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Characterization of HAp Reinforced High Density Polyethylene Biocomposites

Arpan Kumar Mondal S. S Mahapatra arpannitrkl@gmail.com mahapatrass2003@yahoo.com National Institute of Technology Rourkela
Many implant materials has been made in the last three decades made of metal alloys and ceramics polymers. The main problem with the metallic bone implants is the stress shielding and bone regeneration. Polymeric bone implants may overcome these difficulties. This article presents the processing techniques and experimental results of the Hydroxyapatite (HAp)/High Density Poly Ethylene (HDPE) bio-composite by micro-injection molding route. Different mechanical properties like tensile, compressive, flexural, and Izod impact has been examined along with two body abrasive wear. The experimental result shows a good mechanical and tribological behavior. Keywords: Bio-composites, Hydroxyapatite, Wear, Micro-injection Molding

1. Introduction
The human bone can be considered as a composite material, being made up of a collagen fiber matrix stiffened by hydroxyapatite (Ca10 (PO4)6(OH) 2) crystals which consists 69% of the weight of the bone as reported by van Blitterswijk et. al. (1986). Although mechanical property of human cortical bone is very low (Youngs modulus of micro-specimens of cortical boneas measured by Rho et al. (1993) is 18.6 GPa.), but fractured bone is generally replaced by bio-inert bone implants like Ti-Al alloys, Co-Cr-Mo alloys etc. which have very high stiffness. Wolff (1986) in his study (Wolff's law) examined that the remodeling process in living bone are the mechanisms by which the internal architecture of the trabeculae undergoes adaptive changes, followed by secondary changes to the external cortical portion of the bone to changes in its mechanical load environment, perhaps becoming thicker as a result. It has been observed that the metallic fracture fixation devices and prosthetic limbs can alter the mechanical environment, resulting stress shielding phenomenon. Gefen (2002) explained stress shielding, a mechanical effect occurring in structures combining stiff with more exible materials. To overcome the combine effect of stress shielding and bone remodeling the ideal bone replacement material must have a modulus equal to that of bone. As metals are too stiff in addition to their biocompatibility problems, ceramics are too brittle, polymers are too weak and flexible in comparison to the human bone, composites of polymers and ceramic materials may give the desired mechanical and biological properties. Hydroxyapatite is a well-known ceramic material used in biomedical application mainly because of its excellent biocompatibility and bioactivity (Heimann 2002) to bond with the bone tissues. HDPE is generally used in joint replacement (cups of artificial hip joints). Moreover, HDPE parts can be fabricated easily using conventional plastic processing techniques as discussed by Wang (2003). After introduced by Bonefield et. al. (1981), the development of hydroxyapatite reinforced polymer composites have been improved gradually. These findings analyses the mechanical properties of HAp/HDPE bio-composites and suggest that HAp/HDPE bio-composites have the potential for use as a bone substitute material with load-bearing capability.

2. Materials and Methods

Raw Materials Hydroxyapatite (HAp) is prepared by mixing Calcium Hydroxide Ca(OH) 2, Ortho Phosphoric acid (H3PO4) and ammonia solution (NH4OH) through wet chemical precipitation route as described in elsewhere (Binnaz et. al., 2009; Salma et. al., 2010; Ferraz et al., 2004). Initially, ten grams of Calcium Hydroxide is weighted in a weighing machine (Mettler Toledo, 0.01 g accuracy). It is mixed with water about 40 times. The solution is stirred by a magnetic stirrer (Remi Equipments Pvt. Ltd.) at 50C to 60C for 3 to 4 hours. Then after, ortho-phosphoric acid is mixed with the solution at the rate of 30 drops/minute through a burette and continuously stirred but heat input to the solution is stopped. Care is taken to reach at pH value of the solution at 8 to 10. If pH value of the solution drops below the threshold values, ammonia solution may be added to increase the pH value. After 5 to 6 hours, magnetic stirrer is stopped and the mixer is keep for 12 hours at room temperature. Then, precipitations are collected using a

