Polymers - Bioactive Composites Obtained From Bioactive Glass Particles Into Poly (Methyl Methacrylate)

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Polymers - Bioactive Composites Obtained from Bioactive Glass Particles into Poly (Methyl Methacrylate)
Polymers
Print version ISSN 0104-1428
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Polymers vol.11 no.3 So Carlos July / Sept. 2001

http://dx.doi.org/10.1590/S0104-14282001000300009
TECHNICAL SCIENTIFIC ARTICLE
Bioactive Composites Obtained from Bioactive Glass Insertion into Poly (Methyl Methacrylate)
Paul E. Silva Junior, Rodrigo L. Orfice LEPCom, Department of Metallurgical and Materials Engineering, UFMG
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SUMMARY: Several bioceramics are capable of binding to the living tissues (bioactivity) however have mechanical properties quite different from those exhibited by natural tissue. This fact restricts the use of these materials in a more extensive number of biomedical applications. Polymer matrix composites reinforced with a bioactive phase can match the behavior characteristic of some bioactive bioceramics with mechanical properties close to human tissue. The present work aims to synthesize and characterize polymeric matrix composites reinforced by bioactive glass particles. The composites were produced from bulk polymerization of methyl methacrylate in the presence of bioactive glass particles (glass silicate of calcium, phosphorus and sodium). Glass particles were added to the monomer at various concentrations to allow variation of mechanical properties and bioactivity of the composites. The bioactivity of the materials was evaluated by tests in vitro carried out at 37 C in a simulated body fluid for periods of time from 0 hour to 30 days. Then, the composites submitted to tests in vitro have been characterized by infrared spectroscopy. The synthesis procedure was effective in producing composites with different volume fractions of particles homogeneously distributed through the material. The results of the tests in vitro revealed the deposition of a layer of carbonated hydroxyapatite (HCA) on the surface of the material, confirming the bioactivity of the composites. It was also observed that the kinetics of HCA layer can be controlled by the volume fraction of the bioactive. Keywords: composites, biomaterials, bioactivity, poly (methyl methacrylate), bioactive glasses.
Bioactive Composites Obtained from Bioactive Glass Particles into Poly (Methyl Methacrylate) ABSTRACT: Some bioceramics have the ability to bind to tissues but They show mechanical properties very different from the ones of natural tissues. This fact restricts the use of these materials in a wider range of applications. The goal of this research is to synthesize and Characterize polymer matrices reinforced with bioactive glass particles can combine que Potentially ability to bond to tissues (bioactivity), with mechanical properties comparable to damage tissues. The composites were produced by bulk polymerization of methyl
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methacrylate in the presence of bioactive glass particles and an initiator at 60 C. Bioactive glass particles were added to the monomer in several concentrations to modify the mechanical properties and bioactivity of the composites. The bioactivity of the materials was Evaluated by in vitro tests Performed at 37 C in the simulated body fluid for periods of time ranging from 1 hour to 30 days. The composites submitted to in vitro tests were Characterized by infrared spectroscopy. The results revealed the deposition of a Hydroxy-carbonate-apatite layer on the surface of the composites, confirming Their bioactivity. It was the que Also Observed fraction of the bioactive phase in the composites can be used to control the overall kinetics of the bioactivity process. Keywords: Composites, bioactive glasses, biomaterials, poly (methylmethacrylate), bioactivity.
