Xử lý UHMWPE và nanocomposite HA/UHMWPE cho ứng dụng y sinh - Luận án tiến sĩ

PROCESSING OF UHMWPE AND HA/UHMWPE NANOCOMPOSITE FOR BIOMEDICAL APPLICATIONS by FANG Liming A Thesis Submitted to The Hong Kong University of Science and Technology in Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy in Department of Mechanical Engineering August, Hong Kong UMI Number: 3239484 INFORMATION TO USERS The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photographs, print bleed-through, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion.

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Box 1346 Ann Arbor, MI 48106-1346 Authorization I hereby declare that I am the sole author of the thesis. I authorize the Hong Kong University of Science and Technology to lend this thesis to other institutions or individuals for the purpose of scholarly research. I further authorize the Hong Kong University of Science and Technology to reproduce the thesis by photocopying or by other means, in total or in part, at the request of other institutions or individuals for the purpose of scholarly research. Fang Liming FANG Liming Department of Mechanical Engineering August 28, 2006 ii PROCESSING OF UHMWPE AND HA/UHMWPE NANOCOMPOSITE FOR BIOMEDICAL APPLICATIONS by FANG Liming This is to certify that I have examined the above PhD thesis and have found that it is complete and satisfactory in all respects, and that any and all revisions required by the thesis examination committee have been made.

Z Professor LENG Yang, Department of Mechanical Engineering Professor GAO tế, Department of Chemical Engineering Z Head, Professor YU Tongxi, Department of Mechanical Engineering Department of Mechanical Engineering August 30, 2006 iil Acknowledgements First of all, I am most grateful to my supervisors, Prof. LENG Yang and Prof. LENG introduced me to the fantastic world of biomaterials and helped me to build my own interest in biomaterials. GAO’s critical and constructive comments and her urge for excellent work was a great driving force for me to work hard.

Without her excellent contributions, this thesis would not have been possible. WANG Min, Prof. KIM Jang-Kyo, Prof. SUN Qingping, and Prof.

GAO Furong for participating in the committee of this thesis. I would like to thank technicians of the departments of chemical engineering, mechanical engineering, advanced engineering materials facility, and materials characterization & preparation facility, for their kind help. Special thanks going to Ms Pauline LEUNG ST, Mr. CHENG HY, Mr.

YEUNG WL, and Mr. Alex FOK, for their detailed and patient instructions. I wish to express my appreciations to all group members in both mechanical and chemical labs. In particular, Mr.

SUN WZ helped me to run the tedious wear test. LU X and Mr. TANG YH worked with me for several years, your invaluable advice and kind assistance would be a life-long memory. XIN RL and Mr.

ZHAO ZF were always nice to share new ideas with me. I am very glad to have the chance to cooperate with Miss ZHANG WJ, Mr. YANG C, and Dr. RUAN SL, et al.

Also, I must thank all the friends who made my life in HKUST colorful and joyful. Last but not the least, I’d like to give my warmest gratitude to my parents, whose deepest and everlasting love are always my infinitive source of power to overcome all difficulties. I must thank my sister and brother-in-law for considerable supports both spiritually and financially all the time. I pray grandma and grandpa are peaceful in heaven since I lost all of you in the last five years but I could do nothing.

iv Table of Contents Titde.c- co co sS S0 0900 00 00008689868006085960 0666 ii Signature.ensee +49669999669985999698999669966669996086998886950566 sssssssssssese TÍÍ Acknowledgem€H(S.oooco co 033666 66 060166666661 666 96 sessse oe iV Table of Contents .cccccscsssssossccsssscesscorscerscsscsccecssscnees ee we V List of EFigures. 999 S58606008015055586660 690004 seseesssa AX List of Tables. 990993060009900809999090000000000090090008 seeseo XV Chapter 1 Background and objective kedsesssssseseesseseeesssse Ì INN\E i8 -.1 Strucfure and DFOD€TẨV. - GG cọ nọ te 1 1.2 Disorders and treatrn€rifS.2 Ultrahigh molecular weight polyethylene (UHMWPPE).1 Structure of UHMWPEE.

