Reda M. Felfel

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.

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).

In vitro degradation and mechanical properties of PLA-PCL copolymer unit cell scaffolds generated by two-photon polymerization.

The manufacture of 3D scaffolds with specific controlled porous architecture, defined microstructure and an adjustable degradation profile was achieved using two-photon polymerization (TPP) with a size of 2  ×  4  ×  2 mm(3). Scaffolds made from poly(D,L-lactide-co-ɛ-caprolactone) copolymer with varying lactic acid (LA) and ɛ -caprolactone (CL) ratios (LC16:4, 18:2 and 9:1) were generated via ring-opening-polymerization and photoactivation. The reactivity was quantified using photo-DSC, yielding a double bond conversion ranging from 70% to 90%. The pore sizes for all LC scaffolds were see 300 μm and throat sizes varied from 152 to 177 μm. In vitro degradation was conducted at different temperatures; 37, 50 and 65 °C. Change in compressive properties immersed at 37 °C over time was also measured. Variations in thermal, degradation and mechanical properties of the LC scaffolds were related to the LA/CL ratio. Scaffold LC16:4 showed significantly lower glass transition temperature (T g) (4.8 °C) in comparison with the LC 18:2 and 9:1 (see 32 °C). Rates of mass loss for the LC16:4 scaffolds at all temperatures were significantly lower than that for LC18:2 and 9:1. The degradation activation energies for scaffold materials ranged from 82.7 to 94.9 kJ mol(-1). A prediction for degradation time was applied through a correlation between long-term degradation studies at 37 °C and short-term studies at elevated temperatures (50 and 65 °C) using the half-life of mass loss (Time (M1/2)) parameter. However, the initial compressive moduli for LC18:2 and 9:1 scaffolds were 7 to 14 times higher than LC16:4 (see 0.27) which was suggested to be due to its higher CL content (20%). All scaffolds showed a gradual loss in their compressive strength and modulus over time as a result of progressive mass loss over time. The manufacturing process utilized and the scaffolds produced have potential for use in tissue engineering and regenerative medicine applications.

Mimicking Bone Structure and Function with Structural Composite Materials

This paper reviews the progress that has been made in fabricating biomimetic bone structures using synthetic composite materials. The specification for long bone applications is developed and we identify the candidate materials for delivering cortical and cancellous bone properties and function. The role of composite materials is discussed together with the factors influencing fibre and matrix type. Challenges associated with moderating their performance in-vivo are discussed, relating to the properties of the starting materials and the dependence, for fibre reinforced systems, on interface quality. Fabrication routes for producing complex biomimetic structures are also reviewed and the state of current clinical developments is described along with the associated technical and regulatory issues.

Finite element modelling of the flexural performance of resorbable phosphate glass fibre reinforced PLA composite bone plates.

A finite element method is presented to predict the flexural properties of resorbable phosphate glass fibre reinforced PLA composite bone plates. A novel method for meshing discontinuous fibre architectures is presented, which removes many of the limitations imposed by conventional finite element approaches. The model is used to understand the effects of increasing the span-to-thickness ratio for different fibre architectures used for PBG/PLA composites. A span-to-thickness ratio of 16:1 is found to be appropriate for materials with randomly orientated fibres, which agrees well with the test standard. However, for highly aligned materials the model indicates that a span-to-thickness ratio of 80:1 is required, in order to minimise the effects of shear deflection. The model is validated against flexural stiffness data from the literature for a range of polymers, fibres and fibre volume fractions. Generally there is less than 10% error between the FE predictions and experimental values. The model is subsequently used to perform a parametric study to understand what material developments are required to match the properties of PGF/PLA composites to cortical bone. It is concluded that alignment of the fibre is necessary to exceed the 20 GPa target, since the current manufacturing methods limit the fibre length to ∼10 mm, which consequently restricts the flexural modulus to ∼19 GPa (at 50% volume fraction).

Cytocompatibility, degradation, mechanical property retention and ion release profiles for phosphate glass fibre reinforced composite rods

Fibre reinforced composites have recently received much attention as potential bone fracture fixation applications. Bioresorbable composites based on poly lactic acid (PLA) and phosphate based glass fibre were investigated according to ion release, degradation, biocompatibility and mechanical retention profiles. The phosphate based glass fibres used in this study had the composition of 40P2O5-24MgO-16CaO-16Na2O-4Fe2O3 in mol% (P40). The degradation and ion release profiles for the composites showed similar trends with the amount of sodium and orthophosphate ions released being greater than the other cations and anions investigated. This was attributed to low Dietzals field strength for the Na(+) in comparison with Mg(2+) and Ca(2+) and breakdown of longer chain polyphosphates into orthophosphate ions. P40 composites exhibited good biocompatibility to human mesenchymal stem cells (MSCs), which was suggested to be due to the low degradation rate of P40 fibres. After 63 days immersion in PBS at 37 °C, the P40 composite rods lost ~1.1% of mass. The wet flexural, shear and compressive strengths for P40 UD rods were ~70%, ~80% and ~50% of their initial dry values after 3 days of degradation, whereas the flexural modulus, shear and compressive strengths were ~70%, ~80%, and ~65% respectively. Subsequently, the mechanical properties remained stable for the duration of the study at 63 days. The initial decrease in mechanical properties was attributed to a combination of the plasticisation effect of water and degradation of the fibre-matrix interface, with the subsequent linear behaviour being attributed to the chemical durability of P40 fibres. P40 composite rods showed low degradation and ion release rates, good biocompatibility and maintained mechanical properties similar to cortical bone for the duration of the study. Therefore, P40 composite rods have huge potential as resorbable intramedullary nails or rods.

