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Contains fulltext : 48424.pdf (Publisher’s version ) (Closed access) Polyurethanes based on poly(epsilon-caprolactone) (PCL) (750-2800 g/mol) and 1,4-butane diisocyanate (BDI) with different soft segment lengths and constant uniform hard segment length were synthesized in absence of catalysts for the production of a degradable meniscus scaffold. First the polyesterdiols were endcapped with BDI yielding a macrodiisocyanate with a minimal amount of side reactions and a functionality of 2.0. Subsequently, the macrodiisocyanates were extended with 1,4-butanediol in order to obtain the corresponding polyurethane. The polyurethanes had molecular weights between 78 and 160 kg/mol. Above molar masses of 1900 g/mol of the polyesterdiol crystalline PCL was found while the hard segment showed an increase in melting point from 78 to 122 degrees C with increasing hard segment content. It was estimated that the percentage crystallinity of the hard segment varied between 92 and 26%. The Young's modulus varied between 30 and 264 MPa, the strain at break varied between 870 and 1200% and tear strengths varied between 97 and 237 kJ/m2.

Commonly, spontaneous repair of lesions in the avascular zone of the knee meniscus does not occur. By implanting a porous polymer scaffold in a knee meniscus defect, the lesion is connected with the abundantly vascularized knee capsule and heating can be realized. Ingrowth of fibrovascular tissue and thus healing capacity depended on porosity, pore sizes and compression modulus of the implant, To study the lesion healing potential, two series of porous polyurethanes based on 50/50 epsilon-caprolactone/L-lactide with different porosities and pore sizes were implanted subcutaneously in rats. Also, in vitro degradation of the polymer was evaluated. The porous polymers with the higher porosity, more interconnected macropores, and interconnecting micropores of at least 30 mum showed complete ingrowth of tissue before degradation had started. In implants with the lower macro-porosity and micropores of 10-15 mum degradation of the polymer occurred before ingrowth was completed. Directly after implantation and later during degradation of the polymer, PMN cells infiltrated the implant. In between these phases the foreign body reaction remained restricted to macrophages and giant cells. We can conclude that both foams seemed not suited for implantation in meniscal reconstruction while either full ingrowth of tissue was not realized before polymer degradation started or the compression modulus was too low, Therefore, foams must be developed with a higher compression modulus and more connections with sufficient diameter between the macropores. (C) 2002 Elsevier Science Ltd. All rights reserved.

The cytotoxicity of poly(96L/4D-lactide) (PLA96), and of its accumulated degradation products, was investigated following different sterilization methods and pre-determined heat-accelerated degradation intervals. PLA96 samples sterilized by either steam, ethylene oxide, or gamma irradiation were left untreated (SO samples), or were degraded for 30 h or 60 h (S30 and S60 samples) at 90 degrees C in water. Extracts of the samples and of the remaining degradation fluids (F30 and F60) were prepared. The toxicity of both unfiltered and filtered extracts was analyzed in a cell growth inhibition (CGI) assay and a lactate dehydrogenase (LDH) leakage assay. Physical analysis of the extracted samples and of the degradation fluids also was performed. The S0 extracts demonstrated no significant CGI. The CGI of the S30 extracts ranged from 37 to 78%, whereas the CGI of the S60 extracts ranged from 6 to 33%. The CGI of the F30 extracts ranged from 19 to 38% and the CGI of the F60 extracts was 98 to 123%. The LDH leakage assay only showed a high response to the unfiltered F60 extracts. Neither sterilization nor filtration appeared to influence the cytotoxicity of the extracts. Particle accumulation, however, might affect cell membrane permeability resulting in LDH leakage. The results of this study suggest that the cytotoxicity of PLA96 is related to the pH and possibly the osmolarity of the tested extracts. The pH and osmolarity, in turn, may depend on variations in the amounts of solubilized lactic acid and oligomers. These variations appear to result from degradation stage-dependent differences in crystallinity, molecular weight and molecular weight distribution of the PLA96 samples. (C) 2000 Elsevier Science Ltd. All rights reserved.

Linear and star-shaped copolymers of trimethylene carbonat/epsilon-caprolactone were synthesized using different polyol initiators and catalysts. Unexpectedly, when dipentaerythritol was used as an initiator cross-linked rubbers were obtained, that swell in chlorofonn. This network formation can be understood by 'in situ' generation of cross-linker molecules from trimethylene carbonate and initiator tor. SEC analysis showed that with D-sorbitol star-shaped copolymers are synthesized with an average functionality between 4 and 6. These low molecular weight rubbers were used as a macro-initiator for the subsequent lactide/ glycolide polymerization. Star-shaped lactide/glycolide block copolymers with a poly[(trimethylene carbonate)co-(epsilon-caprolactone)] rubber core based on D-sorbitol show good mechanical properties. At relatively low rubber content ductile tensile behavior was observed indicating extensive toughening.

