Tổng hợp và đặc trưng màng hydroxyapatit pha tạp một số nguyên tố vi lượng trên nền thép không rỉ 316L định hướng ứng dụng làm nẹp vít xương (Luận án tiến sĩ)

Tổng hợp và đặc trưng màng hydroxyapatit pha tạp một số nguyên tố vi lượng trên nền thép không rỉ 316L định hướng ứng dụng làm nẹp vít xươngTổng hợp và đặc trưng màng hydroxyapatit pha tạp một số nguyên tố vi lượng trên nền thép không rỉ 316L định hướng ứng dụng làm nẹp vít xươngTổng hợp và đặc trưng màng hydroxyapatit pha tạp một số nguyên tố vi lượng trên nền thép không rỉ 316L định hướng ứng dụng làm nẹp vít xươngTổng hợp và đặc trưng màng hydroxyapatit pha tạp một số nguyên tố vi lượng trên nền thép không rỉ 316L định hướng ứng dụng làm nẹp vít xươngTổng hợp và đặc trưng màng hydroxyapatit pha tạp một số nguyên tố vi lượng trên nền thép không rỉ 316L định hướng ứng dụng làm nẹp vít xươngTổng hợp và đặc trưng màng hydroxyapatit pha tạp một số nguyên tố vi lượng trên nền thép không rỉ 316L định hướng ứng dụng làm nẹp vít xươngTổng hợp và đặc trưng màng hydroxyapatit pha tạp một số nguyên tố vi lượng trên nền thép không rỉ 316L định hướng ứng dụng làm nẹp vít xương

Plasma

q

Society for Testing and Materials)

OCP Octacanxi photphat, Ca8(PO4)4(HPO4)2.5H2O

OD

SBF

Body Fluid)

Electrode)SEM

Microscope)

TEM

Electron Microscope)TKG316L

khoa h c ph c b HAp m t s

m Vi c

khu n: P.aerugimosa, E.coli E.faecalis b

th ch

C D y c sinh ra khi nung d ng l 850 oC trong

n nhi nhi u x tia X c a hai

Ca10(PO4)6(OH)2 + 2HCl 3Ca3(PO4)2+ CaCl2+ 2H2O (1.1)

i b n nhi t, b ch m trong kho ng nhi t 800oC

n 1200 oC t xy - hydroxyapatit theo ph n ng:

Ca10(PO4)6(OH)2 Ca10(PO4)6(OH)2-2xOx+ xH2O (0 x 1) (1.2)

4P2O9ho c CaO:

Ca10(PO4)6(OH)2 2 - Ca3(PO4)2+ Ca4P2O9+ H2O (1.3)

Ca10(PO4)6(OH)2 3 - Ca3(PO4)2+ CaO + H2O (1.4)

Ca10(PO4)6(OH)2+ 18H2O (1.6)

ph n ng (1.7) [14, 17]:

10Ca(NO3)2 + xM(NO3)n+ 6(NH4)2HPO4 + (8+xn)NH3 + (8+xn) H2O

n b t HAp v i ng v ch polyvinyl ancol 1%

1000 oC K t qu c m u HAp d ng kh x p 47 % c l x p kho ng 50 - 120 nm, ng su u 4 - 21 MPa [18]

HPO + OH- PO34 + H2O (1.14)

c Ph n ng k t t c:

10Ca2++ 6PO34 + 2OH- Ca10(PO4)6(OH)2 (1.15)

Thi n t t c n chuy

[56]

a, s k t h p c

Ca(NO3)2 0,036 M + NH4H2PO40,025 M + Mg(NO3)2 0,0084 M sao cho t l (Ca + Mg)/P = 1,67; pH 4,2; nhi 65 oC; m i 0,85 mA/cm2

t li u trong dung d ch mu [59] ho c dung d ch mu i Ringer

37oC [1, 76]

57, 59, 61]