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filter paper. The HAp precipitations are dried at 80C in an oven and calcinated at 850 0Cfar below the decomposition temperature of HAP (~11000C) for eight hours to get rid of any organic material that might be left and to allow the transformation of amorphous phases to the crystalline structure. After calcination, the material was ground in a ceramic hand grinder to avoid any agglomeration. A commercial grade HDPE has been supplied by Haldia Petrochemicals Ltd. with adensityof 0.90. Composite Processing and Testing Sintered HAp powder with a density of 3.15g/cm 3 and mean particle size of 1.20m analyzed in XRD is produced. All the specimens were fabricated as per the ASTM testing standard for HAp/HDPE bio-composites. Compounding of HAp/HDPE composites were carried out in a DSM Xplore micro compounder (Figure 1 (a)) at a temperature of 1800C-2200C and rotor-speed of 40 rpm. Composites with various amounts of HAp (10, 20, 30, 40 vol. %) were prepared. The mixtures were then granulated and dried at 160C. The major micro-injection molding machine(Figure 1 (b)) parameters were; barrel temperature at different zones i.e zone 1, zone 2, zone 3, zone 4 were 180C, 1900C, 2000C, 220C accordingly, mold temperature 60C and injection pressure of 14 MPa. In case of wear testing specimens compression moulding techniques were used with mold temperature of 220 0C and a compression pressure of 20 MPa was applied.

Figure 1(a) DSM Xplore Micro Compounder

Figure 1(b) and Micro Injectiong Molding Machine

3. Results and Discussions

Scanning Electron Microscopy Composites with up to 40% by volume were successfully compounded and SEM images revealed good dispersion of HAp in the HDPE polymer matrix. SEM micrograph of the HAp/HDPE is shown in the Figure 2 which reveals the global dispersion of HAp in both the polymer matrix.

Figure 2 SEM Micrograph reveling Global Dispersion of the 40vol%HAp/HDPE Composite

Density and Void Fraction

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The theoretical density of composite materials in terms of weight fraction can easily be obtained as per the following equations given by Agarwal and Broutman (1990). ct = (1)

where, W and represent the weight fraction and density respectively. The suffix p, m and ct stand for the particulate, matrix and the composite materials respectively. The actual density ( ca) of the composite materials was evaluated by determining the test piece mass using Mettlertoledo weighing machine with the accuracy of 10 -3gm and its volume basing on the apparent mass loss by immersing in water. The volume fraction of voids (V v) in the composites is calculated using the following equation: Vv =
Table 1 Measured and Theoretical Densities of the Composites Composites 10 vol% HAp/HDPE 20 vol% HAp/HDPE 30 vol% HAp/HDPE 40 vol% HAp/HDPE Theoretical Density(gm/cm3) 1.125 1.35 1.575 1.80 Measured Density(gm/cm3) 1.114 1. 340 1.498 1.76 Volume fraction of voids (%) 0.97 0.74 4.88 1.66

(2)

It is clear from the Table 1 that void fraction of the 30 vol% HAp/HDPE bio-composite is much more (4.88%) than other volume fractions. Hence, it may affect the mechanical properties of HAp/HDPE bio-composites. Characterization of Mechanical Properties Tensile, compressive and flexural testsare carried out on Instron 3382 Universal Testing Machine at a temperature of 232Cwith relative humidity of 505RH. Testing procedures were carried out in ASTM D638 Type-1 for tensile testing, ASTM D695 for compressive, ASTM D790 for flexural test. Tinius Olsen high energy pendulum impact tester (Model IT406) for plastics has been used for izodimpact testing considering the ASTM D256 standard. For each composition tested, the average of four readings was presented for all type of the testing. Figure3shows the plot for tensile load/displacement indifferent HAp volume percent for the bio-composite developed. Notably, it can be seen that the HAp/HDPE composite materials exhibited both ductile and brittle behavior, depending on the amount of HAp incorporated into the HDPE polymer matrix. It can be seen that increasing the amount of HA resulted in the composite losing its ductility as seen from the composite brittle mode failure occurring in the elastic region.
1100 1000 900 800 700

(10 vol%) (20 vol%) (30 vol%) (40 vol%)

Youngs Modulus

600

Youngs Modulus

500

400

Load (N)

600 500 400 300 200 100 0 -100 0 5 10 15 20 25 30

300

200

100

0 5 10 15 20 25 30 35 40 45

Extension (mm)

HAp vol%%

Figure 3 Typical Load-extension Curves

Figure 4 Plot of Youngs Modulus versus HAp vol%

Figures 4 and 5 show variation of Youngs modulus and tensile strength with respect to amount of HAp of HAp/HDPE bio-composite respectively. It can be seen that the tensile properties of HAp/HDPE composites were dependent on the HAp content. In Figure 6, it is shown that the main fracture mechanism of the 30 vol% HAp/HDPE bio-composite occurred during tensile test suggesting poor interfacial interaction between HAp and HDPE and denotes a brittle type fracture.