A new approach to the synthesis of biomedical polyurethanes based on epsilon-caprolactone and 1,4-butanediisocyanate with a high modulus, has been developed. By chain extending an epsilon-caprolactone prepolymer with a long uniform-size diisocyanate block, a segmented polyurethane with uniform-size hard segments was obtained. It shows excellent mechanical properties; an extremely high modulus of 105 MPa and a tensile strength of 35 MPa. The polymer is soluble at high concentrations in various volatile solvents such as chloroform and 1,4-dioxane. By a combination of salt-leaching and freeze-drying, porous materials have been obtained in which macropores ranging in size from 150-300 mu m are highly interconnected by micropores. The material shows a sufficiently high compression modulus of 200 kPa and appears to be suitable for biomedical applications such as meniscal prostheses. (C) 1998 Kluwer Academic Publishers.

The influence of morphology on the hydrolytic degradation behavior of poly(L-lactide) has been studied. High molecular weight and highly crystalline as-polymerized poly(L-lactide) was obtained in high yields through melt polymerization. Poly(L-lactide) fiber with a draw ratio of 5.6 was obtained by hot-drawing solution-spun fiber. During the bulk degradation of as-polymerized poly(L-lactide), a rapid decrease of molecular weight and tensile properties was observed. This could be explained by the morphology of the material and the presence of thermal stresses and subsequent generation of microcracks. The lamellar crystallites in as-polymerized poly(L-lactide) appeared to be very stable towards hydrolysis. The resorption time of high molecular weight as-polymerized poly(L-lactide) in vivo was estimated at 40-50 yr by extrapolation of molecular weight data. Hot-drawn poly(L-lactide) fiber showed exceptional hydrolytic stability under a static load and substantially retained its mechanical properties over a period of more than 5 yr. The high perfection of the crystalline fiber and the elimination of micro-voids obtained by hot-drawing prevented penetration of water and induced surface erosion of the fiber.

Surface oxidation of ultra-high molecular weight polyethylene (UHMWPE) powder has an influence on the mixing procedure of chopped fibres and UHMWPE powder. Due to this oxidation hydrogen bonds can be formed between the fibres and powder particles, leading to a more homogeneous fibre-powder mixture. This treatment improves the fibre-matrix interface and thus the physical properties of the composite. Chromic acid treatment also has an influence on the mechanical and tribological properties of the aramid-UHMWPE composite. Although only a relatively small improvement is observed in the modulus, yield stress and stress at break, of 33, 17 and 9%, respectively, a substantial enhancement in wear resistance of 117% is observed.

Polyurethanes based on a 50/50 copoly(L-lactide/epsilon-caprolactone) prepolymer and butanediisocyanate were made. Chain extending a diisocyanate terminated prepolymer with butanediamine was not possible due to the susceptibility of the lactide bond to aminolysis. Chain extension with butanediol resulted in a polymer with poor mechanical properties due to transesterification. When the copolymer prepolymer was chain-extended with an isocyanate terminated block, transesterification with the chain-extender was avoided and the mechanical properties were increased. When the length of the hard segments was increased the mechanical properties increased further. A L-lactide/epsilon-caprolactone based polyurethane with a tensile strength and modulus of respectively 45 MPa and 60 MPa was made. The polymer contained no poly(L-lactide) crystals and was easy to process. Compared to the high molecular weight 50/50 copoly(L-lactide/epsilon-caprolactone) the polyurethane showed better mechanical properties, is expected to have the same adhesive properties and is expected to have a slower degradation rate. These factors makes this polymer excessively useful for in-vivo tissue engineering in for instance meniscal reconstruction material, nerve guide and artificial skin.

New biomedical polyurethanes and a polyurethane urea based on epsilon-caprolactone and 1,4-butanediisocyanate have been developed. On degradation, only non-toxic products are produced. The polyurethane urea with poly(epsilon-caprolactone) soft segments and butanediisocyanate/butanediamine hard segments shows a high tensile strength, a high modulus and a high resistance to tearing but as a result of the strong interactions between the solvent and the polymer processing is difficult. When butanediamine is replaced by butanediol in the chain extension step, a processible polyurethane is obtained but the polymer lacks the desired mechanical properties for biomedical applications. By chain extending with a longer urethane diol block, a processible polymer was obtained with mechanical properties comparable to the polyurethane urea. This polyurethane has been made porous and can be used as a meniscal prosthesis.

Tensile testing of gel-spun hot-drawn ultra-high molecular weight polyethylene (UHMWPE) fibres reveal a ductile-brittle transition temperature. Ductile fracture above the transition temperature is believed to be initiated by a stress-induced orthorhombic-hexagonal phase transition, whereas at lower temperatures brittle fracture occurs in the orthorhombic phase. SEM micrographs of the fracture surfaces of UHMWPE fibres fractured below the transition temperature show fibrillar fracture and cannot be distinguished from fibres fractured in a ductile way above the transition temperature.