2+

v t li u nanocompozit PLLA/HAp Th nghi m ho h sinh h c c a v t li u

t tinh khi t c a Merk c)

2.1.2 V t li u n n

M u TKG316L v ph n c: 0,27 % Al; 0,17 % Mn; 0,56 % Si; 17,98 % Cr; 9,34 % Ni; 2,15 % Mo; 0,045 % P; 0,035 % Fe

DNa1: Ca(NO3)23.10-2 M + NH4H2PO4 1,8.10-2M + NaNO34.10-2M

DNa2: Ca(NO3)2 3.10-2 M + NH4H2PO4 1,8.10-2M + NaNO3 6.10-2M

DNa3: Ca(NO3)23.10-2 M + NH4H2PO4 1,8.10-2M + NaNO38.10-2M

DSr1 DNa2 + Sr(NO3)2 1.10-5 MDSr2 DNa2 + Sr(NO3)2 5.10-5 MDSr3 DNa2 + Sr(NO3)2 1.10-4 MDSr4 DNa2 + Sr(NO3)2 5.10-4 M

FNaHAp

DF1 DNa2 + NaF 5.10-4 MDF2 DNa2 + NaF 1.10-3 MDF3 DNa2 + NaF 2.10-3 M

2.1.4 Pha t p m t s n NaHAp b i ion

t 5 mV/s trong dung d ch DNa2

Th c hi n b t li u NaHAp/TKG316L trong 4 mL dung d ch

ch ng th i Cu(NO3)2 0,02 M + AgNO3 0,001 M + Zn(NO3)2 0,05 M trong

ng trong dung d ch DMgSrFNa, u ki n:

- HAp v i s t ng th i t t c magi , stronti, flo,

th i Cu(NO3)2 0,02 M + AgNO3 0,001 M + Zn(NO3)2 0,05 M trong th i gian 30

n tr c Tafel c th c hi n trong kho n th 0,5

V xung qu n th m ch h E0 trong dung d ch SBF v i t mV/s T

(%) 100 ln ,

ln ,

v corr

corr v corr

i

i i

pha t p trong dung d bi modun

m

C C

9 , 0

h ng v t li u - Vi n Khoa h c V t li u ho c thi t b SEM-JSM-6510LV t i Vi n Kthu t nhi i.

n ISO 4288-1998 t Alpha-Step IQ (KLA-Tencor - USA) t i Vi n

Dung d ch sau khi

th i gian ng u b

nghi m in vivo

khi t v c ch ng 2.3 [103] Sau khi pha, dung d ch thu

T QU O LU N

3.1.1 T ng h p b

p natri c

HPO + OH- PO34 + H2O (3.9)10(Ca2+, Na+) + 6PO34 + 2OH 10(PO4)6(OH)2 (3.10)

-2.2 -2.0 -1.8 -1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 -6.0

-5.5 -5.0 -4.5 -4.0 -3.5 -3.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0

l( [108, 109])

c l a ch m ti p theo M NaHAp c trong

HAp (NIST) K t qu c th hi gi XRD t i v o, pic c a m u NaHAp t ng h i HAp (NIST) kho ng +0,44 o

ng H+trong dung d ch l m t ph n ng t o ion 3

ng ion OH- trong dung d ch l n x y ra hi ng k t t a

0)

-2.0 -1.8 -1.6 -1.4 -1.2 -1.0 -0.8 -0.6 -0.4 -0.2 0.0 -3.5

-3.0 -2.5 -2.0 -1.5 -1.0 -0.5 0.0

s HAp pha t u

ng theo ph n ng ([53, 57, 59]):

10(Ca2+,Mg2+,Na+) + 6PO34 + 2OH 10(PO4)6(OH)2 (3.12)

Ho c: 10(Ca2+,Sr2+,Na+) + 6PO34 + 2OH 10(PO4)6(OH)2 (3.13)

Ho c:

