Author’s Accepted Manuscript

Corrosion behavior of SiC-hyaluronic acid-Sr

doped dicalcium phosphate dihydrate composite
coating in simulated body fluid

Zhang Leilei, Li Hejun, Zhao Yizhi, Li Bingxin,

Ren Fangyuan, Chang Mochen, Zhang Yulei
www.elsevier.com/locate/ceri

PII: S0272-8842(16)31905-8
DOI: http://dx.doi.org/10.1016/j.ceramint.2016.10.165
Reference: CERI14044
To appear in: Ceramics International
Received date: 4 September 2016
Revised date: 12 October 2016
Accepted date: 21 October 2016
Cite this article as: Zhang Leilei, Li Hejun, Zhao Yizhi, Li Bingxin, Ren
Fangyuan, Chang Mochen and Zhang Yulei, Corrosion behavior of SiC-
hyaluronic acid-Sr doped dicalcium phosphate dihydrate composite coating in
simulated body fluid, Ceramics International,
http://dx.doi.org/10.1016/j.ceramint.2016.10.165
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Corrosion behavior of SiC-hyaluronic acid-Sr doped dicalcium phosphate dihydrate composite

coating in simulated body fluid

Zhang Leilei, Li Hejun, Zhao Yizhi, Li Bingxin, Ren Fangyuan, Chang Mochen, Zhang Yulei

State Key Laboratory of Solidification Processing, Northwestern Polytechnical University, Xi’an 710072, China

Abstract: To endow suitable anti-corrosion property in simulated body fluid for biological

carbon/carbon composites (CC), a composite coating consisted of SiC inner-layer and hyaluronic

acid(HYA)-Sr doped dicalcium phosphate dehydrate (SD) outer-layer was fabricated on CC. The

morphology, microstructure and corrosion resistance of the SiC-HYA-SD composite coating were

investigated. The results showed that SiC inner-layer could provide a rough surface for the

nucleation of HYA-SD outer-layer. The SiC inner-layer served as a buffer layer between CC and

HYA-SD outer-layer. HYA and SD combined together to form a hybrid outer-layer after the

electrodeposition process. HYA-SD could enwrap the SiC inner-layer and then form a uniform

coating with villous shape. Potentiodynamic polarization results indicated that SiC-HYA-SD

composite coating exhibited better corrosion resistance in simulated body fluid compared to

HYA-SD coating without SiC inner-layer.

Keywords: SiC; Hyaluronic acid; Coating; Implant

1. Introduction

The combination of organic and inorganic phases is a feature of natural bone, which could be

considered as a kind of composites consisting of collagen and calcium phosphate (Ca-P) phase

[1,2]. Thus, the organic-inorganic composite materials that mimic the bone structure are of

significant interest for biomedical applications.

The inorganic phases in bone mineral are mainly Ca-P phases, such as hydroxyapatite,
fluorapatite, carbonated apatite, monocalcium phosphate, dicalcium phosphate dehydrate(DCPD)

and tricalcium phosphate(TCP)[3,4]. Among these Ca-P phases, DCPD exhibits excellent cell

compatibility with murine fibroblast and promotes the growth of new formed bone in-vivo[5-7].

Further, the Ca ions in DCPD could be substituted by Sr ions, leading to the promotion of

biological properties. Sr element and Ca element have near position in periodic table and process

similar chemical properties. The substitution of Ca ions by Sr ions could have a favorable effect

on the dissolution behavior of Ca-P phase[8]. The in-vitro tests have shown that the substitution of

Sr to Ca leads to an increase in number of osteoblast cells and a decrease in the number of

osteoclast cells[9]. The in-vivo studies have proved that the presence of Sr could stimulate new

bone formation, exhibiting excellent osteointegration[10,11]. As a consequence, Sr substituted

DCPD (SD) has been developed as inorganic biomaterials in which its excellent biological

properties are exploited.

Hyaluronic acid (HYA) is an important organic material in the mammalian extracellular

matrix, which plays key role in bone tissue development, repair, and function[12]. HYA not only

exhibits stability on phosphate buffered saline (PBS) solutions but also contributes significantly to

cell attachment, growth and proliferation[13,14]. Significant interest has been generated in the

development of HYA coatings for prosthetic cartilage and vascular graft applications[15,16].

Given the advantages of SD and HYA, there are considerable interests in using SD and HYA

for biological coatings. In this work, HYA-SD hybrid coatings are prepared on carbon/carbon

composites (CC) by electrodepostion. In addition, a SiC layer is designed between CC and

HYA-SD hybrid coating. SiC has excellent physical and chemical compatibility with CC [17, 18].