Blends of D,L-lactide/glycolide copolymers were synthesized and their properties and in vitro degradation behaviour were evaluated as a function of chain architecture and blend composition. Tensile and impact properties of the blends are hardly influenced by matrix composition and chain architecture, but predominantly vary with the amount of rubber. In vitro degradation showed that hydrolytic degradation is enhanced by the incorporation of glycolide into the poly(D,L-lactide) matrix. Surprisingly, blends based on 6-arm star-shaped poly(D,L-lactide-co-glycolide) retain their mechanical properties for a longer period than blends with linear matrices of comparable composition. Physical aging of the linear copolymers is more severe and faster than that of star-shaped copolymers. (C) 1997 Elsevier Science Ltd.

It has been previously shown that, when used for meniscal reconstruction, porous copoly(L-lactide/epsilon-caprolactone) implants enhanced healing of meniscal lesions owing to their excellent adhesive properties. However, it appeared that the materials had an insufficient compression modulus to accomplish 100% fibrocartilage formation. In addition, to be used for meniscal prosthesis, the compression modulus of the porous materials should be larger than 150 kPa in order to protect the articular cartilage. A technique was developed to prepare stiff porous materials of a high molecular weight 50/50 copoly(L-lactide/epsilon-caprolactone) suitable for fibrocartilage regeneration in meniscal implants and meniscal prosthesis. Porous microspheres (50-250 mu m) were agglutinated in the presence of NaCl crystals (250-300 mu m) The microspheres were mixed with solid solvent in order to obtain a homogeneous distribution of solvent over the spheres. By changing the amount of solvent and crystals, the density and the compression modulus could be varied over a range of 0.07 g ml(-1) to 0.5 g dl(-1) and 40-1100 kPa, respectively.

The aim of this study was to evaluate functional nerve recovery following reconstruction of a 1 cm gap in the sciatic nerve of a rat, using a new biodegradable p (DLLA-epsilon-CL) nerve guide. To evaluate both motor and sensory nerve recovery, walking track analysis and electrostimulation tests were carried out after implantation periods, ranging from 3 to 15 weeks post-operatively. The first signs of functional nerve recovery were observed after 3 weeks. After 15 weeks, 70% of the motor - and 90% of the sensory nerve function was re-established. Return of nerve function was better in comparison with results from other studies. This study demonstrated successful functional nerve recovery after the reconstruction of a 1 cm nerve gap with a biodegradable p(DLLA-epsilon-CL) nerve guide.

Lesions in the avascular part of 20 canine menisci were repaired by implantation of a porous polyurethane. Seven menisci were not repaired and served as controls. The repair tissue was characterized by biochemical and immunological analysis. The role of vascularity in healing was studied by perfusion of menisci with Indian ink. Histologically, repair tissue inside the implants initially consisted of fibrous tissue containing type I collagen. After 2 months, fibrocartilaginous tissue developed inside the implants, whereas control defects only showed repair with fibrous tissue. Both type I and type II collagen, the two major collagen types of normal meniscal fibrocartilage, could be detected in this newly formed fibrocartilage. The implant guided vascular tissue from the periphery towards the lesion resulting in healing of the tear. After fibrocartilage had formed, vascularity decreased and was completely absent in mature fibrocartilage. Control defects remained filled with vascular connective tissue. Two-thirds of the longitudinal lesions were found to be healed partially or completely. It is concluded that implantation of a porous polymer does enhance vascularity sufficiently to result in healing of meniscal lesions extending into the avascular part. Healing takes place by repair tissue strongly resembling normal meniscal fibrocartilage. (C) 1996 Elsevier Science Limited

Several methods of introducing crosslinks into poly(L-lactide) (PLLA) were studied. Electron beam irradiation was not effective in crosslinking PLLA, and, moreover, caused severe polymer degradation and embrittlement of the material. Peroxide crosslinking of PLLA with dicumyl peroxide (DCP), however, resulted in gelation. At high peroxide concentrations (13-25 wt%) and high curing temperatures (192 degrees C), a gel fraction equal to 1 could be determined gravimetrically. Peroxide crosslinking with DCP caused chemical modification of the PLLA polymer chain, with the decomposition products having a plasticizing effect on the resulting network. For the in situ crosslinking, a tetrafunctional monomer, 5,5'-bis(oxepane-2-one) (5,5'-BO), was synthesized and used in the copolymerization with epsilon-caprolactone and L-lactide. Differential scanning calorimetry (d.s.c.) and swelling experiments showed that network formation did take place. A pronounced difference in reactivity between the L-lactide and the 5,5'-BO crosslinker was observed, with this difference in reactivity being found to be comparable to the difference between L-lactide and epsilon-caprolactone. Swelling experiments carried out with crosslinked PLLA showed that incorporation of this crosslinker into the polymer network increased at higher polymerization temperatures and longer polymerization times. When 1 mol% of crosslinker was used in the copolymerization with L-lactide, a significant increase in the impact and tensile strength was obtained when compared to uncrosslinked PLLA. Copyright (C) 1996 Elsevier Science Ltd.