(Ca,Na)10(PO4)6(OH)2 + xF-+ xH+ (Ca,Na)10(PO4)6(OH)2-xFx + xH2O (3.14)

a TKG316L trong dung d

2+

(a), Sr2+ -(c) v

B ng 3.9 bi u di n ng c a kho t i ng, kh i

ng ion OH- PO34 sinh nhi ng NaHAp t o ra nhi u Tuy

t c i trong kho ng th -1,7 V/SCE

y, d t qu c cho th y kho ng th -1,7 V/SCE

10 15 20 25 30 35 40 45 50 55 60 65 70

MgNaHAp

NaHAp SrNaHAp

1 1

kho ng (xem m c 3.1.1 t Mg(NO3)2 3)2

-6 -5 -4 -3 -2 -1 0

DMgSrFNa DNa2

E (V/SCE)

n c c TKG316L trong dung d

c a HAp 46; ov nh [104] t hi n pic c a n n TKG316L, bao g m c a Fe t 45 o

t c i 3,17 mg/cm2 ng v i chi i 50 oC Ti p t hi t

chung gi m khi nhi K t qu c gi

2 )

Gi XRD c ng h p nhi :

oC

t m c 3.1.1.3:

th 5 mV/s, nhi 50 oC trong dung d ch ch a Ca(NO3)2 3.10-2 M +

NH4H2PO4 1,8.10-2 M + NaNO3 6.10-2 M + Mg(NO3)2 1.10-3 M + Sr(NO3)25.10-4 M + NaF 2.10-3M

0,001 0,259 Ca9,021Na0,722Ag0,257(PO4)6(OH)20,002 0,374 Ca8,907Na0,722Ag0,371(PO4)6(OH)20,005 0,569 Ca8,714Na0,722Ag0,564(PO4)6(OH)2

-Zn2+

0,01 0,499 Ca8,783Na0,722Zn0,495(PO4)6(OH)20,05 1,248 Ca8,040Na0,722Zn1,238(PO4)6(OH)20,1 3,858 Ca5,452Na0,722Zn3,826(PO4)6(OH)2

2 Gi XRD c c sau khi i ion gi a NaHAp v i dung d ch: Zn2+ 0,01 M (a); 0,05 M (b); 0,1

Ag+ 0,001 M (d); 0,002 M (e); 0,005 M (f); 0,01 M (g)

nghi m ti p theo, dung d ch Ag+, Zn2+ l t

ng v Ca9,021Na0,722 Ag0,257(PO4)6(OH)2,Ca8,040Na0,722 Zn1,238(PO4)6(OH)2

Zn2+: t n 1,440 mmol/g) V i ion Ag+, sau th

mmol/g, ti p t

3 S bi i ion theo th i gian ti a

3 2

1 1

1 1

1 HAp; 2 CrO.FeO.NiO; 3 Fe

8 Gi XRD c CuAgZnNaHAp (b)

1 1

1 1

1 1

4 N Ca2+ tan khi v t li u trong dung d ch NaCl 0,9 %

Zn

NaHAp, t ng n s t b tan ra t n n TKG316L c a b n v t li u TKG316L, NaHAp/TKG316L, MgSrFNaHAp/TKG316L /TKG316L theo th i gian

35)

35 T ng n s t li u trong dung d ch SBF

i m i th m u, n s t c a m u TKG316L > NaHAp/TKG316L > MgSrFNaHAp/TKG316L > HAp /TKG316L

so m u HAp /TKG316L K t qu nh kh o v n n c

t ion OH- m t m u t quan tr m tinh th apatit

i v i v t li

8 Ph t ng tr d ng Nyquist c a v t li u trong dung d ch SBF

39 S bi i mo un t ng tr c t li u t i t n s 100 mHz

-Ecorr c a TKG316L kho -0,424 V/SCE K t qu

v cho b m t kim lo i n n

-0.8 -0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 -8.5

-8.0 -7.5 -7.0 -6.5 -6.0 -5.5 -5.0 -4.5 -4.0

u qu b o v kim lo i n n cMgSrFNaHAp, HAp l

i thi nh SEM c a v t li u TKG316L, NaHAp/TKG316L,

B ng 3.24 K t qu th nghi m Trypan Blue v n a b t

Na

N MgSrFNaHAp (%)

ch t

T l ch t (%)

