Physically Crosslinked Poly (Vinyl Alcohol)/Kappa-Carrageenan Hydrogels: Structure and Applications
Abstract
:1. Introduction
2. Experimental
2.1. Materials
2.2. Gels Obtaining
2.3. Morphological and Structural Characterization
2.4. Swelling and Sorption Experiments
3. Results and Discussion
3.1. Gels Structure and Morphology
3.2. Gels Swelling and Adsorption Behavior
4. Conclusions
Author Contributions
Funding
Conflicts of Interest
References
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Sample Code | PVA | CAR | wcar | Gels SC* (%) | Shore 00 Hardness * | Thickness * δ (mm) | G (%) | ||
---|---|---|---|---|---|---|---|---|---|
Vol. (mL) | Amount (g) | Vol. (mL) | Amount (g) | ||||||
PVA | 10 | 1 | - | - | 0 | 9.85 | 68 | 2.85 | 82.24 |
K/PVA 1:20 | 7.5 | 0.75 | 2.5 | 0.037 | 0.047 | 7.59 | 64 | 2.94 | 76.15 |
K/PVA 1:6 | 4.8 | 0.48 | 5.2 | 0.078 | 0.139 | 5.98 | 69 | 3.02 | 83.07 |
K/PVA 1:1 | 1.3 | 0.13 | 8.7 | 0.13 | 0.5 | 2.62 | 45 | 3.11 | 64.80 |
K | - | - | 10 | 0.15 | 1 | 1.54 | 12 | 3.16 | 0.75 |
Sample Code | FTIR | XRD | Pore volume Ratio Pr (%) | |||
---|---|---|---|---|---|---|
CrI | R (Å) | EH (kcal) | CrXRD (%) | DXRD (nm) | ||
PVA | 0.143 | 2.926 | 6.523 | 4.2 | 5.79 | 8.63 |
K/PVA 1:20 | 0.119 | 2.927 | 6.386 | 4.0 | 5.05 | 6.42 |
K/PVA 1:6 | 0.188 | 2.920 | 6.592 | 4.8 | 4.81 | 5.53 |
K/PVA 1:1 | 0.024 | 2.924 | 4.914 | 2.3 | 6.02 | 3.48 |
K | - | 2.929 | 5.034 | 1.1 | - | 2.31 |
Sample Code | TGA/DTG Results | DTA Results | DSC Results | ||||
---|---|---|---|---|---|---|---|
Twater (°C) | Tdegrad (°C) | ∆mdegrad (%) | ∆mresidue (%) | TDTA (°C) | Tg (°C) | CrDSC (%) | |
PVA | 100.2 | 146.5 273.5 340.3 | 95.5 | 4.0 | 170.7 | 75.5 | 5.5 |
K/PVA 1:20 | 109.2 | 133.6 167.1 225.5 | 91.4 | 4.6 | 132.7 169.7 | 60.5 | 5.2 |
K/PVA 1:6 | 113.1 | 149.1 185.9 214.7 | 37.8 | 19.4 | 145.8 | 30.5 | 5.9 |
K/PVA 1:1 | 104.0 | 145.7 206.7 268.8 | 90.7 | 3.5 | 145.5 | 29.5 | 3.2 |
K | 106.8 | 176.8 288.1 333.6 | 91.9 | 1.2 | 150.4 | - | - |
Material | Parameter | Swelling Medium | |||||
---|---|---|---|---|---|---|---|
Distilled Water | pH = 3 | pH = 5 | pH = 9 | pH = 13 | PBS | ||
PVA | ν (cm/min × 103) | 1.82 | 1.89 | 1.84 | 1.86 | 2.11 | 1.67 |
De (mm2/min × 105) | 1.82 (0.992) | 1.94 (0.984) | 1.90 (0.990) | 1.84 (0.994) | 2.01 (0.982) | 1.43 (0.992) | |
Dl (mm2/min × 102) | 6.72(0.977) | 8.92 (0.971) | 8.87 (0.989) | 8.79 (0.977) | 8.94 (0.975) | 5.11 (0.976) | |
k (min−0.5 × 103) | 4.10 (0.964) | 4.89 (0.960) | 5.16 (0.976) | 4.63 (0.983) | 4.75 (0.974) | 3.46 (0.988) | |