A porous polyurethane prosthesis was used to replace the lateral meniscus in the dog. After an initial ingrowth of fibrous tissue, the prostheses became filled with tissue strongly resembling normal meniscal fibrocartilage. Although less severe than seen after total meniscectomy, cartilage degeneration was frequent, possibly because tissue ingrowth in the prostheses occurred too slowly. Porous polymers can be useful for replacement of the meniscus, provided that chemical and physical properties are optimized. (C) 1996 Elsevier Science Limited.

The aim of this study was to compare the speed and quality of nerve regeneration after reconstruction using a biodegradable nerve guide or an autologous nerve graft. We evaluated nerve regeneration using light microscopy, transmission electron microscopy and morphometric analysis. Nerve regeneration across a short nerve gap, after reconstruction using a biodegradable nerve guide, is faster and qualitatively better, when compared with nerve reconstruction using an autologous nerve graft. Therefore, we conclude that in the case of a short nerve gap (1 cm), reconstruction should be carried out using a biodegradable nerve guide constructed of a copolymer of DL-lactide and epsilon-caprolactone. (C) 1997 Wiley-Liss, Inc.

In the past, porous materials made of an aromatic polyurethane (PU) were successfully used for meniscal reconstruction in dogs. Since aromatic PUs yield very toxic fragments upon degradation, a linear PU was synthesized by curing a poly(epsilon-caprolactone) and 1,4-trans-cyclohexane diisocyanate I based prepolymer with cyclohexanedimethanol. Porous materials of this polymer were also implanted for meniscal reconstruction. The results were comparable with the most successful implant series so far. Additionally, a porous meniscal prosthesis was developed to replace a total meniscus. Due to the very high shear stresses to which the prosthesis would be exposed, the stress hysteresis phenomenon linear PUs are known to exhibit could be of great consequence. Therefore an aliphatic PU network, synthesized by cross-linking poly(epsilon-caprolactone) and 1,4-trans-cyclohexane diisocyanate with glycerol, was used. Dislocation caused by tearing out of the sutures was found to be a problem because the tear resistance of the material was relatively low. In this study the tearing problem has been partly circumvented by using a complex suturing technique. Meniscal prostheses turned out to induce fibrocartilage upon implantation, and degeneration of articular cartilage was less severe than after meniscectomy.

The impact strength of amorphous lactide copolymers can be significantly improved by blending with biodegradable rubbers. Rubber toughening of amorphous poly(85L/15D-lactide) with the copolymer poly(50/50-trimethylenecarbonate-co-epsilon-caprolactone) results in a high-impact polymer (PDLLA/P(TMC-CL)). In vitro, the PDLLA/P(TMC-CL) blend retained its tensile and impact strength for a long period of time. Up to 45 weeks, the amount of water absorbed by the blend remained very low and no significant mass loss was observed. To test the suitability for fracture fixation, in a dog study mandibular fractures were fixated with PDLLA/P(TMC-GL) bone plates and screws. Bone healing was uneventful without premature failure of the implants. Although long-term degradation studies have to be carried out, PDLLA/P(TMC-CL) seems to be promising for application in fracture fixation.

In this study in vitro predegradation at elevated temperatures, used to obtain an increased degradation rate, was investigated. The in vitro degradation was followed by mass loss, molecular weight loss and changes in thermal properties. Two biodegradable polymers, the homopolymer PLLA and a copolymer PLA96 (96% L4 %D lactide), were hydrolytically degraded at 90 degrees C in a phosphate buffered solution. Both polymers, PLLA and PLA96, showed an initial linear degradation rate, but with longer implantation periods the degradation rate decreased and total degradation was best described as an asymptotic. Mass loss of the copolymer PLA96 was twice that of PLLA. The chemical analysis of the in vitro predegraded polymers coincided for both the decrease in molecular weight and the thermal properties with physiologically degraded poly(lactide). The results of this study show that although the degradation temperature is well above the glass transition temperature and not comparable to physiological temperatures, there seems to be good correlation between the in vitro degraded material and physiologically degraded material. In vitro predegradation enables investigation of the entire degradation process of a polymer in a short-term study. Moreover, in vitro predegradation allows direct comparison of the degradation rate of various polymers.