In addition, the biocompatibility of SiC has been reported by many researchers. Wu et al. tested
the cytocompatability of SiC using osteoblast-like MG63cells. The results showed that the MG63

cells could attach and grow well on the surface of the SiC, indicating that SiC was non-toxic and

possessed good cytocompatibility [19]. D.M. Vranceanu et al. reported that SiC could have

favorable effect on the cell proliferation and viability[20]. S. Santavirta et al. investigated the

in-vitro behavior of SiC coating and concluded that SiC was a promising coating material used for

total hip replacement[21]. P. Aspenberg et al. described the reactions of regenerating bone tissue in

rabbits to SiC particles and concluded that the SiC particles could not cause any decrease in bone

formation and were comparatively harmless[22]. In this work, a SiC-HYA-SD composite coating

consisting of SiC inner-layer and HYA-SD hybrid outer layer is prepared on CC substrates. The

morphology, microstructure and corrosion behavior of the SiC-HYA-SD composite coating are

investigated.

2. Experimental

2.1 Materials and methods

CC substrates (8 mm ×8 mm ×2 mm) were cut from bulk CC with a density of 1.78 g/cm3.

They were hand-abraded using 400 grit SiC paper, cleaned ultrasonically in turn by acetone,

ethanol and distilled water, and dried at 373 K for 4 h. The schematic of the SiC-HYA-SD

composite coating for CC was shown in Fig. 1. The preparation process of the coating was as

follows. Firstly, SiC inner-layer was synthesized on CC by pack cementation. Details information

of the pack cementation process could be found elsewhere[23]. Secondly, HYA-SD hybrid

outer-layer was synthesized by electrodeposition. The electrolyte was consisted of 66.8 mmol/L

NH4H2PO4, 40.0 mmol/L Ca(NO3)2•4H2O and 66.8 mmol/L Sr(NO3)2 in a mixed ethanol-water

solvent (50-70 vol.% ethanol). Sodium hyaluronate was used as starting materials for introducing
HYA during the electrodeposition process. The concentration of the sodium hyaluronate was 0.5

g/L. The current was 2 mA and the temperature was 333±1 K. The deposition times were 120 s, 10

min, 30 min, 1 h and 2 h. After the electrodeposition process, the samples were taken out of the

electrolyte, rinsed with deionized water and dried in air.

2.2 Characterization

The morphology and microstructure of SiC-HYA-SD composite coating were analyzed by

scanning electron microscopy (SEM, SUPRA55), energy dispersive X-ray spectroscopy (EDS,

SUPRA55), X-ray diffractometer (XRD, X’Pert PRO), Raman spectroscope (Raman, Optelics

C130), X-ray photoelectron spectroscopy (XPS, AXIS ULTRA) and Fourier transform infrared

spectroscope (FTIR, EQUINOX55).

The corrosion behavior of SiC-HYA-SD coating was evaluated by testing polarization in

simulated body fluid (SBF) using a three-electrode workstation (CS310, Corrtest). The HYA-SD

hybrid coating without SiC inner-layer acting as reference sample was also tested using same

procedure.

3. Results and discussion

Fig.2 shows the SEM micrographs, EDS and XPS results of SiC inner-layer and

SiC-HYA-SD composite coating. By SEM observation, SiC inner-layer exhibits a homogenous

structure. No cracks could be observed on the surface of SiC inner-layer (Fig.2a). After deposition

for 120 s, only a few part of SiC inner-layer is covered by HYA-SD due to the short deposition

time. The underlying SiC inner-layer could be observed. HYA-SD attaches on SiC inner-layer and

forms a connection between each other (arrow in Fig.2b). By high magnification, it can be found

that HYA-SD forms a three dimensional porous structure on SiC inner-layer. The growth direction
of HYA-SD is nearly vertical to the surface of SiC inner-layer (Fig.2c). After deposition for 1 h,

HYA-SD fully covers SiC inner-layer, exhibiting a villous shape with a thickness of 15-70 nm

(Fig.2d). The EDS results confirm the existence of Si and C elements for SiC inner-layer. For

SiC-HYA-SD composite coating, O, P, Ca, Na, N and Sr elements are detected beside Si and C

elements. The position of Sr element (1.65) is similar to that of Si element (1.74), showing an

overlapped curve in the EDS spectrum. In order to further confirm the existence of Sr element,

XPS test is performed to analyze SiC-HYA-SD composite coating. The XPS spectrum shows that

the Sr element could be detected at 269.5 eV(Fig.2f).

