Addition of Graphene Oxide in Different Stages of the Synthesis of Waterborne Polyurethane-Urea Adhesives and Its Influence on Their Structure, Thermal, Viscoelastic and Adhesion Properties
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials
2.2. Synthesis of the Waterborne Polyurethane-Urea Dispersions without and with 0.04 wt % GO
- (a)
- Synthesis of the prepolymer: The polyol, 5 wt % DMPA (with respect to the total amount of prepolymer) and DBTDL catalyst were added into the reactor at 80 °C under mechanical stirring at 450 rpm for 30 min. Then, IPDI diisocyanate was added slowly, allowing the reaction for 2 h 30 min.
- (b)
- Dissolution of the prepolymer in acetone: The temperature was lowered to 40 °C and the acetone was added to dissolve the prepolymer, maintaining the mechanical stirring at 450 rpm for 30 min.
- (c)
- Neutralization of the ionic groups: TEA in 25 mL acetone was added to neutralize the protons of the DMPA hard segments in the prepolymer under mechanical stirring at 40 °C and 450 rpm for 30 min.
- (d)
- Chain extension: HZ was added under mechanical stirring at 40 °C and 450 rpm for 30 min.
- (e)
- Dispersion in water: The stirring speed was increased to 900 rpm and water was added under mechanical stirring at 40 °C for 30 min.
- (f)
- Distillation of acetone: The residual acetone was removed in rotavapor (Büchi, Flawil, Switzerland) at 50 °C under 300 mbar for 1 h.
2.2.1. PUD Obtained by Adding 0.04 wt % GO before Prepolymer Formation
2.2.2. PUD Obtained by Adding 0.04 wt % GO after Prepolymer Formation
2.2.3. PUD Obtained by Adding 0.04 wt % GO in Water
2.3. Experimental Techniques
2.3.1. Characterization of the Polyurethane-Urea Dispersions (PUDs) without and with 0.04 wt % GO
Solids Content
pH Measurement
Viscosity
2.3.2. Characterization of the Polyurethane-Urea (PU) Films without and with 0.04 wt % GO
Attenuated Total Reflectance Fourier Transform Infrared (ATR-IR) Spectroscopy
Raman Spectroscopy
Differential Scanning Calorimetry (DSC)
Thermal Gravimetric Analysis (TGA)
X-Ray Diffraction (XRD)
Plate-Plate Rheology
Stress-Strain Tests
Confocal Laser Microscopy
Water Contact Angle Measurements
2.3.3. Adhesion Properties
T-peel Tests of Plasticized PVC/Polyurethane-Urea Dispersion/Plasticized PVC Joints
Single Lap-Shear Test of Stainless Steel 304/Polyurethane-Urea Dispersion/Stainless Steel 304 Joints
3. Results and Discussion
3.1. Characterization of the Graphene Oxide (GO)
3.2. Characterization of the PUDs
3.3. Characterization of the PU Films
3.4. Adhesion Properties of the PUDs
4. Conclusions
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
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Polyurethane-Urea Dispersion | Solids Content (wt %) | pH |
---|---|---|
PUD | 38.6 ± 0.6 | 9.5 ± 0.2 |
PUD+0.04 wt % GO in polyol | 36.8 ± 0.7 | 9.2 ± 0.2 |
PUD+0.04 wt % GO after prepolymer | 39.1 ± 0.7 | 9.4 ± 0.2 |
PUD+0.04 wt % GO in water | 39.0 ± 0.4 | 9.1 ± 0.0 |
Polyurethane-Urea Dispersion | Viscosity at 1 s−1 (mPa·s) | Viscosity at 700 s−1 (mPa·s) | Pseudoplasticity Index * |
---|---|---|---|
PUD | 505 | 42 | 12.0 |
PUD+0.04 wt % GO in polyol | 142 | 30 | 4.7 |
PUD+0.04 wt % GO after prepolymer | 31 | 23 | 1.3 |
PUD+0.04 wt % GO in water | 150 | 60 | 2.5 |
Polyurethane-Urea Dispersion | η0 (mPa·s) | η∞ (mPa·s) | τ (s) | m |
---|---|---|---|---|
PUD | 1520 | 42 | 8.1 | 0.0240 |
PUD+0.04 wt % GO in polyol | 360 | 29 | 2.4 | 0.0003 |
PUD+0.04 wt % GO after prepolymer | 37 | 22 | 0.5 | 0.0002 |
PUD+0.04 wt % GO in water | 170 | 59 | 2.6 | 0.0006 |