One of the ways to reconstruct a nerve defect is to use a biodegradable nerve guide. The aim of this study was to establish a nerve guide constructed of an amorphous copolymer of lactic acid-caprolactone. A pilot study was set up to elucidate the effect of the tube dimensions on nerve regeneration. Four types of nerve guides, with internal diameters ranging from 1.12-1.23 mm and wall thicknesses ranging from 0.34-0.68, were tested for this purpose. We evaluated the biodegradation, foreign body reaction and nerve regeneration by light microscopy, after three different implantation times (1, 2, and 3 months). After 2 months, we observed that all types of nerve guides had changed from a transparent to an opaque and swollen state, and that they had lost their strength. The foreign body reaction was characterized by the presence of giant cells and fibroblasts surrounding the degrading nerve guide. From this pilot study, we conclude that nerve guide type 1, with an internal diameter of 1.23 mm and a wall thickness of 0.34 mm, can ensure nerve regeneration in the case of a 1-cm gap in the sciatic nerve of the rat. Nerve guides types 3 and 4, with relatively small lumens, show nerve compression due to a more pronounced swelling of the degrading tube. (C) 1995 John Wiley & Sons, Inc.

In this study, reinforced poly(l-lactic acid) (PLLA) fibers made by a dry-spinning/hot-drawing process were evaluated for use as a suture, The initial tensile strength of the PLLA fibers was lower than the initial tensile strength of the commercially available sutures: PDS, VicrylTM silk, and EthilonTM. However, after 12 weeks immersion in a phosphate saline buffer at 37 degrees C, PDS sutures have lower tensile strength than PLLA sutures and the tensile strength of VicrylTM was unmeasurable because of fragmentation, Initially, PLLA fibers disintegrated into fibrils during degradation triggering an inflammatory response comparable to degradable multifilament sutures, However, the intensity of the inflammatory response against the PLLA fibers decreased and after 80 weeks implantation in the muscle layer of the abdominal wall of rats it was comparable to the one against EthilonTM. The inflammatory response against EthilonTM, which is considered to be nondegradable, increased in the same period, probably due to the change in shape, In practice, the handling characteristics of PLLA sutures are superior to the monofilament sutures like PDS and EthilonTM and comparable with the multifilament sutures like VicrylTM and silk, The knot security of PLLA sutures are expected to be better than the knot security of the monofilament sutures, but this remains to be investigated. It is concluded that dry-spun/hot-drawn (reinforced) PLLA fibers have the potential for use as longterm degradable suture material. (C) 1995 John Wiley and Sons, Inc.

In microvenous prosthetic surgery a continuous search for better patency rates is necessary to enable a clinical application, In this search for better patencies, modifications in the wall structure are being made. Directions found in the literature suggest that pore size plays an important role in achieving better patencies. Thus far, no study has been conducted to evaluate the influence of pore size on the patency rate of polyurethane microvenous prostheses. Since polyurethane is known to yield good patency rates, we conducted this study in which we compared different luminal pore sizes with regard to patency. Pore size varied from 0.6 to 20 mu m in microvenous polyurethane-based prostheses (length 5-6 mm, internal diameter 1 mm). The results showed a favorable patency rate in the pore sizes larger than 5.0 mu m (patency 75%) when compared to pore sizes smaller than 2.0 mu m (patency 50%). This study demonstrates that microvenous polyurethane-based prostheses with a luminal pore size larger than 5.0 mu m may yield better patency rates than prostheses with a luminal pore size smaller than 5.0 mu m. Further studies are currently being performed to elucidate the very reasons for this effect. (C) 1995 Wiley-Liss, Inc.

The observed brittle fracture behavior of amorphous polylactides seems to be contradicted by the low value of C(infinity) = 2 determined for poly(L-lactide) by Flory and coworkers. Such very flexible polymer chains deform by shear yielding, and fracture in a ductile manner. In this study, C(infinity) was estimated in a number of ways, resulting in much higher values of C(infinity) = 11.7 and C(infinity) = 9.1 for poly(L-lactide) and L- and D-lactide copolymers, respectively. These high values of C(infinity) and the low entanglement density account for the brittle fracture behavior of amorphous poly(lactide), as well as for the maximum attainable draw ratios of poly(L-lactide) networks and melt spun fibers. Bulk polymerized poly(L-lactide) networks, where crystallization during polymerization impedes severe entangling, could be hot-drawn most effectively to draw ratios of 8-16, resulting in very strong materials with tensile strengths of 550-805 MPa. By comparison, amorphous, non-crystallizable L/D lactide networks, which do not crystallize during polymerization, could be drawn less, to lambda = 7. These materials with strengths up to 460 MPa could, nevertheless, be oriented much more effectively than linear, amorphous L/D lactide copolymers.

