Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
com
Progress in Natural
Science
Materials International
Abstract
A novel poly-lactic acid (PLA) based biocomposite reinforced with unidirectional high-strength magnesium alloy (Mg-alloy) wires for bone
fracture fixation was fabricated by hot-compressing process. The macroscopical and microscopical impact behaviors of the biocomposite were
investigated using impact experiments and finite element method (FEM), respectively. The results indicated that the biocomposite had favorable
impact properties due to the plastic deformation behavior of Mg-alloy wires during impact process. While the content of Mg-alloy wires reached
20 vol%, the impact strength of the composite could achieve 93.4 kJ/m2, which is approximate 16 times larger than that of pure PLA fabricated
by the same process. According to FEM simulation results, the complete destruction life of the composites during impact process increased with
increasing volume fraction of Mg-alloy wires, indicating a high impact-bearing ability of the composite for bone fracture fixation.
Simultaneously, the energy absorbed by Mg-alloy wires in the composites had a corresponding increase. In addition, it denoted that the impact
properties of the composites are sensitive to the initial properties of the matrix material.
& 2014 Chinese Materials Research Society. Production and hosting by Elsevier B.V. All rights reserved.
Keywords: Impact property; Magnesium alloy wire; Poly-lactic acid; Composite; FEM
1. Introduction are still the strategies [5–10]. Recently, poly-lactic acid (PLA)
based bio-polymer attracted huge interests due to its biodegrada-
Impact loading against bone is a common phenomenon in tion, versatility and biocompatibility [11–16]. Unfortunately, the
day life, as it happens when we do running, jumping, weight impact properties of most investigated PLA were poor, and they
lifting, etc. Most of these impact loadings are beneficial for could not sufficiently meet the requirements of human bones.
maintaining bone mass and structure [1,2], while some power- Thereby, many researches tried to overcome this shortcoming
ful and incident impacts, however, could result in bone fracture [12–14]. A high-strength composite composed with poly-L-lactic
due to the limited impact resistance of bone and osteoporosis acid (PLLA) with high molecular weight as matrix and hydro-
according to the increase of age [3,4]. Then, orthopedic xylapatite (HA) as reinforcement was fabricated [13]. Its impact
immobilization is applied using bone fracture fixation devices. strength could reach 166 kJ/m2 when HA content is 30 wt%.
As the impact is unavoidable during healing, the impact Wan et al. [14] developed a unidirectional continuous carbon
properties of these devices, also concerned as the ability of fiber-reinforced PLA composite with an excellent tensile-resistant
resistance against an impact are significant. performance, but its impact strength was only 25 kJ/m2 with a
Most of traditional metallic materials for bone fracture fixation high content (40 vol%) of carbon fiber. Additionally, it should be
devices have excellent impact properties. However, the non- mentioned that most of these researches on the impact properties
degradation and probable toxic ions release from these materials are macroscopical, while the microscopical studies such as the
impact behavior of each component in the composite during the
n impact have not been analyzed quantitatively.
Corresponding author. Tel.: þ86 25 52090685.
E-mail address: clchu@seu.edu.cn (C. Chu). In this paper, a novel PLA-based biocomposite unidrection-
Peer review under responsibility of Chinese Materials Research Society. ally reinforced with high-strength magnesium alloy wires for
http://dx.doi.org/10.1016/j.pnsc.2014.08.003
1002-0071/& 2014 Chinese Materials Research Society. Production and hosting by Elsevier B.V. All rights reserved.
X. Li et al. / Progress in Natural Science: Materials International 24 (2014) 472–478 473
bone fracture fixation was fabricated. The macroscopical impact Mg-alloy wires were prepared, respectively and unreinforced
behavior of this composite was studied through experimental PLA underwent the same fabrication process was compared as
impact tests and fracture morphologies investigation, while the controls.
microscopical impact behavior was simulated by finite element
method (FEM). The aims of this work were to deeply under- 2.3. Characterization
stand the impact behaviors of the composite, and furthermore
provide scientific basis for the design of this composite. 2.3.1. Impact properties
Unnotched impact samples with a dimension of 60 mm 12
mm 2 mm, as shown in Fig. 1(a), were applied to evaluate
2. Materials and methods impact energy by ZBC impact testing machine. The impact
strength (σi) was calculated using the following equation:
2.1. Materials W
σi ¼ ; ð1Þ
bh
AZ31B magnesium alloy wires with a diameter of 0.3 mm
where W is the absorbed energy of the composite (J), b is the
were utilized in this research, which were fabricated through a
width of the sample (mm), and h is the thickness of the
continuous process including smelting, casting, hot-extrusion,
sample (mm).
wet-drawing and annealing.
