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N. Chowdhury etal.

2.6.5 Triple Network Hydrogel

The BC–PVA–PAMPS triple network hydrogel exhibits similar aggregate permea­bility, and compressive-tensile modulus as cartilage, displaying comparable defor­mation that changes over time under conned compression, while also demonstrating non-toxicity, high tensile modulus 10–30MPa, permeability value (3.2×10 compressive modulus 10–20MPa, 45% lower friction coefcient than cartilage (0.06), and 4.4× more surface wear resistance than a single network PVA hydrogel, 1mm for 105cycles [109]. The physical properties of SB/PVA triple network hydro­gels were tremendously enhanced, with a 461% increase in compressible strength with a 116% increase in stretching strength compared to pure PVA hydrogel [110]. Other triple-network hydrogels, such as PAA/Agar/PVA [118], TN (fracture stress: 450 kPa, compression strength: 1337 kPa), PVA/B TN [119] (toughness, rapid recovery, and self-healing ability), PAA/Gela/PVA TN [120] (fracture stress: 808 kPa, compressive strength: 4443 kPa, compressive modulus: 39 MPa), and PVA/PVP/PAA TN (fracture stress: 1.87MPa, compressive stress: 3.5MPa, friction coefcient: 0.15) as shown in Figs.2.38 and 2.39, also exhibited superior mechani­cal properties and potential applications in biomedicine and human motion monitor­ing [122]. By using PVA, AA, and PVP as three major materials, the PVA/PVP/PAA hydrogel exhibited a maximum friction coefcient of 0.45, which even reduced more to a value of 0.15 when the Zn2+ content reached a low of 0.8g [122]. At an SB content of 0.4wt%, the PVA/SB triple network hydrogels exhibited reduced friction, with a coefcient of friction of 0.077, suggesting that the hydrogel per­ceives more improved compressive properties and uniform porous structure at this particular SB content. The biphasic nature of PVA/SB TN hydrogel, consisting of interstitial water as a uid phase and a permeable solid phase, contributes to its frictional properties through water re-absorption and elastic energy dissipation, while the presence of non-covalent and reversible coordination bonds and oating linear polymer chains further enhances lubrication and reduces shear stress, particu­larly under higher loads [110]. A composite of PVA/PEG-glycerol considered as triple network hydrogel was successfully fabricated via a physical freeze-drying crosslinking method which is also known as physical crosslinking, demonstrating a tensile strength for 270% elongation at a break of 26.6MPa when incorporating
18m2
),
Fig. 2.39 Stress vs compression value for not only triple but also single and double network hydrogel [117]
2 Characterization ofHydrogel Properties intheAdvancement ofBio-Tribology
Fig. 2.40 Compressive stress vs. strain value for three types of network hydrogels [117]
63
glycerol as a percentage of 20wt% as a plasticizer, meeting the requirements close to the characteristics of natural cartilage [142]. Another triple network hydrogel composed of poly (N-isopropyl acrylamide), alginate, and carbon nanobers dem­onstrated impressive mechanical and physical properties, including compression stress of 3MPa, and exhibited notable electric conductivity of 66mS/cm. The suc­cessful synthesis of a hydrogel network with a combination of ionic and covalent entanglement, incorporating carbon nanobers, poly (N-isopropyl acrylamide), and alginate, resulted in an electrically conducting and robust hydrogel. This conductive hydrogel exhibits thermal activation capabilities, which can be achieved through direct Joule heating or uid immersion methods [111]. Though the mechanical properties of most TN hydrogels have been investigated for compressive strength, tensile strength, storage modulus, fracture energy, and fatigue strength, much work has not been accomplished to understand the structural and tribological behaviors of these hydrogels (Fig.2.40).
2.7 Structural andMechanical Property Relation
withSurface Properties