In this study, the effect of chemical crosslinking on the creep behavior of high-strength fibers, obtained by gel-spinning and subsequent hot-drawing of ultra-high molecular weight polyethylene (UHMWPE), is examined. In the first part of the paper, the general aspects of the creep behavior of these fibers are discussed. The second part deals with UHMWPE fibers that are crosslinked by means of a) chlorosulfonation and b) dicumyl peroxide treatment followed by UV irradiation. The latter technique leads to an improvement of the creep resistance of the UHMWPE fibers without affecting their high tensile strengths. In spite of the fact that the network formation is fairly high, the creep cannot be completely removed. The results indicate that the creep process in UHMWPE fibers is associated with a deformation mechanism in the crystalline regions of the fiber, which are not affected by chemical crosslinking.

Copolymers of L-lactide(a)) with D-Lactide(a)), glycolide(b)), epsilon-caprolactone and trimethylene carbonate, and networks with spiro-bis-dimethylene-carbonate (2,4,7,9-tetraoxaspiro[5.5]undecane-3,8-dione) were prepared in bulk at standardized polymerization conditions. The properties of the nascent copolymers were evaluated with respect to the nature of the comonomer. Copolymerization with comonomers entailing low glass transition temperature simultaneously reduces the crystallinity. 300 MHz H-1 nuclear magnetic resonance is shown to be a useful technique for the determination of the average monomer sequence lengths in epsilon-caprolactone and trimethylene carbonate copolymers. The presence of crystallizable L-lactide sequences, due to differences in monomer reactivity, has a large effect on the thermal properties of the copolymer as well as on the long-term degradation characteristics.

The effect of copolymerization of L-lactide with several lactones and cyclic carbonates and the processing variables in compression moulding of poly(L-lactide) homopolymers on the mechanical properties was investigated. Sharp maxima in the impact strength versus comonomer composition and heat of fusion were obtained, reflecting the important role of the presence of a crystalline fraction in the material. Crystalline domains increase the interconnectivity of a physical polylactide network and decrease the molecular weight between these physical crosslinks. The brittle strength concomitantly increases, and as the yield stress remains more or less constant, an increase in impact strength is observed. Very high crystalline as-polymerized poly(L-lactide) prepared with less active catalysts on the other hand has an extremely low entanglement density and therefore a low brittle tensile strength.

The results of an experimental study of the effects of fibre diameter and testing length on the strength of polyethylene fibres prepared by the gel-spinning-hot-drawing process are reported. These size effects have been studied in fibres covering a range of mechanical properties in order to establish how size effects are related to fibre structure. It was found that both types of size effect studied are present in polyethylene fibres, and that the magnitude of both changes with increasing modulus of elasticity of the fibre; length effects become weaker and disappear completely, whereas diameter effects become more pronounced as the fibre modulus increases. This behaviour shows that transverse and longitudinal size effects cannot be described simultaneously within the framework of statistical strength theory. A model is proposed, based on the well known Griffith approach, which shows that a strength-diameter dependence may arise owing to geometrical effects rather than from the presence of flaws and imperfections.

High molecular weight as-polymerized poly(l-lactide) (PLLA) has been successfully used for fracture fixation and orbital floor reconstruction in animals and humans. As this PLLA takes more than 3 years to resorb, a method was developed to obtain insight into the final cellular degradation process of the PLLA by means of short-lasting animal experiments. Pre-degraded PLLA particles (

In the continuous drawing of gel-spun UHMWPE fibres, the diameter of the undrawn fibre appears to have a pronounced effect on its drawing behaviour and on the mechanical properties of the resulting hot-drawn fibres. A highly oriented structure is developed more efficiently upon drawing of thinner fibres, which may be attributed to differences in the deformation mechanism between as-spun fibres of various diameters. By drawing of thin fibres, UHMWPE filaments having a strength of 6.0 GPa and a Young's modulus of 222 GPa can be obtained at a relatively low draw ratio of lambda=70.

Absorbable fibres have been prepared from various copolymers Of L-lactide with either D-lactide or epsilon-caprolactone. The lower crystallinity of these copolymers, compared with the homopolymer, is desirable in the light of their potential use as an absorbable suture material and has a pronounced effect on both preparation procedure and mechanical properties of these fibres. Due to the low crystallinity of the fibres, their mechanical properties are related to the structure of the amorphous phase, as is reflected by the effect of the glass transition temperature and molecular weight on tensile properties. By means of a dry spinning/hot drawing process, low crystalline fibres having strengths of 1 GPa could be prepared, whereas fibres prepared by melt spinning/hot drawing have strengths ranging from 0.19 for a completely amorphous copolymer to 0.53 GPa for the poly(L-lactide) homopolymer.