n | 0.73 (0.964) | 0.85 (0.960) | 0.82 (0.976) | 0.84 (0.983) | 0.91 (0.974) | 0.68 (0.988) | |
K/PVA 1:20 | ν (cm/min × 103) | 1.89 | 1.52 | 0.93 | 0.95 | 1.61 | 0.72 |
De (mm2/min × 105) | 6.31 (0.968) | 6.58 (0.972) | 6.40 (0.992) | 6.61 (0.988) | 6.72 (0.988) | 5.62 (0.995) | |
Dl (mm2/min × 101) | 2.30 (0.979) | 2.65 (0.989) | 2.40 (0.995) | 2.69 (0.985) | 2.73 (0.992) | 1.95 (0.984) | |
k (min−0.5 × 103) | 1.96 (0.967) | 1.99 (0.973) | 1.97 (0.989) | 2.01 (0.9) | 4.75 (0.974) | 3.46 (0.988) | |
n | 0.99 (0.967) | 0.85 (0.960) | 0.82 (0.976) | 0.84 (0.983) | 0.91 (0.974) | 0.68 (0.988) | |
K/PVA 1:6 | ν (cm/min × 103) | 1.65 | 1.78 | 1.69 | 1.71 | 1.82 | 1.38 |
De (mm2/min × 105) | 6.66 (0.986) | 7.80 (0.989) | 6.75 (0.992) | 6.72 (0.994) | 7.84 (0.992) | 5.42 (0.991) | |
Dl (mm2/min × 101) | 2.97 (0.988) | 3.18 (0.978) | 3.08 (0.977) | 3.11 (0.976) | 3.24 (0.972) | 1.47 (0.973) | |
k (min−0.5 × 103) | 4.0 (0.980) | 4.92 (0.991) | 4.27 (0.993) | 4.20 (0.988) | 5.02 (0.987) | 3.20 (0.988) | |
n | 0.93 (0.980) | 0.96 (0.991) | 0.94 (0.993) | 0.96 (0.988) | 1.00 (0.987) | 0.71 (0.988) | |
K/PVA 1:1 | ν (cm/min × 103) | 3.66 | 3.90 | 3.69 | 3.73 | 3.98 | 1.89 |
De (mm2/min × 104) | 8.24 (0.993) | 8.97 (0.998) | 8.28 (0.997) | 8.27 (0.991) | 8.89 (0.992) | 5.43 (0.992) | |
Dl (mm2/min × 101) | 3.95(0.970) | 4.72 (0.975) | 4.12 (0.970) | 4.06 (0.978) | 4.80 (0.980) | 2.99 (0.989) | |
k (min−0.5 × 103) | 5.23 (0.995) | 5.39 (0.994) | 5.28 (0.989) | 5.23 (0.995) | 5.23 (0.995) | 5.23 (0.988) | |
n | 0.95 (0.995) | 0.97 (0.994) | 0.96 (0.989) | 0.95 (0.995) | 0.95 (0.995) | 0.62 (0.988) |
Isotherm Model | Isotherm Equation (Linearized Form) | Equation Parameters | |||
---|---|---|---|---|---|
PVA | K/PVA 1:20 | K/PVA 1:6 | K/PVA 1:1 | ||
Langmuir | KL = 0.092 Qm = 153.84 RL: 0.11 ÷ 0.35 R2 = 0.953 | KL = 0.103 Qm = 76.92 RL: 0.11 ÷ 0.32 R2 = 0.731 | KL = 0.035 Qm = 625.11 RL: 0.26 ÷ 0.58 R2 = 0.789 | KL = 0.176 Qm = 55.55 RL: 0.06 ÷ 0.22 R2 = 0.909 | |
Freundlich | KF = 14.270 1/nF = 0.77 R2 = 0.979 | KF = 5.371 1/nF = 1.70 R2 = 0.976 | KF = 22.510 1/nF = 0.88 R2 = 0.998 | KF = 7.882 1/nF = 1.94 R2 = 0.997 | |
Radke–Prausnitz | KRP = 0.146 Qm = 79.42 m = 0.65 R2 = 0.970 | KRP = 0.763 Qm = 92.90 m = 1.50 R2 = 0.967 | KRP = 0.111 Qm = 123.97 m = 0.90 R2 = 0.998 | KRP = 0.940 Qm = 112.59 m = 2.00 R2 = 0.995 | |
Redlich–Peterson | KR = 8.372 g = 0.74 αR = 0.11 Qm = 76.10 R2 = 0.979 | KR = 1.372 g = 0.79 αR = 0.013 Qm = 99.91 R2 = 0.979 | KR = 1.619 g = 0.81 αR = 0.013 Qm = 124.59 R2 = 0.998 | KR = 1.631 g = 0.86 αR = 0.014 Qm = 116.54 R2 = 0.909 | |
