Ifty Ahmed

Weight loss, ion release and initial mechanical properties of a binary calcium phosphate glass fibre/PCL composite

Composites comprising a biodegradable polymeric matrix and a bioactive filler show considerable promise in the field of regenerative medicine, and could potentially serve as degradable bone fracture fixation devices, depending on the properties obtained. Therefore, glass fibres from a binary calcium phosphate (50P(2)O(5)+50CaO) glass were used to reinforce polycaprolactone, at two different volume fractions (V(f)). As-drawn, non-treated and heat-treated fibres were assessed. Weight loss, ion release and the initial mechanical properties of the fibres and composites produced have been investigated. Single fibre tensile testing revealed a fibre strength of 474MPa and a tensile modulus of 44GPa. Weibull analysis suggested a scale value of 524. The composites yielded flexural strength and modulus of up to 30MPa and 2.5GPa, respectively. These values are comparable with human trabecular bone. An 8% mass loss was seen for the lower V(f) composite, whereas for the two higher V(f) composites an approximate 20% mass loss was observed over the course of the 5week study. A plateau in the degradation profile at 350h indicated that fibre dissolution was complete at this interval. This assertion was further supported via ion release studies. The leaching of fibres from the composite created a porous structure, including continuous channels within the polymer matrix. This offers further scope for tailoring scaffold development, as cells from the surrounding tissue may be induced to migrate into the resulting porous matrix.

Retention of mechanical properties and cytocompatibility of a phosphate-based glass fiber/polylactic acid composite

Polymers prepared from polylactic acid (PLA) have found a multitude of uses as medical devices. The main advantage of having a material that degrades is so that an implant would not necessitate a second surgical event for removal. In addition, the biodegradation may offer other advantages. In this study, fibers produced from a quaternary phosphate-based glass (PBG) in the system 50P(2)O(5)-40CaO-5Na(2)O-5Fe(2)O(3) (nontreated and heat-treated) were used to reinforce the biodegradable polymer, PLA. Fiber properties were investigated, along with the mechanical and degradation properties and cytocompatibility of the composites produced. Retention of mechanical properties overtime was also evaluated. The mean fiber strength for the phosphate glass fibers was 456 MPa with a modulus value of 51.5 GPa. Weibull analysis revealed a shape and scale parameter value of 3.37 and 508, respectively. The flexural strength of the composites matched that for cortical bone; however, the modulus values were lower than those required for cortical bone. After 6 weeks of degradation in deionized water, 50% of the strength values obtained was maintained. The composite degradation properties revealed a 14% mass loss for the nontreated and a 10% mass loss for the heat-treated fiber composites. It was also seen that by heat-treating the fibers, chemical and physical degradation occurred much slower. The pH profiles also revealed that nontreated fibers degraded quicker, thus correlating well with the degradation profiles. The in vitro cell culture experiments revealed both PLA (alone) and the heat-treated fiber composites maintained higher cell viability as compared to the nontreated fiber composites. This was attributed to the slower degradation release profiles of the heat-treated composites as compared to the nontreated fiber composites. SEM analyses revealed a porous structure after degradation, and it is clear that there are possibilities here to tailor the distribution of porosity within polymer matrices.

Quantification of Anion and Cation Release from a Range of Ternary Phosphate-based Glasses with Fixed 45 mol% P2O5

This article reports on the use of ion chromatography (IC) to investigate extensively the release profiles of both cations and anions and characterize the relationship between composition and degradation for a ternary-based Na2O-CaO-P2O5 glass system developed as biomaterials. Studies are carried out on glasses with the formula 45P2O5-55(xCaO-Na2O) in deionized water, where x = 30, 35, and 40 mol%, using a cumulative release method, where the solution is changed at regular intervals. Degradation behavior is linear with time where the degradation rate shows an initial decrease with increasing CaO content. This rate then increases with a further addition of CaO. Cation release profiles follow similar trends to the degradation rates. Anion release profiles show a decrease for the PO4 and linear polyphosphate (P2O7 and P3O10) species with increasing CaO content. This decrease is attributed to the cross-linking of the Ca2+ ions. In contrast, the cyclic P3O9 anion exhibits the highest amount of anionic release, which demonstrates similar trends to the cations. These release patterns suggest that the cyclic P3O9 species dominate the degradation rates. The proposed mode of degradation is a hydrolysis reaction, with the cyclic metaphosphate undergoing acid/base catalysis. The pH remains constant for the 30 and 35 mol% CaO glasses, and drops to about 5.5 for the 40 mol% composition. By using a response factor, it is possible to semiquantitatively analyze the additional peaks observed in the chromatograms. Suggestions are also put forward as to the identity of some of these unidentified peaks.