Poly(L-lactide) and other poly(lactones) can be crosslinked by ring opening polymerization of the corresponding cyclic esters in the presence of a tetrafunctional bicyclic biscarbonate. Spiro-bis-dimethylene-carbonate was synthesized from pentaerythritol and diethylene-carbonate and used to prepare polyester networks for use in biomedical applications. Bulk copolymerization Of L-lactide with only small amounts of this crosslinker leads to networks with very high gel percentages of up to 100%. The initial crystallinity of these crosslinked poly(L-lactides), as well as the melting temperature, is very much reduced when compared with the homo poly(L-lactide). The degradation of the polymer in vivo is therefore expected to be enhanced and more benign at longer durations. Tensile strength and impact resistance are also greatly influenced by copolymerization with spiro-bis-dimethylene-carbonate. Much tougher and stronger materials can be obtained in this way. These favourable properties allow the material to be used in the preparation of degradable implants such as fracture fixation devices.

The kinetics of the L-lactide bulk polymerization was studied using tin(II) bis(2-ethylhexanoate) and zinc bis(2,2-dimethyl-3,5-heptanedionato-O,O'). Up to 80% conversion, the rate of polymerization using tin(II) bis(2-ethylhexanoate) is higher than that with the zinc-containing catalyst, while at conversions beyond 80%, the latter catalyst has the higher rate of polymerization. Crystallization of the newly formed polymer has an accelerating effect on the polymerization. The difference in the rate of polymerization at high conversions for the two catalysts is caused by a difference in crystallinity of the newly formed polymer. Contaminants in the catalyst and monomer are the true initiators in these L-lactide polymerizations. Initiation as well as polymerization proceeds through a Lewis acid catalyzed transesterification reaction between an activated lactone and a hydroxyl group.

As-polymerized poly(L-lactide), (PLLA), has a much higher impact strength than after compression moulding. Several routes have been explored to further increase the impact strength of nascent PLLA. First results on the preparation of composites with carbon fibres, the copolymerization with trimethylene carbonate and epsilon-caprolactone, the block copolymerization with rubbers and the plasticization with ethyl acetate indicate possibilities to prepare much more impact resistant as-polymerized PLLA materials.

Longitudinal lesions in the avascular part of the dog's meniscus were repaired by implantation of a porous polyurethane. Ingrowing repair tissue was characterized by biochemical and immunological analysis. Histologically, repair tissue initially was composed of fibrous tissue containing type I collagen. After 3 months, fibrocartilaginous tissue developed inside the implants, whereas control defects only showed fibrous repair tissue. Both type I and II collagen, the major collagen types of normal meniscal fibrocartilage, could be detected in this newly formed fibrocartilage. It is concluded that fibrocartilage resembling normal meniscal tissue is formed and that longitudinal lesions can be healed after meniscal repair by implantation of a porous polymer.

Full-thickness defects of articular cartilage were repaired by implantation of porous polymer implants in rabbits and dogs. The quality of the repair tissue was determined by collagen typing with antibodies. Implants with varying pore sizes and chemical composition were used. The effect of loading and motion was determined by inserting implants higher than, level with and lower than the surrounding cartilage. It appeared that healing took place by formation of fibrocartilaginous repair tissue containing both type I and type II collagen. Hyaline cartilage was observed in a minority of the rabbits used but not in the dog. Fibrocartilage formation in the dog was simulated by implantation of a porous polymer. Chemical composition of the polymer did not alter the results, neither did loading of the implant. It is concluded that the formation of fibrocartilaginous repair cartilage is stimulated by implantation of a porous polymer. This tissue seemed to function adequately in the dog but did show signs of degeneration in the rabbit.

Artificial meniscal lesions extending into the avascular part of the meniscus, which do not heal by any other means, were repaired by suturing either a porous polymer implant or a synovial flap into the defect. The implant guided the ingrowth of vascular repair tissue into the defect. This fibrous tissue later on transformed into fibrocartilage. Reconstruction with a synovial flap was not successful. It appeared that healing can be achieved by implantation of a porous polymer implant in a large number of cases. Future research will be aiming at improvement of the results of meniscal repair and application of this type of polymer for repair of cartilage defects.

The influence of tensile deformation on gel-spun and hot-drawn ultrahigh molecular weight polyethylene fibers has been investigated. In high modulus polyethylene fibers no deformation energy is used to break chemical bonds during deformation, and flow is predominantly present next to elastic behavior. Flow is reversible after tensile deformation to small strains, but becomes irreversible when yielding occurs. Stress relaxation experiments were used to determine the elastic and flow contribution to tensile deformation. A simple quantitative relation could then be derived for the stress-strain curve that directly links yield stress to modulus. Experimental stress-strain curves could be reasonably described by this relation. Flow during tensile deformation is shown to be correlated with the introduction of the hexagonal phase in crystalline domains. A mechanism of flow is proposed in which, at first, tie molecules or intercrystalline bridges are pulled out of crystalline blocks (reversible), followed by the break-up of crystalline blocks through slip of microfibrils past each other (stress-induced melting, irreversible).