Fig.3 shows the XRD patterns and Raman spectra of SiC inner-layer and SiC-HYA-SD

composite coating. The XRD patterns show that the inner-layer is mainly composed of SiC, with a

few Si being detected because a few Si is residual after the reaction between Si and C during the

pack cementation process. Typical crystallized peaks of DCPD are observed at 2θ values of 11.9o,

20.8o and 38.2o for SiC-HYA-SD composite coating (JCPDS 09-0077). By Raman analysis, three

peaks are found for SiC inner-layer, locating at 521 cm-1, 795 cm-1 and 959 cm-1. There are seven

peaks being observed for SiC-HYA-SD composite coating. Beside the three above mentioned

peaks generating from SiC inner-layer, the other four peaks relating to the functional groups of SD

are found, including PO43- mode at 429 cm-1, 592 cm-1 and 1050 cm-1 as well as HPO42- mode at

876 cm-1[24].

To confirm the formation of HYA-SD hybrid outer-layer on SiC inner-layer modified CC, the

weight gain of SiC inner-layer modified CC versus deposition time during the electrochemical

deposition process is recorded (Fig.4). The weight gain increases with the increase of deposition

time, indicating the formation of HYA-SD hybrid coating.

 To confirm the existence of HYA in the HYA-SD hybrid outer-layer, the HYA-SD hybrid

outer-layer is peeled off for TG and FTIR tests, with the SD without HYA being used as a

reference sample (Fig.5). Fig.5a compares the TG results for SD without HYA and HYA-SD. The

SD without HYA suffers a very low weight loss during the TG test. The low weight loss is

attributed to the dehydration of SD. In contrast, HYA-SD exhibits several steps in weight loss

during the TG test. The weight loss is 15% at 498 K and reaches to 70% at 1073 K. An additional

weight loss caused by the burnout of HYA is observed for HYA-SD when comparing with SD

without HYA, which confirms the existence of HYA in HYA-SD hybrid outer-layer. Fig.5b shows

the FTIR results for SD without HYA and HYA-SD. Different curve shapes are observed for SD

without HYA and HYA-SD. For SD without HYA, the vibrations bands relating to PO43- are found

at 1035 cm−1 and 502 cm−1. The stretching mode of HPO42- could be detected at 868 cm−1. A broad

peak at 3483 cm−1 and a strong peak at 1649 cm−1 are found, which is assigned to the stretching

mode of hydroxyl anions of water. For HYA-SD, beside the above mentioned peaks, characteristic

amide I (1636 cm-1) and amide II (1560 cm-1) peaks of HYA are detected (Fig.5c). Moreover, the

band at 1417 cm-1 can be attributed to the symmetric stretching vibrations of the carboxylic groups

in HYA. The FTIR analysis also indicates the existence of HYA in the HYA-SD hybrid outer-layer.

To investigate the effect of SiC inner-layer on the corrosion behavior in SBF of the

SiC-HYA-SD composite coating, the corrosion behavior of HYA-SD coated CC and SiC-HYA-SD

coated CC are analyzed. Fig.6 shows the potentiodynamic polarization curves for HYA-SD coated

CC and SiC-HYA-SD coated CC. The corrosion potential (Ecorr) for HYA-SD coated CC is -0.059

v, whereas that of SiC-HYA-SD coated CC is -0.033 v. The Ecorr of SiC-HYA-SD coated CC

shows a shift toward the positive side compared to that of HYA-SD coated CC, suggesting that
SiC-HYA-SD coating has better corrosion resistance than HYA-SD coating. In addition, the

improved corrosion resistance could be also demonstrated by the decreased the corrosion current

density (Icorr). The Icorr for HYA-SD coated CC is 87.7 μA/cm2 and that for SiC-HYA-SD coated

CC is 55.1 μA/cm2. The Ecorr and Icorr results confirm that the SiC-HYA-SD coating could provide

better corrosion protection than HYA-SD coating without SiC inner-layer.

4. Conclusions

SiC-HYA-SD composite coatings are prepared on CC by a combination method of pack

cementation and electrodeposition. SiC inner-layer exhibits a homogenous structure and HYA-SD

hybrid outer-layer exhibits a villous shape. SiC-HYA-SD composite coating shows better

corrosion resistance than HYA-SD coating without SiC inner-layer. SiC-HYA-SD composite

coating appears to have potential for biological application with advanced anti-corrosion property

in SBF.