2.7.1 Mechanical Properties

The occurrence of local collagen rupture within articular cartilage could result in a decrease in the effective elastic modulus (En), consequently leading to reduced interlayer lubrication under all circumstances. Extended periods of joint inactivity may lead to a gradual decline in uid pressure, potentially causing harm if joint movement resumes without adequate uid pressure. Although the exact correlation between biochemical response and stress state is not fully understood, the model proposes that osteoarthritis (OA) may increase tribological shear stress in
64
N. Chowdhury etal.
comparison to uid pressure. As a result, the degenerative alterations related to OA could impede interstitial lubrication and substantially modify the stress state, lead­ing to potential adverse cellular reactions [143, 180184]. The stiffness increases with solid matrix concentration, and it affects the tribological properties [66]. With increasing force, the friction coefcient of cartilage decreases [60], the same was observed for the hydrogels too [144]. In brief, during short loading times, the uid phase within cartilage predominantly carries the load, leading to minimal friction. However, as the interval for adding load extends, more synovial uid is displaced from the area of contact, diminishing the capacity of load bearing of the uid phase. The Hertz contact model is used for two elastic spheres, or two elastic bodies defor­mation equation is given below:
123
4
FERd=
3
2
For adhesive contact, Derjaguin-Muller-Toporov (DMT) and Johnson-Kendall­Roberts (JKR) models are used [145]. For rough surface and statistical distribution of asperities, the Greenwood-Williamson model is used and for plastic deformation, the elastic-plastic contact model is used [146, 147]. Consequently, the friction between the sliding surfaces increases during startup as the force is conveyed to the solid area of the cartilage. Surprisingly, despite the coefcient of friction decreasing with higher loads, it was evident that with the applied load, the force generated due to friction did not increase proportionally due to the morphology as shown in Fig.2.41. This observation suggests the presence of an external factor like support
Fig. 2.41 The present summary provides an overview of how the mechanical properties, biochemical content of cartilage, and gross morphology contribute to sustaining tribological function in the diarthrodial joint. In the depicted panels, the left side showcases diseased cartilage, while the right side exhibits healthy cartilage. Notably, the mechanical properties, biochemical content, and gross morphology are found to be compromised when it is diseased cartilage [11]
2 Characterization ofHydrogel Properties intheAdvancement ofBio-Tribology
65
from the interstitial uid that subtly inuences the frictional properties of articular cartilage. Further research is needed to fully comprehend these complexities in car­tilage mechanics [132]. With increasing force, the friction coefcient decreases, once a specic sliding speed threshold is reached, the friction coefcient again increases [60, 124, 125]. The stiffness increases with solid matrix concentration, and it affects the tribological properties.
In the examination of SEM, TEM, and AFM images, a collapsed brous struc­ture in dehydrated articular cartilage models due to uid removal was observed. However, the treated cartilage samples showed complete recovery of their mechani­cal properties, suggesting a potential reconstitution of the network structure upon rehydration, apart from the supercial zone, where permanent alterations were detected. These alterations included reduced surface porosity and a less prominent ber network, which did not signicantly affect the creep and friction behaviors upon physiological rehydration. Despite the cartilage’s limited ability to repair itself, its high endurance and robustness compensate for this deciency [148,
185187].