LG HH ng te 4 1.2 Properties of UHMWPE.3 Biomedical applications of UHMWPPE.4 Bone-analogue polymer matrIx blocOrmpOSIf€S.5 Objective and organ1ZafiOTI.- -s ng HH ni 13 Chapter 2 Processing of UNHMWPE — 15 2.1 Difficulties in processing UHMWPE.1 Chain mobility and crystal phases of polyethylene .2 Chain mobility and processability of UHMWPE .2 Conventional processing methods.3 Processing UHMWPE in hexagonal phase. --QQ TQ ren 22 2.1 Solid state extrusion of UHMWPE nascent powder.2 Temperature window effect of polyethylene 00. eee ee eceeeeeeeeeee 24 2.4 Processing UHMWPE using the temperature wIindow effect.1 UHMWPE nascent DOW€T. ee cee eeseesseecsseeeseeceteeceseeseseecsceeeaesessucesseeeses 27 2.5 Important factors in processing UHMWPE.-- HH HH HH ng 35 2.2 Lamellar crystal thickneSs.

se :sseessseseeseeseseeeeesesesessteesseeeceseeeeees 38 Chapter 3 Microstructure of DH MWP E .1 Scanning electron microscopy (SEM) .2 Transmission electron microscopy (TEM) .2 Microstructure of UHMWPE ex(rudaf€ .- HH ke 43 KV Na oi. ảằnằUPY£NẠIỊIẠạadadđiaia.2 Lamellar SfTUC{UT€. -- - ‹ - coHọ vn 46 Chapter 4 Wear property of UHMWPE. c s c s s es es e es 48 4.1 Wear testing of UHMWPPE.

- - --- cọ TH gi 0 i4 49 4.2 Sample Dr€DATAtÍOT. - HT cv 50 LÍ NI.- ng Họ th 54 4.1 Mass loss and volume 1088 .3 Factors affect wear property of UHMWPPE. - HH ng ng 62 Chapter 5 Processing of HA/UHMWVPE nanocompoSÏÌte .1 Conventional processing methods of UHMWPE-based composites .2 Processing method of HA/UHMWPE nanocompOoSIf€.1 Twin-screw extrusion (TSE) compounding.2 Swelling UHMWPE to improve chain mobi]ity.3 Processing details of HA/UHMWPE nanocomposife .4 Important factors in processing HA/UHMWPE nanocomposite .1 Swelling effect on the viscosity of UHMWPE gel.2 Compounding parameters on the exfrUSIOII .3 HA content on the consolidation at the final stage. 80 Chapter 6 Mierostructure of HA/UHMWPE nanocomposite .1 Character1zation mmethOdS.

-- -- - so ng ng 82 6.2 Scanning electron microscopy (SEM).3 Transmission electron microscopy (TEM|).5 Fourier transform 1nfrared spectroscopy (FTIR).2 Chemical anaÌyS1S. chì HH HH no TT” 85 6.1 HA and UHMWPE in the composite (XXRD).3 Oxidation and paraffin oil residue (F TÌIR).3 Microstructure of HA/UHMWPE nanocomposife.1 HA nano particle dispersion (SEM, EDS).2 HA/UHMWPE interface (TEM).3 UHMWPE chann alignment (SEM, WAXD).4 Processing effects on microstructure of the compOSIf€. «co 94 Chapter 7 Mechanical properties of HA/UHMWPE nanocomposite .1 HA content effect on mechanical prODe€FI€S.2 Hot drawing effect on mechanical properties .4 Phenomenologlcal modeling of mechanical properti€s.-<~5 103 Chapter 8 Biological evaluation of HA/UHMWPE nanocomposite.1 BiocompatIbility test: Acute systeImiC fOXICI(Y.2 Bloactivity test: Simulated body fluid (SBE).- ác TH HH He 111 8.2 HA conftent efÍ€ct.3 Ca-P layer characf€r1ZzatIOn\. cv S9 TK tk, 113 Chapter 9 Concluding remarks and future WOF.--o co sec «nen 61660068666 117 9,1 Concluding rernarKS.

HH HH 119 References. 121 vii Appendices ee 135 Appendix A Pin-on-disc wear test of UHMWPE/CoCr alloy in literature. 135 Appendix B Mechanical properties of bio-analogue composites of interest. 139 Appendix C Acute systemic toxicity Study .cccccccscscsssessserscscecesecesessssnenes 141 Publication list.„‹ 146 Vili List of Figures Figure 1.1 Hierarchical structural organization of bone.2 Anatomy ofhuman hip jOITI.3 Typical metal-on-UHMWPE total hip joint replacement.4 Chain structure of UHMWPE.5 Loose hip prosthesis caused by bone resorption.6 Crosslinking process of UHMWPE.