Acknowledgments

This work was supported by the National Natural Science Foundation of China under Grant

No. 51521061, the Research Fund of the State Key Laboratory of Solidification Processing

(NWPU), China (Grant No. 136-QP-2015) and “111” project of china (B08040).

Reference

[1] S. Mukherjee, S.K. Nandi, B. Kundu, A. Chanda, S. Sen, P.K. Das. Enhanced bone

regeneration with carbon nanotube reinforced hydroxyapatite in animal model, Journal of the

Mechanical Behavior of Biomedical Materials. 60 (2016) 243-255.

[2] X. Ma, Z.W. He, F.X. Han, Z.Y. Zhong, L. Chen, B. Li. Preparation of

collagen/hydroxyapatite/alendronate hybrid hydrogels as potential scaffolds for bone regeneration,

Colloids and Surfaces B-Biointerfaces. 143 (2016) 81-87.

[3] S.C. Cox, J.A. Thornby, G.J. Gibbons, M.A. Williams, K.K. Mallick. 3D printing of porous

hydroxyapatite scaffolds intended for use in bone tissue engineering applications, Materials

Science & Engineering C-Materials for Biological Applications. 47 (2015) 237-247.

[4] Y.C. Tsui, C. Doyle, T.W. Clyne. Plasma sprayed hydroxyapatite coatings on titanium

substrates Part 1: Mechanical properties and residual stress levels, Biomaterials. 19 (1998)

2015-2029.

[5] N. Koga, K. Ishikawa, K. Tsuru, I. Takahashi. Effects of acidic calcium phosphate

concentration on mechanical strength of porous calcite fabricated by bridging with dicalcium

phosphate dihydrate, Ceramics International. 42 (2016) 7912-7917.

[6] X. Li, Z.Y. Weng, W. Yuan, X.Z. Luo, H.M. Wong, X.M. Liu, S.L. Wu, K.W.K. Yeung, Y.F.

Zheng, P.K. Chu. Corrosion resistance of dicalcium phosphate dihydrate/poly(lactic-co-glycolic

acid) hybrid coating on AZ31 magnesium alloy, Corrosion Science. 102 (2016) 209-221.

[7] G.A. Fielding, M. Roy, A. Bandyopadhyay, S. Bose. Antibacterial and biological

characteristics of silver containing and strontium doped plasmasprayed hydroxyapatite coatings,

Acta Biomaterialia. 8 (2012) 3144-3152.

[8] M. Mhaede, F. Pastorek, B. Hadzima. Influence of shot peening on corrosion properties of

biocompatible magnesium alloy AZ31 coated by dicalcium phosphate dihydrate (DCPD),

Materials Science & Engineering C-Materials for Biological Applications. 39 (2014) 330-335.

[9] C. Capuccini, P. Torricelli, E. Boanini, M. Gazzano, R. Giardino, A. Bigi. Interaction of

Sr-doped hydroxyapatite nanocrystals with osteoclast and osteoblast-like cells, Journal of

Biomedical Materials Research Part A. 89 (2009) 594-600.

[10] V. Aina, L. Bergandi, G. Lusvardi, G. Malavasi, F.E. Imrie, I.R. Gibson, G. Cerrato, D.

Ghigo. Sr-containing hydroxyapatite: morphologies of HA crystals and bioactivity on osteoblast

cells, Materials Science & Engineering C-Materials for Biological Applications. 33 (2013)

1132-1142.

[11] P. Melnikov, R.V. Goncalves. Preparation and characterization of strontium hydroxyapatite

suitable for orthopedic applications, Materials Letters. 150 (2015) 89-92.

[12] S. Federico, U. Nochel, C. Lowenberg, A. Lendlein, A.T. Neffe. Supramolecular hydrogel

networks formed by molecular recognition of collagen and a peptide grafted to hyaluronic acid,

Acta Biomaterialia. 38 (2016) 1-10.

[13] S. Subramaniam, Y.H. Fang, S. Sivasubramanian, F.H. Lin, C.P. Lin.

Hydroxyapatite-calcium sulfate-hyaluronic acid composite encapsulated with collagenase as bone

substitute for alveolar bone regeneration, Biomaterials. 74 (2016) 99-108.