2.7.2 Structural Properties

The frictional characteristics of both cartilage and hydrogels are predominantly inuenced by permeability and uidic support within the interstitial joints, resulting in an articular cartilage-like response. A notable improvement in the frictional response can be achieved in both cartilage and hydrogels by reducing their respec­tive pore sizes. Interestingly, friction tests conducted on these materials revealed minimal wear, with surface morphology changes observed during the early phases of wear, which are completely unrelated to the equilibrium friction coefcient. Therefore, it is essential to consider both wear and friction measurements to accu­rately investigate the tribological and structural performance of both cartilage and hydrogels. Furthermore, changing mesh size and pore size not only enhances the frictional behavior but also enhances the mechanical rigidity of both silk broin hydrogels and cartilage, without compromising either of these aspects. This simul­taneous enhancement demonstrates the promising potential of pore size reduction as an effective approach for optimizing the performance of both cartilage and hydro­gels [66, 149, 150, 188190]. It is observed that the alloy design and fabrication plays an integral role in the performances [191197]. Laser-assisted fabrication can be a potential method in tuning the surface and texture [198200].
However, there has been a contradiction in the mesh size relation with friction properties in many other works on hydrogels. They nd an inverse correlation between friction and mesh size. The permeability effect of these hydrogels for fric­tion is yet to be investigated [124, 125, 144]. In the context of cartilage, minor varia- tions in the coefcient of friction were observed between fresh and rehydrated samples. Upon analyzing different rehydration uids, it was found that hypotonic rehydration substantially raised friction coefcients for all sliding speeds, except
66
[]
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N. Chowdhury etal.
the slowest [148, 201204]. In articular cartilage, the elastic resistance of collagen contributes to stiffness elastic energy storage capacity, and rigidity of the compact framework in shear, while proteoglycans within the collagen matrix induce pre­existing tensile stress in collagen bers, enhancing its properties [205209]. Therefore, the design of the systems is very important in considering the inuences of vacuum [210, 211], temperature, and humidity on the characterization of hydro­gel properties in bio-tribology [212, 213]. Vacuum environments eliminate trapped gases, providing clearer insights into intrinsic hydrogel properties. Temperature variations affect swelling behavior and mechanical responses, while humidity alters hydration states and mechanical properties. Regarding machining methods, particu­larly CNC, precise control over cutting parameters enables tailored surface topogra­phies. These surfaces can optimize bio-tribological performance by reducing friction and wear and promoting tissue integration. CNC machining offers a path­way to engineer hydrogel-based components for enhanced functionality in biologi­cal environments [214].
Additionally, the solid matrix structure of cartilage demonstrates intrinsic poro­elastic and viscoelastic behavior under shear stress, with collagen brils playing a crucial role in imparting energy storage capabilities and shear stiffness [151].
kke
Ny
=
0
The coefcient N represents the permeability-strain logarithmic relationship obtained and the strain was transformed to porosity, using the following equation, where p0 represents initial porosity with no strain, k0 represents intrinsic permeabil­ity [151].
ε
0
=
+
p
1
0

2.8 Conclusion

The surface properties of cartilage decide the comfort to humans. Various factors, such as direct trauma, obesity, immobilization, and repetitive loading, have been identied to predispose articular cartilage to degeneration. This degeneration could increase the friction behavior by altering the lubrication as numerous factors inu­ence the tribological characteristics, such as or including the composition, ultra­structure, and roles or purposes of articular cartilage are interconnected, applied force, sliding speed, viscous shear, and any disease, injury, or abnormal loading condition that alters its composition or ultrastructure can negatively impact the joint’s load-bearing capacity. It is yet to fully understand the lubrication and friction mechanism because of the biphasic nature of these materials of articular cartilage
2 Characterization ofHydrogel Properties intheAdvancement ofBio-Tribology
67
and prospective hydrogels for articular cartilage replacement. Articular cartilage has complex synovial uidwhich is composed of various components like HA, lubricin, and Aggrecan. Separating these components and dening the individual effect of these components from the synovial uid are complicated and yet to be fully understood. Additionally, the phases of lubrication are explained in this review but their transition parameters and reasons for transitioning from one phase to another are not completely understood by researchers. Understanding the complex interplay of friction and lubrication in cartilage is essential for developing effective strategies to address joint disorders and osteoarthritis. By exploring the molecular and mechanical properties of cartilage, researchers can gain valuable insights into optimizing hydrogel formulations to mimic natural cartilage and enhance wear resistance. Academic investigations into novel biomaterials and lubrication mecha­nisms hold promise in creating functional cartilage substitutes that can provide long-lasting relief to patients suffering from joint degeneration. Many other com­posite materials can evolve like triple network hydrogels to optimize the character­istics of articial articular cartilage by understanding their mechanical, structural, and tribological behaviors.

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