Investigation of crystallinity, molecular weight change, and mechanical properties of PLA/PBG bioresorbable composites as bone fracture fixation plates.

In this study, bioresorbable phosphate-based glass (PBG) fibers were used to reinforce poly(lactic acid) (PLA). PLA/PBG random mat (RM) and unidirectional (UD) composites were prepared via laminate stacking and compression molding with fiber volume fractions between 14% and 18%, respectively. The percentage of water uptake and mass change for UD composites were higher than the RM composites and unreinforced PLA. The crystallinity of the unreinforced PLA and composites increased during the first few weeks and then a plateau was seen. XRD analysis detected a crystalline peak at 16.6° in the unreinforced PLA sample after 42 days of immersion in phosphate buffer solution (PBS) at 37°C. The initial flexural strength of RM and UD composites was ∼106 and ∼115 MPa, whilst the modulus was ∼6.7 and ∼9 GPa, respectively. After 95 days immersion in PBS at 37°C, the strength decreased to 48 and 52 MPa, respectively as a result of fiber–matrix interface degradation. There was no significant change in flexural modulus for the UD composites, whilst the RM composites saw a decrease of ∼45%. The molecular weight of PLA alone, RM, and UD composites decreased linearly with time during degradation due to chain scission of the matrix. Short fiber pull-out was seen from SEM micrographs for both RM and UD composites.

Cytocompatibility and effect of increasing MgO content in a range of quaternary invert phosphate-based glasses.

Recently, phosphate-based glass (PBG) fibers have been used to reinforce the biodegradable polymers polycaprolactone and polylactic acid, in order to fabricate materials suitable for use as resorbable bone fracture fixation devices. However, the PBG fibers investigated tended to degrade too quickly for application. Therefore, more durable PBG formulations were sought with emphasis remaining firmly placed on their biocompatibility. In this study, four invert PBG formulations (in the system P2O5—CaO—MgO—Na 2O) were produced with fixed phosphate and calcium content at 40 and 25 mol%, respectively. MgO was added at 10—30 mol% in place of Na 2O and the maximum divalent cation to phosphate ratio obtained was 1.375. Thermal analyses showed a linear increase in Tg with increasing MgO content. This was proposed to be due to an increase in the cross-link density of the glass network, which also improved the chemical durability of the glass. EDX analyses were also conducted to verify the final composition of the glass. XRD analyses confirmed the amorphous nature of the glasses investigated. Rapid quenching of the Mg30 glass revealed a degree of surface crystallization, which was shown to be a CaMgP2O7 phase. The degradation rates of the glasses investigated decreased with increasing MgO content. The decrease in rate seen was almost two orders of magnitude (a ×50 difference was seen between glass Mg0 and Mg30). The cytocompatibility studies of the formulations investigated showed good cellular response over time for up to 14 days. Statistical analysis revealed that the formulations investigated gave a response comparable to the tissue culture plastic control. It is suggested that invert PBG provide degradation profiles and the cytocompatibility response desired to make these glasses useful for bone repair applications.

Phosphate Glass Fibre Composites for Bone Repair

We investigate high-modulus degradable materials intended to replace metals in biomedical applications. These are typically composites comprising a polylactide (PLA) matrix reinforced with phosphate glass fibres, which provide reinforcement similar to E-glass but are entirely degradable in water to produce, principally, calcium phosphate. We have made composites using a variety of fibre architectures, from non-woven random mats to unidirectional fibre tapes. Flexural properties in the region of 30 GPa modulus and 350 MPa strength have been achieved — directly comparable to quoted values for human cortical bone. In collaboration with other groups we have begun to consider the development of foamed systems with structures mimicking cancellous bone and this has shown significant promise. The fibres in these foamed structures provide improved creep resistance and reinforcement of the pore walls. To date the materials have exhibited excellent cellular responses in vitro and further studies are due to include consideration of the surface character of the materials and the influence of this on cell interaction, both with the composites and the glass fibres themselves, which show promise as a standalone porous scaffold.

In vitro degradation, flexural, compressive and shear properties of fully bioresorbable composite rods.