Ti u c u (G/L) ng

NaHAp (n = 6)

B ng 3.27 N GPT (U/L) c a m

Ch ng (n = 6)

NaHAp (n = 6)

NaHAp (n = 6)

NaHAp (n = 6)

MgSrFNaHAp

> 0,0515,95 > 0,05

Ti u c u (G/L) ng

B ng 3.31 N GOT (U/L) c m

Ch ng (n = 8)

NaHAp (n = 8)

ch ng, NaHAp, MgSrFNa u n m trong gi i h

NaHAp (n = 8)

NaHAp (n = 8)

B ng 3.34 N Creatinin ( ) c m

Ch ng (n = 8)

NaHAp (n = 8)

u ng i v ng vi khu n

DANH M

1 Pham Thi Nam, Nguyen Thi Thom, Nguyen Thu Phuong, Vo Thi Hanh,

Nguyen Thi Thu Trang, Vu Thi Hai Van, Trinh Hoang Trung, Tran Dai Lam,

Dinh Thi Mai Thanh Electrodeposition of substainable fluoridated

Hydroxylapatite coatings on 316L stainless steel for application in bone implaint Green Processing and Synthesis, 5, 499-510, 2016 (ISI).

Mai Thanh T ng h

3 Vo Thi Hanh, Pham Thi Nam, Dinh Thi Mai Thanh Electrodeposition and

characterization of strontium hydroxyapatite coatings on 316L stailess steel

Vietnam Journal of Chemistry, 55(3e12), 346-350, 2017

ng i 62(3), 51-59, 2017

Nguyen Thu Phuong, Dinh Thi Mai Thanh Electrodeposition and

characterization of Mg 2+ , Sr 2+ , F - , Na + co-doped hydroxyapatite coatings on 316L stailess steel Processdings of 6th Asian Symposium on Advanced Materials, 740-746, 2017

7 Vo Thi Hanh, Pham Thi Nam, Nguyen Thu Phuong, Nguyen Thi Thom, Le

Thi Phuong Thao, Dinh Thi Mai Thanh Electrodeposition and

characterization of magnesium hydroxyapatite coatings on 316L stailess steel.

Vietnam Journal of Chemistry, 55(5), 657-662, 2017

8 Vo Thi Hanh, Pham Thi Nam, Nguyen Thu Phuong, Dinh Thi Mai Thanh

Electrodeposition of co-doped hydroxyapatite coatings on 316L stailess steel.

Vietnam Journal of Science and Technology, 56 (01), 94-101, 2018

tr b T Khoa h ng

-1059.2017-0011,

U THAM KH O

1 A Sharifnabi, M Fathi, B Eftekhari, M Hossainalipour The structural and

bio - corrosion barrier performance of Mg - substituted fluorapatite coating

on 316L stainless steel human body implant Applied Surface Science, 2014,

288, 331 - 340.

2 Sumathi, Shanmugam, Buvaneswari, Gopal Copper substituted

hydroxyapatite and fluorapatite: Synthesis, characterization and antimicrobial

properties Ceramics International, 2014, 40(10A), 15655 - 15662.

Synthesis, characterization and antimicrobial activity of copper and zinc doped hydroxyapatite nanopowders Applied Surface Science, 2010,

-256(20), 6083 - 6089.

4 M Honda, Y Kawanobe, K Ishii, T Konishi, M Mizumoto, N Kanzawa,

M Matsumoto, M Aizawa In vitro and in vivo antimicrobial properties of

silver - containing hydroxyapatite prepared via ultrasonic spray pyrolysis

route Materials Science and Engineering, 2013, 33(8), 5008 - 5018.