Introduction
The introduction of biomaterials in the human body is one of the most common ways to restore or replace parts or all of nonwoven production, the result of trauma or tumors. A number of factors have encouraged the development of new biomaterials with better performance and new applications. Among these factors, it stands out: the poor performance of currently used materials that are designed to perform their functions for a maximum period of 10 years (with increasing average lifespan of the population, it becomes necessary to develop biomaterials properties upper and able to fulfill their activities for longer times [1,2] ); need to reduce the number of revision surgeries intended to replace damaged implants [1] , (in Brazil) need to meet a growing domestic demand the product and to reduce the cost of the materials involved, shortage of donors for transplantations. More than 50 different devices consisting of more than 40 different materials are currently used as a form of repair, replacement or aid to parts of the body. The choice of a material for use as a biomaterial necessarily involves the analysis of a set of requirements that must be met. Thus, a material capable of entering the class of biomaterials should exhibit properties consistent with the intended purpose of the implant (mechanical, in the case of the skeletal system, and optics in the case of intraocular lenses). In addition, the effect of environment on organic materials (corrosion, degradation) and the effect of the material in the body are phenomena that are to be studied carefully, because they are associated with so-called "biocompatibility". The interaction of the biomaterial with the live tissue associated with the type of organism's response to the presence of the material, is the most challenging development of biomaterials. The types of interaction between tissue and implant are fundamentally dependent on the type of material and can be assembled in the following groups [1] : toxic, nontoxic (often called bioinert), bioactive and biodegradable. More recently, the development of materials considered biodegradable and bioactive already been emphasized that in addition to replace traumatized tissues, these materials can also provide for the recovery of damaged tissue metabolism by acting on intracellular and extracellular responsible for cell reproduction and propagation in tissue growth. The bioactivity of materials has been described for calls initially bioceramics (hydroxyapatite, bioactive glass, etc.). [3] . The bioactivity was associated with the ability of materials to bind or adhere to living tissues. It should be noted that when the introduction of said inert material in the body, such as silicone, poly (methyl methacrylate), gold, platinum and others for the formation of a thin fibrous layer around the implant that prevents adhesion between the implant and the host tissue. However, obtaining this membership proves crucial for implants introduced in order to replace body parts that carry structural functions. Thus, we see the importance of the concept of bioactivity. This concept should be understood more generally as the ability of the material to interact with the living tissues to stimulate such chemical processes inherent in biological systems capable of allowing the integration of the biomaterial in the receiving environment. When a bioactive material is implanted in the human body, a series of biochemical and biophysical reactions occur in tissue-implant interface. These reactions result in a strong interfacial interaction associated with the formation of a carbonated hydroxyapatite layer (HCA) at the implant surface [3] . The bioactivity of the materials can be evaluated both in vivo as in vitro. assays in vitro are able to show some of the characteristic reactions of the bioactivity of materials. These tests are still important to study and establish the stages of the linkage mechanism between the living tissue and bioactive materials, which are described in Table 1 [2] .
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Bioceramics have a high degree of bioactivity. On the other hand, have mechanical properties in general need not suitable for the production of implants for structural purposes [4] . Ceramics are characterized by having low fracture toughness (such as bioactive glass have values of k C I less than 1 MPa.m 1/2 ) and high moduli of elasticity (Young's modulus of bioactive glasses is 80 GPa) when compared to the human cortical bone (elastic modulus ranges from 7-20 GPa) [3] that compromise the use and processing of such materials for biomedical applications. As a solution to the need for production of bioactive materials with mechanical properties more comparable to that of cortical bone tissue as might be provided by the production of bioactive composites involving phase (ceramic) and a second component. The aim of this work is related to the production of bioactive materials that present bioactive behavior typical of bioactive ceramics (binding capacity with fabrics) and also has mechanical properties comparable to tissue such as bone. As a way to reconcile these factors (bioactivity and mechanical properties), it is proposed here the preparation of polymer matrix composites reinforced by bioactive ceramic phases. In such case, ceramic phases would be responsible not only for reinforcing polymeric matrix, as usually occurs when the introduction of glass fibers into polymers, but also provide the bioactive characteristics desired. This work is part of a line of research aimed at the development of biomaterials able to elucidate inflammatory and immune responses controlled when in contact with living tissue.