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Hence, the drop in tensile strength with increasing HAp content is clearly evident. Comparing the Youngs modulus of the natural bone, it was found that the modulus of (10-40%) HAp/HDPE composite is less than the low to medium range of the natural bone modulus which ranges from 3 to 30 GPa as reported by Boneld et. al. (1998), which may not fulfill the requirement.
(Tensile Strength)
18

Tensile Strength(MPa)

16

14 0 10 20 30 40

(HAp vol%)

Figure 5 Effect of HAp Contents on the Tensile Strength

Figure 6 Fracture Mechanism of the 30vol%HAp/HDPE Biocomposite

90

15 14

Compressive Strength

Compressive Strength (MPa)

13 12 11 10 9 8 7 6 5 5 10 15 20 25 30 35 40 45
50 10 15 20 25 30 80

Shore D Hardness

Shore D Hardness

70

60

35

40

HAp vol%

HAp Vol%

Figure 7 Effect ofHAp Content on the Compressive Strength

Figure 8 Effect of HAp Content on Hardness

Effect of HAp reinforcement in the composite compressive strength plotted in the Figure7upto 20 vol% of HAp incorporation in the HDPE matrix shows an increase in compressive strength of the HAP/HDPE bio-composite, but a sharp fall can be seen in 30 and 40 vol% of HAp due to lack of global dispersion of Hap content in the 30 vol% composite but in case of 40 vol% due to uneven bonding among HAp and HDPE matrix and because of brittle nature of the HAp compressive strength decreases.
23
Interlaminar Shear Stress

22

Flexural Strength
Interlaminar Shear Stress (MPa)

1.0

Flexural Strength (MPa)

21

0.8

20

0.6

19

0.4

18

0.2

17
0.0 5 10 15 20 25 30 35 40 45

16 10 15 20 25 30 35 40

HAp(Vol%)

HAp(Vol%)

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Figure 9 Effect of HAp Content on Flexural Strength

Figure 10 Reinforcement Effect of HAp on ILSS

Shore-D hardness test has been carried out which prompts the hard and brittle nature of the HAp as a ceramic material. A plot between HApvol% and Shore-D hardness (Figure8) Shows 30 vol% HAp/HDPE composite have the maximum hardness. Flexural testing is carried out on aninstron 3382 universal testing machine system as per ASTM D790 standard at a rate of 0.77 mm/min. The loading arrangement is shown in the Figure11 the dimension of sample specimen is 3.2mm x 12.7mm x 125mm. The Flexural strength (FS) of the specimen is calculated as follows: FS = (3)

where, P is maximum load, b is width, t is the thickness and L is length of the specimen. The data recorded in the flexural test is also used to determine the inter-laminar shear stress (ILSS) values, calculated as follows. ILSS = (4)

(a)

(b)

(c)

(d)

(e)

Figure 11 Loading Arrangement of the (a) Flexural, (b) Tensile, (c) Impact, (d) Compressive and (e) Abrasion Wear Sample

The flexural properties are of great importance for any structural element. Bio-composite used in hip joints may fail in bending loads and therefore the development of new composites with improved flexural characteristics is very essential. From the results it may now be suggested that HAp/HDPE bio-composites to be used in bio-medical applications making high flexural strength bio-composites. The flexural strength of the HAp/HDPE bio-composites shows an approximately linier increase with the HApvol% (Figure 9).The inter-laminar shear strength values of the particulate filled bio-composites are shown along with the flexural strength. It can be seen (Figure 10) that with increase in filler content from 30 wt% to 40 wt% there is sharp drop in the inter-laminar shear strength. The stresses acting on the interface of two adjacent laminas are called inter-laminar shear stress. The stresses cause relative

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deformation between the lamina and if these are sufficiently high, they may cause failure along the common plane between the laminas. It is therefore, of considerable interest to evaluate inert-laminar shear strength through tests in which failure of laminates initiates in a shear (delaminating) mode.

44 42 40 38 36 34 32 30 28 26 10 15 20 25 30 35 40

0.016

(Resilience J/m)

Weight Loss in Two Body Abrasion Wear (gm)

(Waight Loss)

0.014 0.012 0.010 0.008 0.006 0.004 0.002 0.000 15 20 25 30 35 40 45

Resilience(J/m)

HAp vol%

HAp (Vol%)

Figure 12 Effect of Resilience with respect to HApvol%

Figure 13 Effect of HApvol% on Abrasion Wear

Tinius Olsen High Energy Impact System - IT406 Pendulum Impact Tester was used to do the pendulum type impact testing. ASTM D256is the standard used impact strength determination. It can be suggest from the Figure 12 that the 20 vol% HAp/HDPE bio-composite shows very high resilience. High strain rates or impact loads may be expected in bone structures in case of running or accidental conditions. The suitability of a bio-composite for such applications should therefore be determined not only by usual design parameters, but by its impact or energy absorbing properties. Thus, it is important to have a good understanding of the impact behavior of composites for both safe and efficient design of artificial bone structures and to develop new composites having good impact properties. The two body abrasion wear has been carried out in TABER industriesAbrasion Resistance Testeras shown in the Figure11 (e). Gingu O.et. al. (2010) studied that at the present time low back pain and cervical pain are a common health problem in patients aged above 40 years. So that vertebrae implants (partial or total) may be the solution. Two body abrasive wear test has been conducted considering the two body abrasion process in the vertebrae. It can be revealed from the Figure 13 that 20vol% HAp/HDPE composite gives the lowest weight loss.