HH HH ng me 8 Figure 1.7 Various applications of different polymer composite biomaterials.1 Equilibrium phase đdiagram of polyethylene.2 Typical processing steps in the manufacture of UHMWPE implants.3 Schematics of ram extrusion, compression molding, hot 1sostatic 94-0 ae.4 Fusion defects due to bad consolidation.5 Particle size đistribution of UHMWPE powder.---àcc- cà 27 Figure 2.6 SEM micrographs of UHMWPE powder morphology.7 Schematic drawing of Géttfert Rheograph 2003 capillary rheometer. A: test chamber; B: test barrel; C: locking nut; D: heater element; E: capillary block; F: round hole capillary; G: capillary nut; H: pressure transducer; I: thermocouple (mounting sleeve); J: thin wall là 416441 Phố .8 Schematic drawing of the extrusion đie. - - «s sen vn 28 Figure 2.9 Photo Of ©XÍTU(CIA€.10 Schematic of flow field and pattern during extrusIon.11 Force profile during extrusion,. ce cccccsessesoreessecceusnsasceeennsceseueesecenes 38 Figure 2.12 Crystal growth and size dependent phase stability diagram.1 SEM micrographs indicate the fusion defects of UHMWPE.

a) Microtome cut; b) Cryogenically fractured; c) Polished & etched. 1) GUR 1050 ram extruded; 2) Basell 1900 capillary extruded.2 SEM micrographs show lamellae structures in crystalline regions revealed after etching the amorphous phase of UHMWPE (etched specimen). a) GUR1050 ram extruded; b) Basell1900 capillary ©4409" .3 TEM micrograph shows the lamellar structure of capillary extruded UHMWPE (unsftainedÌ). - - --- ng nọ 0t 45 Figure 3.4 XRD patterns of as-received UHMWPE powder and capillary extruded UHMWPE rod indicate the chain orientation in as- extruded UHMWPE.

a) Equipment setup; b) Pin-on-disc configuration; c) Environrnental chamber.2 Photos of UHMWPE pin and CoCrMGO đỉsc.- --- Su nen ese 51 Figure 4.3 Schematic drawing of CoCrMG đ1§C.4 Wear loss of UHMWPE against wear testing cycles and sliding CiStANCE.5 Mass loss of UHMWPE against wear testing cycles in the steady WEALP SLAZE.6 Morphology of as-extruded UHMWPE wear debris characterized by SEM after different wear cycles.7 Morphology of as-received UHMWPE wear debris characterized by SEM after different wear cycles.8 Morphology of as-received UHMWPE wear debris characterized by SEM after different wear cycles.9 Surface topography of UHMWPE pin and CoCr disc before and after wear testing examined by optical pro fẨiÏ€r. --- x1 se vee« 60 Figure 4.10 SEM morphology of UHMWPE worn surface. a~c) as-received; d~f) as-extruded UHMWPE.1 Schernatic Of twin-SCT€W ©XÍTU€T.2 Improved chain mobility of polymer swollen gel.3 As-received HA powder size đistrIDbutiOT.- dc n1 1 seeese 72 Figure 5.4 SEM micrographs of as-received HA powder.5 Left: Twin-screw extruded fibers; Right: Pelletized granules.6 Viscosity dependence on HMWPPE concentration.7 Compounding variables effect on exfruSIOn.1 Angles y and y defining the position of the normal to a given hkl crystal plane in the sample reference system. DD, draw direction or fiber axis; ND, normal direction; TD, transverse direction; /,, incident x-ray beam; Jgiy, diffracted intensity.2 XRD patterns of UHMWPE (a), HA powder (h), and HA/UHMWPE nanocomposite (b~g) with HA volume content from 0 (b) to 50% (2.3 a) TGA measurement of pure paraffin oil, HA, and UHMWPE powder.

b) Derivative of weight against temperature.4 TGA thermographs show the actual weight percentage of HA filler content and thermal degradation temperature of HA/UHMWPE nanocomposites with nominal HA volume percentage increasing from 0 (€) to 0 10.5 TGA thermograph of the composite with nominal HA content of 77wt% after paraffin oil extraction in hexane.6 FTIR spectra of UHMWPE powder (a), paraffin oil (b), HA powder (c), HA/UHMWPE powder mixture (d), and HA/UHMWPE nanocomposite (e). Small figure: Enlarged spectra in the wave number range of 2800~2975 0 88 Figure 6.7 SEM micrographs of HA/UHMWPE compounds cross section after twin-screw extrusion (a~f: HA vol. Sàn se Figure 6.8 Dispersion of HA nano particles (SO0vol%) in UHMWPE matrix characterized by SEM and EDS. Top surface of compression molded sheet: a) Global HA dispersion and b) Inter-penetration network of HA particles and UHMWPE fibrils; Cryogenically fractured cross section surface: c) Homogeneous dispersion of HA nano particles in the composite; d) EDS elemental analysis; and e) EDS map scanning of the element Calcium (Ca) of HA (bright so) .9 TEM micrographs of the HA/UHMWPE nanocomposite with HA volume percentage 12.

a) Composite morphology; b) Selected area for SAED and HRTEM analysis; c) SAED pattern of the area in b); and d) HRTEM image of the ellipse area In b).10 SEM micrographs show the homogeneous dispersion of HA nano- particles and highly oriented UHMWPE fibrils after hot drawing (DR = 20).11 WAXD patterns show the orientation of UHMWPE fibrils decreases „20:85.