Experimental
In the synthesis of composites were used the following reagents: methyl methacrylate (Aldrich Chemical Company, Inc.), poly (methyl methacrylate) (Metacril), benzoyl peroxide (VETEC Fine Chemicals Ltda.) (initiator) and bioactive glass particles . We used bioactive glass particles with an average size of 75 m I molar composition of 46.1% SiO 2 , 24.4% Na 2 O, 26.9% CaO and 2.6% P 2 The 5 . Bioactive glass was obtained via post merger, then this material has undergone rapid cooling, grinding and classification by granulometric sieves. In this work were synthesized composites with 0%, 10%, 20% and 50% by weight bioactive glass particles. Procedures Synthesis The methyl methacrylate was purified on a chromatography column filled with alumina. The introduction of poly (methyl methacrylate) monomer was performed in order to increase the viscosity thereof (25 wt%) so that the particles stay in suspension. To this mixture was added the initiator benzoyl peroxide (1% by weight of monomer) and glass particles. The mixture was stirred until complete homogenization and then poured into a mold made of two glass plates
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separated by an elastic hose. Finally, it took until the mold well sealed oven at about 60 C for twelve hours. To eliminate unpolymerized monomer residues, the samples were subjected to a final heat treatment at 130 C for about twenty minutes in an oven. The fracture surface of composites was investigated by Scanning Electron Microscopy. Samples containing polymer glass particles were fractured after cooling to cryogenic temperatures. The fracture surface was coated with Au-Pd alloy and then observed in a scanning electron microscope (JEOL). Tests in vitro In order to reveal the particles introduced, the sample surfaces were sanded with silicon carbide sandpaper (# 320, # 600). The samples were then cut in a mean size of 1 x 1 x 0.3 cm. The bioactivity of the composites was evaluated following a procedure commonly used for characterization in vitro of bioactive glasses. Previous studies in vivo [5] showed that the essential condition for a material to bond with the fabric is the formation of a layer of carbonated hydroxyapatite (HCA) in organic environment. The test in vitro constituted to introduce composites prepared with different concentrations of bioactive glass (0%, 10%, 20%, 50 mass%) in a simulated body fluid (SBF). The ion SBF has a composition similar to that of blood [6] . The tests were performed at 37 C for different periods of time ranging from 1 hour to 30 days. After the tests performed in vitro , the composites were characterized by diffuse reflectance spectroscopy for mid-infrared Fourier transform spectroscopy (FTIR). The FCS solution volume used in the bioactivity assay depends on the surface area of the sample. Previous studies [5] demonstrated that a relationship between surface area and volume of the sample solution PBS (SA / V) equal to 0.1 cm -1 is satisfactory deployment environments. The characterization of composites was performed by thermal analysis, diffuse reflectance spectroscopy by mid infrared spectroscopy and atomic absorption. Thermal analyzes by means of thermogravimetry (Shimadzu TGA50H) and Differential Scanning Calorimetry (Shimadzu DSC-50) evaluated the percentage respectively of particulate material inserted into the polymeric matrix and the glass transition temperature of the samples. Thermogravimetry the technique of samples weighing approximately 10 mg were placed in the machine and subjected to a temperature of 1000 C under a heating rate of 10 C / min and nitrogen. For scanning calorimetry analysis of samples weighing approximately 10 mg were placed in the equipment and heated to 250 C at a heating rate of 10 C / min. The spectroscopy of diffuse reflectance mid-infrared Fourier transform (Perkim-Elmer Paragon 1000) was chosen due to its ability to provide information for rough surfaces, and other particulates. The atomic absorption technique quantitatively evaluate changes in calcium ion concentration in the SBF solution as a function of test time in the test in vitro .
Results
The thermogram shown in Figure 1 to monitor the presence of waste in the TGA curves and correlation with the amount of residue content of the composite particles embedded. It is observed that the result of the batter after burning the polymer at temperatures above 600 C confirms the fractions of bioactive glass particles embedded in the composite (10%, 20% and 50%).
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DSC thermograms for pure PMMA and PMMA-composite bioactive glass particles of 20% by weight of particulate showed that the glass transition temperature of PMMA (about 105 C) is shifted to higher temperature 5 C with the addition of particulate material. It is known that a machine error is 3 C, demonstrating that the increase in Tg is significant. This result indicates that composite particles are introduced in modifying the viscoelastic behavior of the polymer matrix by introducing obstacles to free movement of the chains. Thus, there is a strong indication that the interfacial interactions are responsible for an increase of the relative viscosity of the polymer in regions near the interface. The presence of interfacial interactions predicts that medium to high levels of interfacial strength in the composite there are prepared. The Figure 2 shows a micrograph obtained by scanning electron microscopy of the fracture surface of the composite with 20 wt% of bioactive glass particles. The analysis of this surface allows to identify the presence of glass particles. Such particulate matter on the surface suggests, through an analysis of the morphology of the fracture surface, the interfacial strength between particles and matrix may be classified as intermediate in magnitude. Low interfacial resistances are generally identified by the absence of fracture surfaces of particles, which denotes the propagation of cracks through the interfacial region. Already high interfacial resistances are common to fracture surfaces characterized by the presence of polymeric films on particles. In the case of fracture surface analysis in the presence of particles with surface features revealed the existence of intermediate resistance levels between cases cited extremes (high and low interfacial resistance).
