei in PLA spherulites decreased and the crystal size gradually increased, indicating that the addition of PAMAM molecules inhibited the formation of PLA crystal nuclei, but promoted the growth of PLA crystals.
Because PLA / CA system was a nucleation control system, on the one hand, the addition of PAMAM dendrimer improved the dispersion of CA in PLA, which was conducive to nucleation. PAMAM with three-dimensional spherical structure can promote the movement of PLA molecular segment, reduce the free energy barrier of crystallization, promote the contact between PLA segment and crystal nucleus [32]. On the other hand, due to the high content of PAMAM dendrimer, the intermolecular force was too strong, which increased the size of CA particles and inhibited the formation of crystal nuclei, resulting in the decrease of the difficulty of nucleation and decrease of crystallinity of PLA.
3.4 Thermal Properties
Fig. 4a- 4b shows the first cooling and second heating scan curves of the PLA / CA blends with different content of PAMAM. The obtained parameters of thermal behavior such as glass transition temperature (Tg), cold crystallization temperature (Tcc), melting point (Tm), crystallization enthalpy (∆Hc) and melting enthalpy(∆Hm) of the PLA / CA blends with different content of PAMAM were summarized in Tab. 1.
Fig. 4a shows that there was no crystallization peak during the cooling process because CA limited the chain movement of PLA. It can be seen from Fig. 4b that with the increase of PAMAM content, Tg and Tm gradually decreased to 52.83 °C and155.82 °C, respectively, Tcc decreased first and then increased, reaching the minimum value of 100.35 °C when the content was 3phr. It suggested that the addition of PAMAM could play a plasticizing role in accelerating the movement ability of molecular segments, reduce the hydrogen bond of CA, improve the molecular chain movement and crystallization capacity [33]. The crystallization enthalpy increased with the addition of PAMAM, while the melting enthalpy increased first and then decreased, reaching the maximum at 3 phr. This indicated that with the increase of PAMAM, the crystallinity was improved and the crystal was more stable and the optimum value was reached at 3 phr, and then the defects in the crystal began to increase and the instability increased.
Fig. 4c- 4d shows the thermogravimetric curves and the weight loss rate of the blends with different PAMAM content. Tab. 1 included thermal decomposition parameters such as the temperature with 5% weight loss (Td5%), the temperature at the maximum weight loss rate (Tdmax) and the residue (Rd). The weight loss of PLA / CA blends mainly occurred in the temperature range of 250 °C to 450 °C, excepted for the weight loss caused by the volatilization of moisture and residual solvents at lower temperature. In the range of 250 °C to 340°C, the curve became steep from horizontal, indicating that the PLA / CA blend began to thermal degradation. Because of the low thermal degradation temperature of PAMAM, the thermal degradation of PLA / CA blend was advanced by the addition of PAMAM. The weight loss rate of the blend film was the highest in the range of 350 °C- 380 °C. When the temperature reached 400 °C, the mass loss gradually decreased and the weight tended to be stable, indicating that the thermal decomposition of the blend was basically completed. When the temperature exceeded 450 °C, the weight of the blend had no obvious change, and the residue could be regarded as the ash content of the blend. Compared with pure PLA / CA blend, Tdmax decreased first and then increased, Td5% and Rd increased first and then decreased with the PAMAM addition. When PAMAM was less than 3 phr, the decrease of Td5% and Tdmax with the addition of PAMAM indicated that the thermal stability of PAMAM was reduced due to the low decomposition temperature of PAMAM, and the increase of residue indicated that the interaction between PAMAM and PLA / CA blends was enhanced and the undecomposed component was increased. When PAMAM was 3 phr, Td5% was 285.02 °C, Tdmax was the lowest at 354.31 °C and Rd was the highest at 8.69%, which exhibited the best thermal stability. Then with the increase of PAMAM content, Td5% and Tdmax increased slightly and the residual decreased, indicating that the interaction between PAMAM and PLA / CA blends was strong and the decomposition was more serious.
Tab. 1 Thermal performance and thermal stability parameters of the PLA/CA blends with different content of PAMAM.