Wavenumber (cm−1) | Relative Contribution of Species (%) | |||
---|---|---|---|---|
PU | PU+0.04 wt % GO in Polyol | PU+0.04 wt % GO after Prepolymer | PU+0.04 wt % GO in Water | |
1727 (free urethane) | 58 | 45 | 38 | 42 |
1711–1709 (H-bonded urethane) | 9 | 35 | 33 | 38 |
1693–1687 (free urea) | 22 | 9 | 14 | 12 |
1658–1652 (H-bonded urea) | 11 | 11 | 15 | 8 |
Polyurethane-Urea Film | Tg1 (°C) | Tg2 (°C) | Tg3 (°C) |
---|---|---|---|
PU | −49 | 30 | 198 |
PU+0.04 wt % GO in polyol | −52 | 28 | 195 |
PU+0.04 wt % GO after prepolymer | −52 | 27 | 174 |
PU+0.04 wt % GO in water | −52 | 26 | 197 |
Polyurethane-Urea Film | T5% (°C) | T50% (°C) |
---|---|---|
PU | 255 | 356 |
PU+0.04 wt % GO in polyol | 239 | 352 |
PU+0.04 wt % GO after prepolymer | 244 | 352 |
PU+0.04 wt % GO in water | 253 | 354 |
Polyurethane Urea Film | T1 (°C) | Weight Loss1 (%) | T2 (°C) | Weight Loss2 (%) | T3 (°C) | Weight Loss3 (%) | T4 (°C) | Weight Loss4 (%) |
---|---|---|---|---|---|---|---|---|
PU | 114 | 2 | 270 | 10 | 315 | 24 | 380 | 62 |
PU+0.04 wt % GO in polyol | 196 | 4 | 275 | 10 | 312 | 21 | 376 | 63 |
PU+0.04 wt % GO after prepolymer | 211 | 5 | 271 | 11 | 304 | 18 | 377 | 64 |
PU+0.04 wt % GO in water | 126 | 4 | 270 | 10 | 312 | 21 | 377 | 63 |
Polyurethane-Urea Film | T cross-over (°C) | Gcross-over (kPa) |
---|---|---|
PU | 81 | 78.5 |
PU+0.04 wt % GO in polyol | 67 | 106.7 |
PU+0.04 wt % GO after prepolymer | 79 | 81.0 |
PU+0.04 wt % GO in water | 83 | 80.8 |
Polyurethane-Urea Film | Yield Stress (MPa) | Yield Strain (%) | Tensile Strength (MPa) | Elongation At-Break (%) |
---|---|---|---|---|
PU | 14 ± 1 | 7 ± 1 | 34 ± 4 | 725 ± 16 |
PU+0.04 wt % GO in polyol | 23 ± 1 | 3 ± 1 | 20 ± 5 | 637 ± 40 |
PU+0.04 wt % GO after prepolymer | 19 ± 5 | 11 ± 3 | 33 ± 5 | 728 ± 41 |
PU+0.04 wt % GO in water | 13 ± 1 | 13 ± 1 | 54 ± 3 | 695 ± 3 |
Polyurethane-Urea Film | Water Contact Angle (°) |
---|---|
PU | 40 ± 0 |
PU+0.04 wt % GO in polyol | 45 ± 2 |
PU+0.04 wt % GO after prepolymer | 50 ± 2 |
PU+0.04 wt % GO in water | 54 ± 4 |
Polyurethane-Urea Dispersion | T-peel Strength—1 h (kN/m) | T-peel Strength—72 h (kN/m) | Locus of Failure |
---|---|---|---|
PUD | 4.6 ± 0.4 | 6.2 ± 0.7 | CA+CS |
PUD+0.04 wt % GO in polyol | 6.9 ± 0.7 | 12.0 ± 2.0 | S+CA |
PUD+0.04 wt % GO after prepolymer | 7.4 ± 0.1 | 9.3 ± 0.1 | CS+CA |
PUD+0.04 wt % GO in water | 6.3 ± 0.4 | 7.1 ± 0.3 | CS+CA |
Polyurethane-Urea Dispersion | Shear Strength (kPa) | Locus of Failure |
---|---|---|
PUD | 95 ± 10 | A |
PUD+0.04 wt % GO in polyol | 226 ± 29 | A |
PUD+0.04 wt % GO after prepolymer | 190 ± 60 | A |
PUD+0.04 wt % GO in water | 721 ± 49 | A |
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Tounici, A.; Martín-Martínez, J.M. Addition of Graphene Oxide in Different Stages of the Synthesis of Waterborne Polyurethane-Urea Adhesives and Its Influence on Their Structure, Thermal, Viscoelastic and Adhesion Properties. Materials 2020, 13, 2899. https://doi.org/10.3390/ma13132899
Tounici A, Martín-Martínez JM. Addition of Graphene Oxide in Different Stages of the Synthesis of Waterborne Polyurethane-Urea Adhesives and Its Influence on Their Structure, Thermal, Viscoelastic and Adhesion Properties. Materials. 2020; 13(13):2899. https://doi.org/10.3390/ma13132899
Chicago/Turabian StyleTounici, Abir, and José Miguel Martín-Martínez. 2020. "Addition of Graphene Oxide in Different Stages of the Synthesis of Waterborne Polyurethane-Urea Adhesives and Its Influence on Their Structure, Thermal, Viscoelastic and Adhesion Properties" Materials 13, no. 13: 2899. https://doi.org/10.3390/ma13132899