In Figure 3-a shows the FTIR spectrum of poly (methyl methacrylate) pure, which are observed absorption bands
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characteristic wave number of carbonyl groups (1706 cm -1 ) Methyl (2800 cm -1 ), CO (1100 cm - 1 ) of the polymer, among others. In Figures 3b , 3c and 3d , the spectra observed on the surface of the composites of 10%, 20% and 50% by mass of particles, respectively, prior to testing in vitro . The difference between the spectra of pure PMMA and composites revealed primarily in the regions of wave number characteristic of the SiO-Si (stretching, 1090 cm -1 ) SiOH (stretch, 950 cm 1 ) and SiO (bending, 400 cm -1 ) as shown in the spectrum in the upper left of Figure 3 , which was obtained by subtracting the spectra (a) and (d) of the same figure.
The results of the tests in vitro are shown in Figure 4 and 5 . In these figures, FTIR spectra were collected to analyze the surface transformation process which usually occurs during the introduction of bioactive materials in an environment body (or simulator environment body). The Figure 4 shows the FTIR spectra for all compositions investigated after twenty hours in vitro , while in Figure 5 , the spectra relating to the same compositions to Figure 4 , but after 30 days in vitro , are shown. Bioactivity is observed only in the composites of 50% by mass of particles in the periods from twenty hours and 30 days can be clearly seen that the bands of 1040, 600 and 560 cm -1 related to the formation of the HCA layer (PO linkages .) Composites with other compositions, the FTIR spectra obtained if spectra show very similar to the composites before the test in vitro , suggesting the lack of a uniform thick film and carbonated hydroxyapatite across the surface of the composite.
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The surface reactions that occur during the test in vitro can be followed through changes in ion concentration Ca 2 + present in the SBF solution used during the test. In Figure 6 shows the variation of the concentration of Ca 2 + in solution SBF as a function of testing time. This result, when combined with the FTIR spectra allows to analyze the bioactivity in vitro and identify the stages of reactions that culminate in the formation of the HCA layer, according to Table 1 .
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Discussion
The results shown in Figures 1 to 3 show the effectiveness allow the method used in the processing of composites in obtaining materials with compositions previously designed ( Figure 1 , TGA), a high degree of uniformity of particle distribution in the polymer matrix ( Figure 2 , SEM , and this result can be extended to other compositions since the methodology was the same) and indication of interfacial interactions (particle-polymer interface) median ( Figure 2 SEM). Furthermore, the information provided in Figures 4 , 5 and 6 are important for a more complete analysis of the bioactivity of these materials. Previous studies [5] have identified the existence of 5 stages of reactions occurring bioactive materials (as in bioactive glasses), which spontaneously arise in connection with living tissues, called fixation bioactive. These reactions produce a surface layer of carbonated hydroxyapatite in the implanted material which is recognized by biological entities as part of the body system. This bioreconhecimento promotes interaction and finally adhesion between these entities and the material surface (characterizing the bioactivity). In Figures 4-d and d-5 are shown the peaks relating to HCA formation of the composite particles with 50%, respectively after 20 hours, 30 days. Moreover, these bands spectra for the pure polymer are not identified, indicating the presence of a thick film HCA and evenly distributed throughout the material surface. The formation of this layer is not uniformly thick and HCA in samples with compositions poor particles up to 30 days, possibly reveals that are required longer times to testing. Thus, the kinetics of HCA depends on the composition of the composite. In addition, this result shows the possibility of manipulating the composite bioreatividade from the composite design variables such as the fraction of particles. Through quantitative chemical analysis of the calcium ion present in the solution SBF as a function of test time in vitro , it is possible to establish a connection with the stages of formation of the HCA layer. The concentration of Ca +2 was measured as a function of test time for pure PMMA for composites containing 10%, 20% and 50% by weight of particles. The pure PMMA by not showing any level of bioactivity due to the absence of this ion in its composition, has not provided any variation in the calcium concentration of the solution. The variations for the curve of the composite containing 10 wt% of the particles are within the range of measurement error is detected. In the curve for samples of 20% by weight of bioactive glass particles, we observed an increase in calcium concentration up to 3 days, this peak results from the migration of Ca +2 of the composite solution to SBF for the stages 1 and 2 ( Table 1 ). A mild reduction in the concentration of calcium in the solution after this time can mean the deposition of a layer of small thickness and HCA dispersed on the surface of the material which was not noticed by FTIR. The solution for the test in vitro , performed on the composite composition with 50 wt% of particles had a pronounced elevation of calcium concentration 20 hours, this being a result of the leaching process the calcium present in the composite structure for SBF (stages 1 and 2 - Table 1 ). At this point, the solution reaches