4. Conclusions
A new bio-composite was developed with a high amount of HApupto 40 vol%. The biocomposite having 20 vol% HAp has shown the highest mechanical characteristics with having Tensile strength 18.7 MPa, Compressive strength 14.18 MPa, Youngs Modulus in tenion and compression are 543.64 MPa and 646.54 MPa accordingly. Flexural and Inter Laminar Shear Strength are 19.30 MPaand 1.07Mpa. Resieliance in the impact test was 46.81 J/m. During daily activities bones are subjected to a stress of approximately 4 MPa whereas RamakrishnaS. et. al. (2001) reported that the tendons and ligaments experience peak stresses in the range 40-80 MPa. The mean load on a hip joint is up to three times body weight and peak load during jumping can be as high as 10 times body weight. More importantly these stresses are repetitive and fluctuating depending on the activities such as standing, sitting, jogging, stretching, and climbing. Hence the HAp/HDPE composite developed may only fulfill the stress requirement in static portion of the body or in the low load region.

5. References
1. 2. 3. 4. Blitterswijk V., C.A., Grote, J.J., Kuijpers, W., Daems, W.T. and de Groot, K., (1986), A Quantitative and Qualitative Study on Hydroxylapatite Ceramic, Biomaterials, Vo1.7, p 137-143. Rho, J.Y., Ashman, R.B., Turner, C.H. (1993) Youngs modulus of trabecular and cortical bone material: ultrasonic and microtensile measurements, Journal of Biomechanics, Vol. 26(2), p 111-119. Wolff, J. (1986), The Law of Bone Remodeling. Berlin Heidelberg New York: Springer (translation of the German 1892 edition). Gefen, A. (2002). Computational simulations of stress shielding and bone resorption around existing and computer-designed orthopaedic screws, Medical and Biological Engineering and Computing, Vol. 40, p 311-322.

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5. 6. 7. 8. 9. 10.

11. 12. 13. 14.

Heimann, R.B. (2002), Materials Science of Crystalline Bioceramics: A Review of Basic Properties and Applications, Chiang Mai University Journal, Vol. 1(1), p 23-31. Wang, M. (2003), Developing bioactive composite materials for tissue replacement, Biomaterials, Vol. 24, p 2133-2151. Boneld, W., Grynpas, M.D., Tully, A.E., Bowman, J., and Abram, J. (1981), Hydroxyapatite reinforced polyethylene-a mechanically compatible implant material for bone replacement, Biomaterials, Vol. 2, p 185-186. Agarwal, B.D. and Broutman, L.J. (1990), Analysis and performance of fiber composites, Second edition, John Wiley & Sons, Inc, p. 216. Boneld, W., Wang, M., and Tanner, K. E. (1998), Interfaces in analogue biomaterials, Acta Materialia, Vol. 46, p 2509-2518. Gingu, O., Benga, G., Olei, A., Lupu, N., Rotaru, P., Tanasescu, S., Mangra, M., Ciupitu, I., Pascu, I., and Sima, G., Wear behaviour of ceramic biocomposites based on hydroxyapatite nanopowders, Proceedings of Institution of Mechanical Engineering, Part E, Journal of Process Mechanical Engineering, Vol. 225, p 62-71. Ramakrishna, S., Mayer, J., Wintermantel E, and Leong, K. (2001), Biomedical applications of polymercomposite materials: a review, Composites Science and Technology, Vol.61, p 1189-1224. Binnaz, A., and Koca, Y. (2009), Double step stirring: a novel method for precipitation of Nano-sized hydroxyapatite powder, Digest Journal of Nanomaterials and Biostructures, Vol. 4(1), p 73- 81. Salma, K., Berzina-Cimdina, L., and Borodajenko, N. (2010), Calcium phosphate bioceramics prepared from wet chemically precipitated powders, Processing and Application of Ceramics, Vol. 4(1), p 45-51. Ferraz, M.P., Monteiro, F.J., and Manuel, C.M. (2004), Hydroxyapatite nanoparticles: A review of preparation methodologies, Journal of Applied Biomaterials and Biomechanics, Vol.2, p 74-80.