PLA with a low viscosity-average molecular weight of
60,000 g/mol was purchased from Shenzhen Esun Industrial 2.3.2. Surface morphology
Co., Ltd., China. Its crystallinity, glass transition temperature A Philips XL30 FEG SEM was used to characterize the
and density was 38%, 64 1C and 1.24 g/cm3, respectively. fracture surface morphologies with an accelerating voltage of
The tensile properties of magnesium alloy (Mg-alloy) wires 22 kV. Before SEM, fracture surfaces of the samples were
and PLA are illustrated in Table 1 and Table 2. The wires have sputtered with a gold layer in an argon atmosphere.
an excellent deforming performance, as the value of its tensile
strain is as large as 16%, while their tensile strength is 2.4. Finite element method (FEM)
316 MPa. PLA exhibits an elastic deformation, as its tensile
strain and tensile strength is 1.15% and 46 MPa, respectively. Finite element method (FEM), also referred as finite element
analysis (FEA), was applied to stimulate the impact process.
The material parameters are illustrated in Tables 1 and 2, and
2.2. Fabrication of the composites
the impact model is depicted in Fig. 1(b). During simulation,
the impact head and supporters were regarded as the rigid body
The composites were fabricated with a lamina-stacked
with a density of 7.8 g/cm3, while beam and solid element type
method. First, thin composite laminas were produced through
was assigned for Mg-wires and PLA, respectively. A tension
pouring PLA/chloroform solution to overlay unidirectional
and shear-based failure criteria was applied for both Mg-alloy
Mg-alloy wires and subsequently evaporating in the air. Then
wires and PLA, while Lagrange multipliers were used for
several composite laminas were stacked symmetrically in a
interaction coupling [17]. Meanwhile, an hourglass control
mold cavity. Thereafter, hot-compression process was applied
method based on the formulation of Belytschko and Tsay [18]
to compress the stack under the condition of the temperature of
was utilized to inhibit hourglass modes and a mesh erosion
190 1C and the pressure of 5 MPa. Lastly, the samples were
technique was used to remove distorted elements. The initial
free cooled down to room temperature under the pressure
velocity of impact head was 5.24 m/s and the span was 40 mm,
of 5 MPa. Different composites with 5, 10 and 20 vol%
which were the same as that in practice.
Table 1
Tensile properties of Mg-alloy wires (ϕ 0.3 mm). 3. Results
Poisson Density Elastic Elastic Tensile Tensile
ratio (g/cm3) modulus strength strength strain (%) 3.1. Impact characterizations acquired by experimental tests
(GPa) (MPa) (MPa)
Fig. 2 shows the change of the impact strength of the
0.35 1.8 45 270 316 16
composites with the volume fraction of Mg-alloy wires.
Apparently, the impact strength increases significantly in
proportion to the volume fraction of Mg-alloy wires. The
Table 2 impact strength of pure-PLA was only 5.5 kJ/m2, while the
Tensile properties of poly-lactic acid (PLA).
impact strength of the composite with 5 vol% Mg-alloy wires
Poisson ratio Density Elastic Tensile Tensile was 17.8 kJ/m2, about twice larger than that of pure-PLA.
(g/cm3) modulus strength (MPa) strain (%) As the content of Mg-alloy wires increases, the impact strength
(GPa) of the composite further achieves 93.4 kJ/m2 at 20 vol%
Mg-alloy wires. This amazing increase sufficiently reflected
0.36 1.24 4.0 46 1.15
an excellent resistance ability of the composites against the
474 X. Li et al. / Progress in Natural Science: Materials International 24 (2014) 472–478
Fig. 1. Samples with different contents of Mg-alloy wires for impact tests (a) and their model for FEM (b).