Bioresorbable screws reinforced with phosphate glass fibre: Manufacturing and mechanical property characterisation

Use of bioresorbable screws could eliminate disadvantages associated with metals such as removal operations, corrosion, MRI interference and stress shielding. Mechanical properties of bioresorbable polymers alone are insufficient for load bearing applications application as screws. Thus, reinforcement is necessary to try and match or surpass the mechanical properties of cortical bone. Phosphate based glass fibres were used to reinforce polylactic acid (PLA) in order to produce unidirectionally aligned (UD) and unidirectionally plus randomly distributed (UD/RM) composite screws (P40 UD and P40 UD/RM). The maximum flexural and push-out properties for the composite screws (P40 UD and P40 UD/RM) increased by almost 100% in comparison with the PLA screws. While the pull-out strength and stiffness of the headless composite screws were ∼80% (strength) and ∼130% (stiffness) higher than for PLA, those with heads exhibited properties lower than those for PLA alone as a result of failure at the heads. An increase in the maximum shear load and stiffness for the composite screws (∼30% and ∼40%) in comparison to the PLA screws was also seen. Maximum torque for the PLA screws was ∼1000 mN m, while that for the composite screws were slightly lower. The SEM micrographs for P40 UD and P40 UD/RM screws revealed small gaps around the fibres, which were suggested to be due to buckling of the UD fibres during the manufacturing process.

Bioresorbable composite screws manufactured via forging process: pull-out, shear, flexural and degradation characteristics.

Bioresorbable screws have the potential to overcome some of the complications associated with metallic screws currently in use. Removal of metallic screws after bone has healed is a serious issue which can lead to refracture due to the presence of screw holes. Poly lactic acid (PLA), fully 40 mol% P(2)O(5) containing phosphate unidirectional (P40UD) and a mixture of UD and short chopped strand random fibre mats (P40 70%UD/30%RM) composite screws were prepared via forging composite bars. Water uptake and mass loss for the composite screws manufactured increased significantly to ∼1.25% (P=0.0002) and ∼1.1% (P<0.0001), respectively, after 42 days of immersion in PBS at 37 °C. The initial maximum flexural load for P40 UD/RM and P40 UD composite screws was ∼60% (P=0.0047) and ∼100% (P=0.0037) higher than for the PLA screws (∼190 N), whilst the shear load was slightly higher in comparison to PLA (∼2.2 kN). The initial pull-out strengths for the P40 UD/RM and PLA screws were similar whereas that for P40 UD screws was ∼75% higher (P=0.022). Mechanical properties for the composite screws decreased initially after 3 days of immersion and this reduction was ascribed to the degradation of the fibre/matrix interface. After 3 days interval the mechanical properties (flexural, shear and pull-out) maintained their integrity for the duration of the study (at 42 days). This property retention was attributed to the chemical durability of the fibres used and stability of the matrix properties during the degradation process. It was also deemed necessary to enhance the fibre/matrix interface via use of a coupling agent in order to maintain the initial mechanical properties acquired for the required period of time. Lastly, it is also suggested that the degrading reinforcement fibres may have the potential to buffer any acidic products released from the PLA matrix.

Bioactive calcium phosphate–based glasses and ceramics and their biomedical applications: A review:

An overview of the formation of calcium phosphate under in vitro environment on the surface of a range of bioactive materials (e.g. from silicate, borate, and phosphate glasses, glass-ceramics, bioceramics to metals) based on recent literature is presented in this review. The mechanism of bone-like calcium phosphate (i.e. hydroxyapatite) formation and the test protocols that are either already in use or currently being investigated for the evaluation of the bioactivity of biomaterials are discussed. This review also highlights the effect of chemical composition and surface charge of materials, types of medium (e.g. simulated body fluid, phosphate-buffered saline and cell culture medium) and test parameters on their bioactivity performance. Finally, a brief summary of the biomedical applications of these newly formed calcium phosphate (either in the form of amorphous or apatite) is presented.

In-situ polymerisation of fully bioresorbable polycaprolactone/phosphate glass fibre composites: in vitro degradation and mechanical properties

Fully bioresorbable composites have been investigated in order to replace metal implant plates used for hard tissue repair. Retention of the composite mechanical properties within a physiological environment has been shown to be significantly affected due to loss of the integrity of the fibre/matrix interface. This study investigated phosphate based glass fibre (PGF) reinforced polycaprolactone (PCL) composites with 20%, 35% and 50% fibre volume fractions (Vf) manufactured via an in-situ polymerisation (ISP) process and a conventional laminate stacking (LS) followed by compression moulding. Reinforcing efficiency between the LS and ISP manufacturing process was compared, and the ISP composites revealed significant improvements in mechanical properties when compared to LS composites. The degradation profiles and mechanical properties were monitored in phosphate buffered saline (PBS) at 37°C for 28 days. ISP composites revealed significantly less media uptake and mass loss (p<0.001) throughout the degradation period. The initial flexural properties of ISP composites were substantially higher (p<0.0001) than those of the LS composites, which showed that the ISP manufacturing process provided a significantly enhanced reinforcement effect than the LS process. During the degradation study, statistically higher flexural property retention profiles were also seen for the ISP composites compared to LS composites. SEM micrographs of fracture surfaces for the LS composites revealed dry fibre bundles and poor fibre dispersion with polymer rich zones, which indicated poor interfacial bonding, distribution and adhesion. In contrast, evenly distributed fibres without dry fibre bundles or polymer rich zones, were clearly observed for the ISP composite samples, which showed that a superior fibre/matrix interface was achieved with highly improved adhesion.