Content
|
Tg
|
Tcc
|
Tm
|
∆Hc
|
∆Hm
|
Td(5%)
|
Td tmax
|
Rd
|
phr
|
°C
|
°C
|
°C
|
kJ mol-1
|
kJ mol-1
|
°C
|
°C
|
%
|
0
|
58.25
|
108. 78
|
159.58
|
20.04
|
20.52
|
336.31
|
378.75
|
7.07
|
1
|
56. 66
|
105.53
|
159.09
|
20.61
|
21.99
|
324.75
|
381.59
|
7.08
|
2
|
55. 09
|
102.63
|
158.05
|
21.30
|
23.96
|
297.51
|
374.42
|
8.68
|
3
|
54.01
|
100.35
|
157.53
|
21.39
|
24.85
|
285.02
|
354.31
|
8.69
|
4
|
54.60
|
102.16
|
157.23
|
21.85
|
22.57
|
275.42
|
362.78
|
8.25
|
5
|
52.83
|
101.66
|
155.82
|
22.02
|
22.27
|
279.20
|
361.78
|
6.44
|
3.5 Mechanical properties
Fig. 5 shows the tensile and tearing properties of PLA/ CA blends with different PAMAM contents. It can be seen that with the increase of PAMAM, the tensile strength, elongation at break, fracture energy and tearing strength all increased first and then decreased. When the content of PAMAM was 3 phr, the mechanical properties of PLA / CA blends reached the maximum, the tensile strength, elongation at break, fracture energy and tearing strength were 22.56 MPa, 14.95 %, 279.232 MJ∙m-2 and 49.94 kN∙m-1, respectively, which were increased by 120 %, 183 %, 551 % and 141 % compared with PLA / CA blends. With the increase of PAMAM content, the Young's modulus of the blends decreased, indicating that the main deformation of the blends was plastic deformation, and the part with elastic deformation decreased.
PAMAM enhanced the interface compatibility between PLA and CA, reduced stress concentration, and transferred the stress to CA uniformly, thereby increasing the tensile strength. PAMAM was combined with active groups in PLA and CA to form hydrogen bond physical crosslinking, which improved the toughness and tear resistance of the blends. At the same time, PAMAM promoted the slip of the interface between PLA and CA by increasing the molecular chain motion, and the crack propagation caused by CA stress concentration also played a toughening effect. In addition, PAMAM contained a large number of cavities, which could absorb energy during tearing and stretching, playing a role of strengthening and toughening [34]. However, when the content of PAMAM exceeded 3 phr, the overall mechanical properties of PLA / CA decreased. The strong hydrogen bond of high content of PAMAM promoted the aggregation of CA, which increased the particle size, reduced dispersion degree, restricted the movement of molecular chain, and improved the stress concentration.. As a result, both the strength and toughness of the blends were reduced.
3.6 Hydrophilicity
Fig. 6a shows the contact angle image of PLA/CA blend films. Polylactic acid is a hydrophobic material, while cellulose acetate with a certain number of hydroxyl groups is hydrophilic. The contact angle of neat PLA/CA blends was 66.3°. With the addition of PAMAM, the contact angle increases first and then decreased. When 3 phr PAMAM was added, the maximum contact angle of the blend film was 79.9 °. This was mainly due to the large number of ester end groups in the dendrimer, which improved the hydrophobicity of the blend. In addition, the wettability of the material surface is not only related to the hydrophilicity of the material, but also related to the interinterface compatibility of PLA and CA. When the amount of PAMAM was less than 3phr, the compatibility between PLA and CA was improved, and the dispersion of CA in PLA matrix was promoted, thus the contact angle and hydrophobicity of PLA / CA blends was increased. When the content of PAMAM was greater than 3 phr, the interaction between PAMAM and CA was enhanced, and the increase of CA particle size resulted the decrease of compatibility, the decrease of contact angle and the increase of hydrophilicity. The hydrophilic and hydrophobic properties of PLA / CA blend films can be adjusted by changing the addition amount of PAMAM.