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saturation and the calcium concentration starts to fall, because the groups Ca +2 and PO 4 -3 solution migrate to the surface of biomaterials, forming an amorphous layer of CaP (stage 4). Finally, the incorporation of the anions OH - and CO 3 -2 leads to crystallization of the HCA layer (stage 5). The ratio between fraction of the components and the induction kinetics of precipitation of carbonated hydroxyapatite layer is associated with the time required for the occurrence of a supersaturated solution with the ion particles released by the system. Thus, the behavior in vitro of composites with small volume fraction of bioactive phase can thus be proposed: glass particles arranged on the surface of composites contribute to an almost immediate release of ions (Ca 2 + , Na + and PO 4 -3 ) present in a mobile structure for the SBF solution; increased concentration resulting from initial release is not sufficient to induce precipitation of HCA, with the passage of time, ions derived from the most distant particle surfaces are released into the solution through migration processes the interfaces of the composite, and finally the concentration of the SBF solution reaches super-saturation levels which may then lead to precipitation of the HCA layer. The presence of multiple surfaces composites may also explain the fact that composites containing 50% by weight of bioactive material were able to reproduce the behavior of pure bioactive materials, on the precipitation kinetics of HCA layer [6] . That is, both the composites with 50% by weight of bioactive glass particles as bioactive glasses induce precipitation of the HCA layer after the first 20 hours in contact with a simulated body environment. Since such composites have inherent greater facilities for processing (machinability, for example) and greater potential strength and fracture toughness than the pure own bioceramics, it is clear that the materials developed in this work have to be extremely interesting from the point of view of replace the bioceramics with gains in biomedical applications.
Conclusions
This study demonstrated the ability to produce bioactive glass-PMMA composite by bulk polymerization of methyl methacrylate in the presence of glass particles. The composites presented with good uniformity of particle distribution in the matrix and interfacial mechanical strength (particle-matrix) of intermediate to high magnitude, as suggested by DSC and SEM analysis. The composites obtained with 50 wt% of particles had bioactivity After twenty hours when subjected to tests in vitro in the simulated environment body solution at 37 C. This bioactivity was evidenced from the detection of the presence of a layer of carbonated hydroxyapatite on the surface of the composite. Thus, composites containing bioactive glass exhibit bioactivity in vitro characteristic of bioactive materials and controllable from the composition of the system. Such composites thus appear as potential candidates to replace with gains, bioceramics in biomedical applications.
Thanks
The authors thank FAPEMIG for the financial support to this project.
References
1. Hench, LL - The challenge of orthopedic materials. Current Orthopaedics , n. 14, p. 5-15 (2000). [ Links ] 2. Hench, LL, West JK - Bioactive Materials, Life Chem. Report. , 13, p. 187 (1996). [ Links ] 3. Hench, LL - Bioceramics: from concept to clinic, J. Am Ceram. Soc , 74, n.7, p.1487-1510 (1991). [ Links ] 4. Orfice, RL, Latorre, GP, West JK, Hench LL-Processing and Characterization of Bioactive Composites Polysulfone-Bioglass , Bioceramics 8 , p.400-414 (1995). [ Links ] 5. Latorre, GP, Hench, LL Analysis of bioactive glass interfacial reactions using Fourier Transform Infrared Reflection Spectroscopy. In: Characterization methods for the solid solution in ceramic interface systems, Ed ACS (1993). [ Links ] 6. Orfice, RL; Hench, LL, Brennan, AB - In vitro bioactivity of polymer matrices reinforced with a bioactive phase. J. Brazilian Chemical Society , vol. 11, n. 1, p. 78-87 (2000). [ Links ]
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Received: 03/23/01 Accepted: 27/09/01
Corresponding author: Rodrigo L. Orfice , LEPCom, Department of Metallurgical and Materials Engineering, UFMG, Rua Espirito Santo, 35/316, CEP: 30160-030, Belo Horizonte, MG. E-mail: rorefice@demet.ufmg.br
All the contents of this journal, except where otherwise noted, is licensed under a Creative Commons Attribution License
ABPol Rua So Paulo, 994 PO Box 490, So Carlos-SP Tel. / Fax: +55 16 3374-3949 revista@abpol.org.br
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Polymers - Bioactive Composites Obtained From Bioactive Glass Particles Into Poly (Methyl Methacrylate)

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8/1/13

Print version ISSN 0104-1428

Polymers vol.11 no.3 So Carlos July / Sept. 2001

TECHNICAL SCIENTIFIC ARTICLE

Received: 03/23/01 Accepted: 27/09/01

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