Dubinin–Radushkevich | Qm = 63.10 β: = 9 10−7 E = 745 R2 = 0.914 | Qm = 142.25 β: = 3 10−6 E = 408 R2 = 0.995 | Qm = 130.08 β: = 8 10−7 E = 791 R2 = 0.865 | Qm = 112.44 β: = 2 10−6 E = 500 R2 = 0.992 | |
Flory–Huggins | KFH = 2.2 10−5 n = 2.85 ∆G° = −26.48 R2 = 0.774 | KFH = 5.378 n = 2.27 ∆G° = 4.16 R2 = 0.951 | KFH = 1.8 10−10 n = 1.90 ∆G° = −55.44 R2 = 0.879 | KFH = 6.529 n = 2.05 ∆G° = 4.65 R2 = 0.996 | |
− | Thermodynamic parameters according to Equations (5) and (6) and Figure 9b for c0 = 80 mg/L (at 25 °C) | ∆H° = −6.7 ∆S° = 15.6 ∆G° = −11.3 | ∆H = 10.5 ∆S° = 23.4 ∆G° = 11.1 | ∆H° = −14.5 ∆S° = 22.0 ∆G° = −21.0 | ∆H° = 19.7 ∆S° = 36.5 ∆G° = 20.7 |
Kinetic Model | Model Equation (Linearized Form) | Equation Parameters | |||
---|---|---|---|---|---|
PVA | K/PVA 1:20 | K/PVA 1:6 | K/PVA 1:1 | ||
Pseudo-first-order | k1 = 1.8 × 10−3 R2 = 0.920 | k1 = 6.3 × 10−3 R2 = 0.899 | k1 = 0.018 R2 = 0.839 | k1 = 9.1 × 10−3 R2 = 0.849 | |
Pseudo-second-order | k2 = 0.4 × 10−5 R2 = 0.956 | k2 = 1.1 × 10−4 R2 = 0.961 | k2 = 7.5 × 10−4 R2 = 0.974 | k2 = 9.4 × 10−3 R2 = 0.908 | |
Intraparticle diffusion | (20% of the first portion of the kinetic data) | kd = 0.144 C = 3.9 × 10−8 R2 = 1 | kd = 2.314 C = 3.1 × 10−12 R2 = 1 | kd = 2.354 C = 0.254 R2 = 1 | kd = 1.739 C = 3.6 × 10−16 R2 = 1 |
Liquid film diffusion | kfd = 2.1 × 10−3 R2 = 0.891 | kfd = 1.5 × 10−2 R2 = 0.901 | kfd = 2.6 × 10−2 R2 = 0.924 | kfd = 1.2 × 10−2 R2 = 0.973 | |
Elovich | α = 2.1 × 10−17 β = 2.1 × 10−3 R2 = 0.634 | α = 1.2 × 10−8 β = 5.8 × 10−2 R2 = 0.325 | α = 6 × 10−7 β = 0.199 R2 = 0.251 | α = 9.1 × 10−4 β = 2.9 × 10−2 R2 = 0.929 |
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Croitoru, C.; Pop, M.A.; Bedo, T.; Cosnita, M.; Roata, I.C.; Hulka, I. Physically Crosslinked Poly (Vinyl Alcohol)/Kappa-Carrageenan Hydrogels: Structure and Applications. Polymers 2020, 12, 560. https://doi.org/10.3390/polym12030560
Croitoru C, Pop MA, Bedo T, Cosnita M, Roata IC, Hulka I. Physically Crosslinked Poly (Vinyl Alcohol)/Kappa-Carrageenan Hydrogels: Structure and Applications. Polymers. 2020; 12(3):560. https://doi.org/10.3390/polym12030560
Chicago/Turabian StyleCroitoru, Catalin, Mihai Alin Pop, Tibor Bedo, Mihaela Cosnita, Ionut Claudiu Roata, and Iosif Hulka. 2020. "Physically Crosslinked Poly (Vinyl Alcohol)/Kappa-Carrageenan Hydrogels: Structure and Applications" Polymers 12, no. 3: 560. https://doi.org/10.3390/polym12030560