5 W John, A Richard, W Kenneth, C BladhMonte Hydroxylapatite.

Handbook of Mineralogy, Chantilly, VA, US, Mineralogical Society of America, ISBN 0962209732, 2000

6 A Dey, S Gangadharan, K Mukhopadhyay, K Sinha, D Basu, R

Bandyopadhyay Nanoindentation study of microplasma sprayed

hydroxyapatite coating Ceramics International, 2009, 35, 2295 - 2304.

7 B Fowler, M Markovic, M Tung Preparation and Comprehensive

Characterization of a Calcium Hydroxyapatite Reference Materials.

Technol, 2004, 9, 552 - 568.

8 D Phebe, B Narasaraju Some Physico-Chemical Aspects of Hydroxyapatite.

Journal of Materials Science, 1996, 31, 1 - 21.

9 P Ylinen Applications of Coralline Hydroxyapatite with Bioabsorbable

Containment and Reinforcement as Bone Graft Substitute Academic

Dissertation, University of Helsinki, 2006

10 A Ivanov, E Krylova, S Krylov, I Plashchina, P Nefedov

Hydroxyapatite-Alginate Sructure as Living Cells Supporting System N.N Emanuel Institute

of Biochemical Physics RAS, Russia, 2004

11 C Paluszkiewicz, A Pijocha, M Sitarz, M Zima,

A , M Lewandowska Synthesis, structural properties and

thermal stability of Mn - doped hydroxyapatite Journal of Molecular

14 W Chen, Z Huang, Y Liu, Q He Preparation and characterization of a

novel solid base catalyst hydroxyapatite loaded with strontium Catalysis

Communications, 2008, 9(4), 516 - 521.

15 A Yelten, S Yilmaz Various Parameters Affecting the Synthesis of the

Hydroxyapatite Powders by the Wet Chemical Precipitation Technique.

Materials Today, Proceedings, 2016, 3(9), 2869 - 2876.

16 S Waheed, M Sultan, T Jamil, T Hussain Comparative Analysis of

Hydroxyapatite Synthesized by Sol - gel, Ultrasonication and Microwave

Assisted Technique Materials Today, Proceedings, 2015, 2(10), 5477 - 5484.

17 A Yasukawa, T Yokoyama, K Kandori, T Ishikawa Ion - exchange of

magnesium - calcium hydroxyapatite solid solution particles with Cd 2+ ion.

Colloids and Surfaces, Physicochemical and Engineering Aspects, 2008,

317(1), 123 - 128.

18 G Fuentes, E Peon, A Delgado, L Morejon, A Almirall, R Garcia

Preparation and characterization of porous blocks of synthetic

hydroxyapatite Latin American Applied Research, 2006, 34, 225 - 228.

19 C Y Tang, P S Uskokovic, C P Tsui, D J Veljovic, R Petrovic, D J

Janackovic Influence of microstructure and phase composition on the

nanoindentation characterization of bioceramic materials based on

hydroxyapatite Ceramics International, 2009, 35(6), 2171 - 2178.

20 Y Zhang, Y Yokogawa, X Feng, Y Tao, Y Li Preparation and properties

of bimodal porous apatite ceramics through slip casting using different

hydroxyapatite powders Ceramics International, 2010, 36(1), 107 - 113.

21 H Zhang, Q Fu, T Sun, F Chen, C Qi, J Wu, Z Y Cai, Q R Qian, Y J

Zhu Amorphous calcium phosphate, hydroxyapatite and poly (d,l - lactic

acid) composite nanofibers: Electrospinning preparation, mineralization and

in vivo bone defect repair Colloids and Surfaces B: Biointerfaces, 2015,

136, 27 - 36.