3.7 Gas permeability.
Fig. 6b shows the oxygen penetration of PLA / CA blends with different PAMAM contents. With the addition of PAMAM, the oxygen permeability was firstly increased and then decreased. When 4 phr PAMAM were added, the oxygen permeability of the film reached 2.025×10-10 m3∙m-2·(1d·atm)-1, which was 3 orders of magnitude higher than that of PLA / CA blend films with 0phr PAMAM, indicating that the addition of dendritic macromolecule greatly increased the oxygen permeability of the blends.
The addition of PAMAM promoted the movement of PLA molecular chain segments, caused the change of crystallinity, leading to the change of oxygen permeability of blend film. Meanwhile, the oxygen permeability of PLA / CA blend films is related to the void of the blend. PAMAM has a spherical dendritic structure with many voids between the branched chains that facilitate the passage of oxygen. The greater the number and size of voids, the faster the oxygen permeates. When the content of PAMAM was low, the number of voids in the film increased with the increase of the content of PAMAM, and the oxygen permeability of the film increased. However, when the content of PAMAM was 5 phr, CA was agglomerated due to the over-strong hydrogen bond of PAMAM, which resulting in the decrease of oxygen permeability.
3.8 Biodegradation Behavior
The composting experiment was carried out on PLA / CA blends, and the influence of PAMAM content on the degradation performance of the blend film was explored through morphology, thermal properties and thermal stability.
Fig. 7 shows the appearance and micromorphology of PLA / CA blend films surface during composting degradation. When the time was 10 d, the surface of PLA / CA blend films containing 1 phr and 3 phr PAMAM appeared many holes and became rough, while the surface of neat PLA / CA films had no obvious change. When the degradation time was 20 days, the blend containing 3 phr PAMAM began to disintegrate and appeared large cracks. The disintegration of the blend containing 3 phr PAMAM was more obvious at 30 days, but only a small amount of the blends with 1 phr PAMAM disintegrated and appeared cracked at that time. When the degradation time was 40 days, both the PLA / CA blends containing 1phr and 3phr PAMAM showed significantly disintegration and formed many fragments, while the blank films just started to disintegrate. It indicated that the degradation time of the blends was earlier with the increase of PAMAM.
Fig. 8 shows the micro-morphology of PLA / CA blend films surface during composting degradation. It can be clearly observed that when the degradation time was 10 days, a large crack appeared on the PLA / CA blend film containing 3 phr PAMAM, only tiny cracks appeared on the film containing 1 phr PAMAM, and no obvious change was found on the film with 0phr PAMAM. After 20d, many spherical particles appeared on the surface of all the films, the number and range of cracks on the film with 1 phr PAMAM increased, and the crack on the film with 3 phr PAMAM became deeper. On the 30th day, deep cracks appeared in the film with 1 phr and 3 phr PAMAM, while only a lot of small cracks appeared in film contained 0 phr PAMAM indicated the beginning of degradation at that time. When the degradation time was 40 days, cracks and concave-convex morphology appeared on the surface of all PLA / CA blend films and degradation occurred in all of them. It could be concluded that with the increase of PAMAM content, the degradation of PLA / CA blend film was gradually accelerated, from surface erosion to internal erosion.
As shown in Fig. 9a- 9c and Fig. S3, Tg, Tcc and Tm of the blends decreased with the increase of composting degradation time. With the increase of degradation time, the thermal parameters of PLA / CA blends containing 0 phr PAMAM decreased a little, while the Tg, Tcc and Tm of the blend with 1 phr PAMAM increased, and the variation range was less than that of blend with 0phr PAMAM. When the content of PAMAM was 3 phr, the decrease of thermal parameters was the most obvious, indicating that these parameters decreased with the increase of PAMAM.
The thermogravimetric curves and initial decomposition temperature (Td) of PLA / CA blends during degradation were shown in Fig. 9d and Fig. S4. It was obvious that the Td of PLA / CA blends decreased with the increase of PAMAM content and degradation time, and the decrease of Td was the most significant when the PAMAM content was 3phr.