The large difference in reactivity of L-lactide and epsilon-caprolactone in ring opening polymerization with stannous octoate, leads to the formation of copolymers with blocky structures. By varying the polymerization temperature, copolymers with different average sequence lengths and molecular weights can be synthesized. It is shown that the average monomer sequence length has a large effect on the thermal and mechanical properties of these copolymers.

High-strength and high-modulus poly(p-xylylene) (PPX) fibers show no creep at room temperature and retain at 200-degrees-C, in air or in nitrogen atmosphere, still 50 to 60 % of their tensile strengths at room temperature, whereas the modulus does not change. In stress relaxation experiments PPX fibers have relaxed after 17.4 hours less than 4 % of the initial stress whereas during the same period of time polyethylene fibers relax over 75 % of the initial stress.

The mechanical properties of amorphous carbon fibers, derived from linear low density polyethylene strongly depend on the fibre diameter, which may be attributed to the presence of a skin/core structure in these fibres. High strength carbon fibres could thus be prepared by using thin precursor filaments, that are obtained by a melt-spinning process, in which the spinline is stretched at an elevated surrounding temperature. Careful carbonization of these precursors gives carbon fibres with a strength of 2.16 GPa, a modulus of 130 GPa and a high strain at break of 3%.

High molecular weight copolymers of L-lactide and epsilon-caprolactone have been synthesized by ring opening copolymerization with stannous octoate as catalyst. The good mechanical properties of the 50/50 copolymers make it a suitable material for biomedical applications such as nerve guides etc., where degradation of the elastomeric implant is required. In contrast to the frequently used MDI containing polyurethanes, degradation products of the P(LLA-epsilon-CL) are non toxic. The use of such a material is therefore preferable.

Samples of high-molecular-weight poly (L-lactide) (PLLA) (MBAR(v) = 9.0 x 10(5)), a biomaterial developed for plates and screws used in internal fixation of jaw fractures, were implanted subcutaneously in the backs of rats to study tissue reaction to PLLA and to follow the degradation process. The PLLA seemed to follow the degradation pattern typical of biodegradable polyesters. After pure hydrolysis up to about 104 wk, phagocytic activity of macrophages was found at about 143 wk. Full resorption of PLLA was not demonstrated in this study. Except for the early and final parts of the implant period, no acute or chronic inflammatory reaction was observed. No implant was rejected. It is estimated that more than 3 yr will be required for total resorption of PLLA. For bone-healing this long period is of no practical importance. There is no need for removal of PLLA after fracture healing as is the case with metal fixation devices. Thus, PLLA has potential application in internal fixation of fractures and osteotomies in the maxillofacial region and other fractures that are not too heavily loaded in the human body.

Several series of porous, biodegradable PU/PLLA foams were used for meniscus reconstruction in dogs. PLLA-fiber reinforced PU/PLLA composites, PU/PLLA, and PU foams were implanted in severe meniscus lesions. The healing process was initiated as a result of blood vessels' and other cells' ingrowth into these porous materials. To accomplish good ingrowth of fibrocartilaginous tissue, the materials should have interconnected macropores of 200-300-mu-m with a high total pore volume. PLLA fibers were used to reinforce the materials, but seem to retard the degradation process and the ingrowth of fibrocartilaginous tissue.

Porous biodegradable poly(urethanes) for reconstructing menisci have been prepared using two different combinations of techniques: freeze-drying/salt-leaching and in-situ polymerization/salt-leaching. Using these methods, homogenous porous materials with a controllable and reproducible morphology can be prepared. The materials were made of three different poly(urethanes): a methylenediphenyldiisocyanate-based polyurethane, a lysine diisocyanate-based poly(urethane), and a poly(epsilon-caprolactone)-based poly(urethane). The compressive stress-strain behavior of the Estane foams was determined. Foams made by the freeze-drying/salt-leaching technique implanted in dogs showed healing and good ingrowth of fibrocartilaginous tissue.

Metallic bone plates have been shown to affect radiation in vitro. Although no damage has ever been demonstrated in vivo these plates may cause dose enhancements and shielding of the adjacent tissue. Resorbable high molecular weight as-polymerized poly(L-lactide) (PLLA) bone plates have recently been used for reconstruction in the maxillofacial area. To determine their influence on dose distribution, a 4-hole bone plate and screws of PLLA were exposed to electron and photon beams. A tissue-equivalent phantom of perspex was irradiated and measurements were made with LiF thermoluminescent dosimeters. No significant changes in dose deviations could be determined when the dose distribution in the homogeneous phantom was compared with that of the phantom in which the PLLA material was placed. From this study it can be concluded that the PLLA material can be regarded as tissue-equivalent and can, thus, be safely used for fracture fixation of bone fragments when postoperative irradiation is anticipated.