22 H Wang, Y Li, Y Zuo, J Li, S Ma, L Cheng Biocompatibility and

osteogenesis of biomimetic nano - hydroxyapatite/polyamide composite

scaffolds for bone tissue engineering Biomaterials, 2007, 28(22), 3338

-3348

23 F Wenpo, L Gaofeng, F Shuying, Q Yuanming, T Keyong Preparation

and characterization of collagen - hydroxyapatite/pectin composite.

International Journal of Biological Macromolecules, 2015, 74, 218 - 223.

24 L Chen, J Hu, J Ran, X Shen, H Tong Preparation and evaluation of

collagen-silk fibroin/hydroxyapatite nanocomposites for bone tissue

engineering International Journal of Biological Macromolecules, 2014, 65, 1

-7

25 L Pighinelli, M Kucharska Chitosan - hydroxyapatite composites.

Carbohydrate Polymers, 2013, 93(1), 256 - 262.

26 C Sundaram, N Viswanathan, S Meenakshi Fluoride sorption by nano

-hydroxyapatite/chitin composite Journal of Hazardous Materials, 2009,

172(1), 147 - 151.

27

E Axente, J Werckmann, I Mihailescu Study of the gradual interface

between hydroxyapatite thin films PLD grown onto Ti - controlled sublayers.

Applied Surface Science, 2007, 254(4), 1150 - 1154.

28 Nik Norziehana, Che Isa, Yusairie Mohd, Norjanah Yury Electrochemical

Deposition and Characterization of Hydroxyapatite (HAp) on Titanium

Substrate APCBEE Procedia, 2012, 3, 46 - 52.

29 A Kar, K Raja, M Misra Electrodeposition of hydroxyapatite onto

nanotubular TiO 2 for implant applications. Surface and Coatings

Technology, 2006, 201(6), 3723 - 3731.

30 K Khor, Y Gu, P Cheang In vitro studies of plasma-sprayed

hydroxyapatite/Ti 6Al

-(SBF) Biomaterials, 2003, 24, 1603 - 1611.

31 A Sakaguchi, M Nakano, J Hieda, N Ohtake, H Akasaka Dependence of ion

concentration in simulated body fluid on apatite precipitation on titania surface.

Applied Surface Science, 2015, 347, 610 - 618.

32 X Fan, J Chen, J Zou, Q Wan, Z Cheng, Z Ruan Bone-like apatite

formation on HA/316L stainless steel composite surface in simulated body

fluid Transactions of Nonferrous Metals Society of China, 2009, 19(2), 347

-352

33 K K Chew, S Hussein, S Zein, A L Ahmad, David Phail, Muhammad

Faiq Abdullah The electrochemical studies of the corrosion resistance

behaviour of hydroxyapatite coatings on stainless steel fabricated by electrophoretic deposition Journal of Industrial and Engineering Chemistry,

2013, 19(4), 1123 - 1129.

34 J Chen, X Fan, J Zou, Q Wan, Z Zhou, J Ruan Bone - like apatite

formation on HA/316L stainless steel composite surface in simulated body

fluid Transactions of Nonferrous Metals Society of China 2009, 19, 347 - 352.

35 P T Nam, D T M Thanh, N T Phuong, L X Que, N V Anh, T Hoang,

T D Lam Controlling the electrodeposition, morphology and structure of

hydroxyapatite coating on 316L stainless steel Materials Science and

Engineering, 2013, C 33( 4), 2037 - 2045.

36 X X Wang, D Y Lin Electrodeposition of hydroxyapatite coating on

CoNiCrMo substrate in dilute solution Surface & coatings Technology,

2010, 204, 3205 - 3213.

37 M B Kannan 13 - Hydroxyapatite coating on biodegradable magnesium and

magnesium - based alloys, in Hydroxyapatite (Hap) for Biomedical Applications Michael Mucalo, Editor, 2015, Woodhead Publishing, 289 - 306.