Several studies have investigated self-reinforced polylactic acid (SR-PLA) and polyglycolic acid (SR-PGA) rods which could be used as intramedullary (IM) fixation devices to align and stabilise bone fractures. This study investigated totally bioresorbable composite rods manufactured via compression moulding at ~100 °C using phosphate glass fibres (of composition 50P(2)O(5)-40CaO-5Na(2)O-5Fe(2)O(3) in mol%) to reinforce PLA with an approximate fibre volume fraction (v(f)) of 30%. Different fibre architectures (random and unidirectional) were investigated and pure PLA rods were used as control samples. The degradation profiles and retention of mechanical properties were investigated and PBS was selected as the degradation medium. Unidirectional (P50 UD) composite rods had 50% higher initial flexural strength as compared to PLA and 60% higher in comparison to the random mat (P50 RM) composite rods. Similar initial profiles for flexural modulus were also seen comparing the P50 UD and P50 RM rods. Higher shear strength properties were seen for P50 UD in comparison to P50 RM and PLA rods. However, shear stiffness values decreased rapidly (after a week) whereas the PLA remained approximately constant. For the compressive strength studies, P50 RM and PLA rods remained approximately constant, whilst for the P50 UD rods a significantly higher initial value was obtained, which decreased rapidly after 3 days immersion in PBS. However, the mechanical properties decreased after immersion in PBS as a result of the plasticisation effect of water within the composite and degradation of the fibres. The fibres within the random and unidirectional composite rods (P50 RM and P50 UD) degraded leaving behind microtubes as seen from the SEM micrographs (after 28 days degradation) which in turn created a porous structure within the rods. This was the main reason attributed for the increase seen in mass loss and water uptake for the composite rods (~17% and ~16%, respectively).

Effect of cellulose nanowhiskers on surface morphology, mechanical properties, and cell adhesion of melt-drawn polylactic Acid fibers.

Polylactic acid (PLA) fibers were produced with an average diameter of 11.2 (± 0.9) μm via a melt-drawing process. The surface of the PLA fibers was coated with blends of cellulose nanowhiskers (CNWs) (65 to 95 wt %) and polyvinyl acetate (PVAc). The CNWs bound to the smooth PLA fiber surface imparted roughness, with the degree of roughness depending on the coating blend used. The fiber tensile modulus increased 45% to 7 GPa after coating with 75 wt % CNWs compared with the uncoated PLA fibers, and a significant increase in the fiber moisture absorption properties at different humidity levels was also determined. Cytocompatibility studies using NIH-3T3 mouse fibroblast cells cultured onto CNWs-coated PLA surface revealed improved cell adhesion compared with the PLA control, making this CNW surface treatment applicable for biomedical and tissue engineering applications. Initial studies also showed complete cell coverage within 2 days.

Effect of Boron Addition on the Thermal, Degradation, and Cytocompatibility Properties of Phosphate-Based Glasses

In this study eight different phosphate-based glass compositions were prepared by melt-quenching: four in the (P2O5)45-(CaO)16-(Na2O)15-x -(MgO)24-(B2O3)x system and four in the system (P2O5)50-(CaO)16-(Na2O)10-x-(MgO)24-(B2O3)x, where x = 0,1, 5 and 10 mol%. The effect of B2O3 addition on the thermal properties, density, molar volume, dissolution rates, and cytocompatibility were studied for both glass systems. Addition of B2O3 increased the glass transition (T g), crystallisation (T c), melting (T m), Liquidus (T L) and dilatometric softening (T d) temperature and molar volume (V m). The thermal expansion coefficient (α) and density (ρ) were seen to decrease. An assessment of the thermal stability of the glasses was made in terms of their processing window (crystallisation onset, T c,ons minus glass transition temperature, T g), and an increase in the processing window was observed with increasing B2O3 content. Degradation studies of the glasses revealed that the rates decreased with increasing B2O3 content and a decrease in degradation rates was also observed as the P2O5 content reduced from 50 to 45 mol%. MG63 osteoblast-like cells cultured in direct contact with the glass samples for 14 days revealed comparative data to the positive control for the cell metabolic activity, proliferation, ALP activity, and morphology for glasses containing up to 5 mol% of B2O3.

The structure of phosphate glass biomaterials from neutron diffraction and P-31 nuclear magnetic resonance data

Neutron diffraction and 31P nuclear magnetic resonance spectroscopy were used to probe the structure of phosphate glass biomaterials of general composition (CaO)0.5-x(Na2O)x(P2O5)0.5 (x = 0, 0.1 and 0.5). The results suggest that all three glasses have structures based on chains of Q2 phosphate groups. Clear structural differences are observed between the glasses containing Na2O and CaO. The P-O bonds to bridging and non-bridging oxygens are less well resolved in the neutron data from the samples containing CaO, suggesting a change in the nature of the bonding as the field strength of the cation increases [Formula: see text]. In the (CaO)0.5(P2O5)0.5 glass most of the Ca2+ ions are present in isolated CaOx polyhedra whereas in the (Na2O)0.5(P2O5)0.5 glass the NaOx polyhedra share edges leading to a Na-Na correlation. The results of the structural study are related to the properties of the (CaO)0.4(Na2O)0.1(P2O5)0.5 biomaterial.