[14] Y.X. Huang, X.L. Zhang, A.M. Wu, H.Z. Xu. An injectable nano-hydroxyapatite

(n-HA)/glycol chitosan (G-CS)/hyaluronic acid (HyA) composite hydrogel for bone tissue

engineering， Rsc Advances. 6 (2016) 33529-33536.

[15] A. Dey, U. Koli, P. Dandekar, R. Jain. Investigating behaviour of polymers in nanoparticles

of chitosan oligosaccharides coated with hyaluronic acid, Polymer. 93 (2016) 44-52.

[16] S.S. Kelkar, T.K. Hill, F.C. Marini, A.M. Mohs. Near infrared fluorescent nanoparticles

based on hyaluronic acid: Self-assembly, optical properties, and cell interaction, Acta

Biomaterialia. 36 (2016) 112-121.

[17] B.S. Mojarad, A. Nourbakhsh, R.E. Kahrizsangi, M. Masoud, K.J.D. MacKenzie. Synthesis

of nanostructured SiC by magnesiothermal reduction of silica from zeolite ZSM-5 and carbon:
The effect of carbons from different sources, Ceramics International. 41 (2015) 5287-5293.

[18] H.B. Ouyang, H.J. Li, L.H. Qi, Z.J. Li, J Wei, J.F. Wei. Synthesis of a silicon carbide coating

on carbon fibers by deposition of a layer of pyrolytic carbon and reacting it with silicon monoxide,

Carbon. 46 (2008) 1339-1344.

[19] L. Wu, X.X. Xu, L.Z. Wang, X.F. Rong, C.Tian, J.S. Zhang. Study on cytocompatability and

animal implantation test of foam SiC, Journal of Inorganic Materials. 25(2010)211-215.

[20] D.M. Vranceanu, C.M. Cotrut, M. Bramowicz, I. Titorencu, S. Kulesza, A. Kiss, A.

Berbecaru, V. Pruna, M. Branzei, A. Vladescu. Osseointegration of sputtered SiC-added

hydroxyapatite for orthopaedic applications, Ceramics International. 42(2016)10085-10093.

[21] S. Santavirta, M. Takagi, L. Nordsletten, A. Anttila, R. Lappalainen, Y.T. Konttinen.

Biocompatibility of silicon carbide in colony formation test in vitro. A promising new ceramic

THR implant coating material, Archives of Orthopaedic and Trauma Surgery. 118(1998)89-91.

[22] P. Aspenberg, A. Anttil, Y. T. Konttinen, R. Lappalainen, S. B. Goodman, L. Nordsletten, S.

Santavirta. Benign response to particles of diamond and SiC: bone chamber studies of new joint

replacement coating materials in rabbits, Biomaterials. 17(1996)807-812.

[23] L.L. Zhang, H.J. Li, K.Z. Li, J.H. Lu, X.T. Shen, F.T. Lan. MG63 osteoblast-like cells

response of SiC coating for carbon/carbon composites, Surface Review and Letters. 16 (2009)

683-687.

[24] K. Suchanek, A. Bartkowiak, A. Gdowik, M. Perzanowski, S. Kac, B. Szaraniec, M.

Suchanek, M. Marszalek. Crystalline hydroxyapatite coatings synthesized under hydrothermal

conditions on modified titanium substrates, Materials Science & Engineering C 51(2015) 57-63
Figure captions

Fig.1 The schematic of SiC-HYA-SD composite coating for CC

Fig.2 SEM micrographs, EDS and XPS results of SiC inner-layer and SiC-HYA-SD composite

coating

(a) SEM micrograph of SiC inner-layer; (b, c) SEM micrograph of SiC-HYA-SD composite

coating with deposition time of 120 s; (d) SEM micrograph of SiC-HYA-SD composite coating

with deposition time of 1 h; (e) EDS spectra of SiC inner-layer and SiC-HYA-SD composite

coating; (f) XPS spectrum of SiC-HYA-SD composite coating

Fig.3 XRD patterns and Raman spectra of SiC inner-layer and SiC-HYA-SD composite coating

(a) XRD patterns; (b) Raman spectra

Fig.4 The weight gain of SiC inner-layer modified CC versus deposition time during the

electrochemical deposition process

Fig.5 TG and FTIR results of SD without HYA and HYA-SD hybrid outer-layer

(a) TG curves; (b) FTIR spectra; (c) Magnification of rectangle area in Fig.5b

Fig.6 Potentiodynamic polarization curves for HYA-SD coated CC and SiC-HYA-SD coated CC
(a) (b)

(c) (d)

(e) (f)
(a)

(b)
(a)

(b)

(c)