The degradation of PLA / CA blends promoted by PAMAM had been described qualitatively. In order to quantitatively study the effect of PAMAM on the biodegradation of PLA / CA blends, the changes of carbon, hydrogen and nitrogen during the degradation were studied by using the method of element analysis. Fig. 10 shows the change of PLA / CA with different content of PAMAM during degradation, and the ratio of carbon to hydrogen and carbon to nitrogen were listed in Tab. 2. It can be seen from Fig. 10 that with the increase of degradation time, the carbon content and hydrogen content of all PLA / CA blends decreased, while the nitrogen content increased, indicating that PLA / CA blends were biodegradable. As shown in Fig. 10a, when the degradation time was 10 days, the C content increased with the increase of PAMAM content, which was due to the introduction of PAMAM. At the same time, the C content of PLA / CA blend with 3 phr PAMAM decreased most at 40 days, from 45.1 % to 43.7 % (decreased by 1.4 %), while that of PLA / CA blend without PAMAM (0 phr) decreased only by 0.5 %, indicating that with the increase of PAMAM content, the content of C decreased more and PLA / CA degraded faster. Fig. 10b showed that the addition of PAMAM reduced the reduction of H content and delayed the reduction of H, indicating that more C was consumed during the degradation process. It can be seen from Fig. 10c that with the increase of PAMAM content, N content increased, indicating that PAMAM was one of nitrogen source. However, the N content of PLA / CA blends containing 0 phr PAMAM is not zero, which indicated that the N element was produced by microbial decomposition of PLA / CA. At the same time, the addition of PAMAM increased the N content more, indicating that PAMAM could promote the microbial decomposition of PLA / CA and improve the degradation degree. Tab. 2 showed that with the increase of degradation time, the C / H ratio only increased slightly, indicated that the decomposition rates of C and H were basically the same during the degradation process. The C / N ratio decreased with the extension of degradation time and the increase of PAMAM content, indicating that the degradation degree of PLA / CA increased with the increase of degradation time and PAMAM content, which confirmed that PAMAM promoted the degradation of PLA / CA.
In addition, it can be seen from Fig. 10 and Tab. 2 that the nitrogen content of PLA / CA blends containing 3 phr PAMAM is not more than 0.9 % during the degradation process, and its ratio to carbon content is less than 2 %, while the nitrogen content introduced by PAMAM is only 0.2 % at most.
Tab. 2 Element ratio of PLA / CA blends during degradation.
|
C/H
|
C/N
|
|
0 phr
|
1 phr
|
3 phr
|
0 phr
|
1 phr
|
3 phr
|
10day
|
11.2
|
12.1
|
11.3
|
97.6
|
81.6
|
69.3
|
20days
|
11.3
|
12.1
|
11.7
|
89.4
|
74.6
|
61.2
|
30days
|
12.4
|
12.6
|
11.7
|
85.5
|
63.6
|
55.5
|
40days
|
12.7
|
12.7
|
11.8
|
74.0
|
55.4
|
50.6
|
In the process of composting, polyester degradation mainly consists of two stages: the first stage is the breakdown of ester bonds to form oligomers, and the second stage is the absorption of oligomers by microorganisms [35]. At the initial stage of degradation, due to the invasion of water, the molecular chains of polylactic acid and CA were randomly broken. PLA / CA blend films with more cracks and voids were more susceptible to water erosion and hydrolyze, resulting in lower molecular weight and enhanced mobility of molecular chains. Therefore the thermal parameter of PLA / CA blends decreased [36]. As time went on, the molecular weight of the blend film further decreased, microorganisms began to erode the film to produce CO2 and H2O, and gradually spread from the surface to the interior of the material, and the blend film disintegrated into small pieces. Lactic acid disappeared in the process of microbial assimilation[37].
PAMAM enhanced water erosion by increasing voids number and increasing the movement of molecular chains for decomposition and microbial erosion. In addition, because the peptide bond structure of PAMAM can be hydrolyzed and aminated, PAMAM has good biodegradability and can promote the decomposition of PLA / CA [38, 39]. When the content of PAMAM was 3 phr, the degradation effect was significant and the degradation time was shortened, indicating that the biodegradability of PLA / CA blends could be improved by using a smaller amount of PAMAM.