Fig. 3. Impact fracture morphologies of the composites with different volume fraction of Mg-alloy wires: (a) 5 vol%, low magnification; (b) 5 vol%, high
magnification; (c) 10 vol%, low magnification; (d) 10 vol%, high magnification; (e) 20 vol%, low magnification; (f) 20 vol%, high magnification. (For interpretation
of the references to color in this figure legend, the reader is referred to the web version of this article.)
Table 3
Average internal energy per wire in the composites.
greater strain at failure than the fiber to obtain the maximum [9] M. Niinomi, Recent metallic materials for biomedical applications,
energy absorption from a particular fiber. Metall. Mater. Trans. A 33 (2002) 477–486.
[10] L.L. Tan, X.M. Yu, P. Wan, K. Yang, Biodegradable materials for bone
Apparently, the average energy of wires per volume could be
repairs: a review, J. Mater. Sci. Technol. 29 (2013) 503–513.
easily calculated, and the value was 5.19 106 J/m3 at 20 vol% [11] N.A. Weir, F.J. Buchanan, J.F. Orr, D.F. Farrar, A. Boyd, Processing,
Mg-alloy wires, while that was approximately 2.83 106 J/m3 annealing and sterilisation of poly-l-lactide, Biomaterials 25 (2004)
at 5 vol% and 10 vol% Mg-alloy wires. Accordingly, the average 3939–3949.
energy of PLA per volume was 7.7 104, 4.82 104, 6.32 [12] Y. Shikinami, M. Okuno, Bioresorbable devices made of forged
104 and 2.43 105 J/m3, corresponding to the content of composites of hydroxyapatite (HA) particles and poly L-lactide (PLLA).
Part II: Practical properties of miniscrews and miniplates, Biomaterials 22
Mg-alloy wires at 0, 5, 10 and 20 vol%, respectively. These (2001) 3197–3211.
changes explained the nonlinear change of impact strength of the [13] Y. Shikinami, M. Okuno, Bioresorbable devices made of forged
composites versus the content of Mg-alloy wires. In addition, composites of hydroxyapatite (HA) particles and poly-L-lactide (PLLA):
these values are much less than that of their toughness under Part I. Basic characteristics, Biomaterials 20 (1999) 859–877.
tension, indicating further improvement on the impact properties [14] Y.Z. Wan, Y.L. Wang, Z.R. Wang, F.G. Zhou, J.Y. Xin, C3D/PLA
composite—a promising material for osteosynthesis devices, J. Mater.
of the composites. Sci. Lett. 19 (2000) 1207–1210.
[15] R.M. Felfel, I. Ahmed, A.J. Parsons, P. Haque, G.S. Walker, C.D. Rudd,
5. Conclusion Investigation of crystallinity, molecular weight change, and mechanical
properties of PLA/PBG bioresorbable composites as bone fracture
fixation plates, J. Biomater. Appl. 26 (2012) 765–789.
Macroscopical and microscopical impact behaviors of the
[16] Z.K. Hong, P.B. Zhang, C.L. He, X.Y. Qiu, A.X. Liu, L. Chen,
novel magnesium alloy wires unidirectionally-reinforced PLA X.S. Chen, X.B. Jing, Nano-composite of poly(L-lactide) and surface
composites were investigated. The results indicate that this grafted hydroxyapatite: mechanical properties and biocompatibility,
kind of composites has an excellent versatility of impact Biomaterials 26 (2005) 6296–6304.
strength which could meet different requirements of bones, [17] U. Ralf, C.H. Matthias, H. Peter, Application of Lagrange multipliers for
while its great impact properties are attributed to the plastic coupled problems in fluid and structural interactions, Comput. Struct. 85
(2007) 796–809.
performance of the Mg-alloy wires during impact process. [18] T. Belytschko, JS-J Ong, W.K. Liu, J.M. Kennedy, Hourglass control in
FEM results show Mg-alloy wires are already the main impact linear and nonlinear problems, Comput. Meth. Appl. Mech. Eng. 43
bearing supporter of the composites at a relative low content of (1984) 251–276.
5 vol% Mg-alloy wires. Changes of the percentage of energy [19] E. Madenci, I. Guven, The Finite Element Method and Applications in
Engineering Using ANSYSs, Springer, 2007.
absorption of PLA matrix to the composite demonstrate that
[20] W. Schubert, M. Khanal, J. Tomas, Impact crushing of particle–particle
the initial mechanical properties of PLA play an important role compounds—experiment and simulation, Int. J. Miner. Process. 75
on the impact strength of the composites. Moreover, a long (2005) 41–52.
time needed for the complete destruction of the composites [21] H. Shiuh Chuan, L. Yu Cheng, The finite element analysis of composite
suggests these composites could provide a great impact- laminates and shell structures subjected to low velocity impact, Compos.
bearing ability for bone fracture fixation. Struct. 66 (2004) 277–285.
[22] T. Zeng, D.N. Fang, T.J. Lu, Dynamic crashing and impact energy
absorption of 3D braided composite tubes, Mater. Lett. 59 (2005)
References 1491–1496.
[23] Y.H. Wu, N. Li, Y. Cheng, Y.F. Zheng, Y. Han, In vitro study on
[1] C. Cassell, M. Benedict, B. Specker, Bone mineral density in elite 7- to biodegradable AZ31 magnesium alloy fibers reinforced PLGA composite,
9-yr-old female gymnasts and swimmers, Med. Sci. Sports Exerc. 28 J. Mater. Sci. Technol. 29 (2013) 545–550.
(1996) 1243–1246. [24] J. Suganuma, H. Alexander, Biological response of intramedullary bone
[2] P.C. Fehling, L. Alekel, J. Clasey, A. Rector, R.J. Stillman, A comparison to poly-L-lactic acid, J. Appl. Biomater. 4 (1993) 13–27.
of bone mineral densities among female athletes in impact loading and [25] M.S. Taylor, A.U. Daniels, K.P. Andriano, J. Heller, Six bioabsorbable
active loading sports, Bone 17 (1995) 205–210. polymers: in vitro acute toxicity of accumulated degradation products,
[3] H. Ari, K. Pekka, S. Harri, O. Pekka, P. Matti, R. Marjo, et al., J. Appl. Biomater. 5 (1994) 151–157.
Randomised controlled trial of effect of high-impact exercise on selected [26] D.C. John, B. Kevin, Z. Peter, The effects of ageing and changes in
risk factors for osteoporotic fractures, Lancet 348 (1996) 1343–1347. mineral content in degrading the toughness of human femora, J. Biomech.
[4] E.J. Bassey, S.J. Ramsdale, Increase in femoral bone density in young 29 (1996) 257–260.
women following high-impact exercise, Osteoporos. Int. 4 (1994) 72–75. [27] Z. Shiming, R. Guruswami, E.G. Dennis, An experimental investigation
[5] Y.F. Zheng, X.N. Gu, F. Witte, Biodegradable metals, Mater. Sci. Eng., of shock wave propagation in periodically layered composites, J. Mech.
R 77 (2014) 1–34. Phys. Solids 51 (2003) 245–265.
[6] O. Böstman, H. Pihlajamäki, Clinical biocompatibility of biodegradable [28] Y. Sugimura, P.G. Lim, C.F. Shih, S. Suresh, Fracture normal to a
orthopaedic implants for internal fixation: a review, Biomaterials 21 bimaterial interface: effects of plasticity on crack-tip shielding and
(2000) 2615–2621. amplification, Acta Metall. Mater. 43 (1995) 1157–1169.
[7] D.A. Puleo, W.W. Huh, Acute toxicity of metal ions in cultures of [29] A.T. Dibenedetto, M.R. Gurvich, Effect of friction between fiber and
osteogenic cells derived from bone marrow stromal cells, J. Appl. matrix on the fracture toughness of the composite interface, J. Mater. Sci.
Biomater. 6 (1995) 109–116. 33 (1998) 4239–4248.
[8] J.J. Jacobs, A.K. Skipor, L.M. Patterson, N.J. Hallab, W.G. Paprosky, [30] G.L. Farley, Effect of fiber and matrix maximum strain on the energy
J. Black, et al., Metal release in patients who have had a primary total hip absorption of composite materials, J. Compos. Mater. 20 (1986) 322–334.
arthroplasty. a prospective, controlled, longitudinal study, J. Bone Joint
Surg. 80 (1998) 1447–1458.