Accepted Manuscript

Full Length Article

Laser Surface Modification of Mg-Gd-Ca Alloy for Corrosion Resistance and

Biocompatibility Enhancement

Chengpeng Ma, Ge Peng, Lu Nie, Haifeng Liu, Yingchun Guan

PII: S0169-4332(18)30860-2
DOI: https://doi.org/10.1016/j.apsusc.2018.03.174
Reference: APSUSC 38922

To appear in: Applied Surface Science

Received Date: 4 January 2018

Revised Date: 16 March 2018
Accepted Date: 21 March 2018

Please cite this article as: C. Ma, G. Peng, L. Nie, H. Liu, Y. Guan, Laser Surface Modification of Mg-Gd-Ca Alloy
for Corrosion Resistance and Biocompatibility Enhancement, Applied Surface Science (2018), doi: https://doi.org/
10.1016/j.apsusc.2018.03.174

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 Laser Surface Modification of Mg-Gd-Ca Alloy for Corrosion Resistance and Biocompatibility
Enhancement

Chengpeng Maa,1, Ge Pengb,1 , Lu Niec, Haifeng Liub,3, Yingchun Guana,d,e,2,

a
School of Mechanical Engineering and Automation,
Beihang University, 37 Xueyuan Road, Beijing 100191, P.R. China
b
School of Biological Science and Medical Engineering,
Beihang University, 37 Xueyuan Road, Beijing 100191, P.R. China
c
Beijing Institute of Space Long March Vehicle, FengTai District, Beijing 100076, P.R. China
d
International Research Institute for Multidisciplinary Science,
Beihang University, 37 Xueyuan Road, Beijing 100191, P.R. China
e
National Engineering Laboratory of Additive Manufacturing for Large Metallic Components,
Beihang University, 37 Xueyuan Road, Beijing 100191, P.R. China
1
Chengpeng Ma and Ge Peng contributed equally to this work.
2
Corresponding author: E-mail: guanyingchun@buaa.edu.cn (Yingchun Guan),
3
Co-corresponding author: E-mail: haifengliu@buaa.edu.cn (Haifeng Liu).

Abstract:
Magnesium alloy has attracted much attention as biodegradable material for medical devices
including implants and stents in recent years. However, poor corrosion resistance is the main
problem to limit practical applications because high degradation rate will cause fast increase in pH,
while the large release of ions into the medium can lead to cytotoxicity. In this work, we
demonstrate the capability of laser surface modification for better corrosion resistance of Mg-Gd-Ca
alloy to avoid rapid degradation, which helps to enhance the biocompatibility. Microstructure of
both as-received surface and laser-modified surface were analyzed carefully by Scanning Electron
Microscopy and X-ray Diffraction. Electrochemical corrosion behavior and immersion test was
investigated in order to examine the degradable behavior of laser-modified Mg-Gd-Ca alloy. The
enhanced corrosion resistance was found to be caused by the combined effect of the dissolution of
secondary phase and the decrease of galvanic corrosion in the laser-modified zone. Moreover,
results of direct cell culturing suggested that the laser-modified surface exhibited good cell adhesion
property, spreading performance and proliferation capacity.

Keywords: Laser surface modification, biodegradable magnesium alloy, microstructure, corrosion

resistance, biocompatibility.

1. Introduction
Magnesium (Mg) alloys have great potential applications in biomedical implants due to their
degradation behavior in physiological environments, which would avoid a second surgery after
tissue healing and have a closer Young’s modulus to human bones than titanium alloys and stainless

1
steels [1-6]. Mg-Gd-based alloy has been researched as new potential material for medical implant
due to better biocompatibility and appropriate mechanical properties than standard commercial Mg
alloy. Gadolinium (Gd) is a suitable alloying element for Mg alloy as one of the rare earth elements
with good biocompatibility. It also contributes to solid solution strengthening precipitation
strengthening of Mg alloys, because of large solubility in Mg at the eutectic temperature and the
formation of intermetallic phases [7-10].
However, high degradation rate is still the main problem to limit medical applications of Mg
alloys. Generally, precipitate phases in Mg-Gd system are more electrochemically stable than • -Mg
matrix, which could result in galvanic corrosion at the grain boundary [10]. Rapid degradation
would cause fast increase in local pH and the large release of ions into the medium.
Correspondingly, cells are difficult to survive at Mg alloy surface, leading to reduction in cell
viability [11].
Laser surface modification has been studied as an effective anti-corrosion technology for Mg
alloys. Compared with other surface modification methods like chemical conversion, anodic
oxidation, micro-arc oxidation, organic coating, thermal spraying [12-17], the main advantages of
laser method are lack of contaminates, high surface integrity, and low cost with high quality. In the
decades, laser surface modification has been used successfully for commercial biodegradable Mg
alloys. Guan et al. [18,19] reported that laser melting refined β -Mg17Al12 phases and increased Al
concentration for AZ91 Mg alloy, resulting in about 70% decrease of corrosion rate in simulated-
modified body fluid (SBF) at 37 ℃. Ho et al.[20] studied the bio-wettability of AZ31B in SBF after
continuous-wave laser radiation, and acquired SBF contact angle decrease (from 75.0° to 41.2°) due
to refinement of grain structure and higher surface energy. Florian et al. [21] investigated that laser
irradiated AZ31B alloy obtained better corrosion resistance, and bio-wettability was also improved.
The laser irradiated samples exhibited a 50% reduction in mass loss after immersion in SBF, contact
angle measurements revealed a contact angle below 10° for the laser processed specimen compared
to a 43° angle of the as-received material. Khadka et al. [22] carried out the bio-wettability
improvement of WE54 Mg alloys using 500W Nd:YAG pulsed laser. The improved wettability was
proposed to be associated with changes in the laser treated surface chemical composition,
microstructure and surface morphology. However, it should be noted that commercial Mg alloy as
AZ series may has risks of biotoxicity caused by their Aluminum content, known to be toxic in
small amounts. No effort is available in the public domain on laser surface treatment of Mg-Gd-
based alloy. Moreover, little literature has been worked on cell culture of laser-treated Mg alloy
surface for biocompatibility test.
In this paper, the effect of laser surface modification on Mg-Gd-Ca alloy was investigated. The
aim is to establish a simple and effective approach to enhance corrosion resistance. As large metal
ion release during rapid corrosion could be the major contributing factors to influence the viability
of cells, this laser method helps to enhance the biocompatibility of Mg alloy with the enhancement
of corrosion resistance. Direct cell culture method is used to investigate initial cell adhesion and cell
viability for biocompatibility comparison between as-received and laser-modified Mg-Gd-Ca alloy.

2
2. Experimental Procedures

2.1 Materials
Hot extruded Mg-6Gd-0.6Ca (wt.%) alloy bars with a diameter of 9mm were chosen in this alloy,
because Ca exists as a solid solution element in Mg matrix and Mg-Gd eutectic phase and leads to
grain refinement and improvement of the yield strength of the alloy. 4 mm thick cylindrical slices
were cut from the extruded bars perpendicular to the extrusion direction. The slices were polished
with SiC abrasive paper and washed with ethanol. The microstructures of the alloy was etched with
a solution of 0.5% picric acid (1 g picric acid + 24 ml distilled water + 24 ml acetic acid + 200 ml
ethanol).

2.2 Laser processing

A continuous wave (CW) fiber laser (wavelength 1060 nm, spot size 100µm) was used in this study
to modify the surface of Mg-6Gd-0.6Ca alloy. The alloy surface was irradiated by the laser spot
with the power density of 2.04×106 W/cm2 and the scanning speed of 70 mm/s, there parameters
were carried out with 50% overlapping beam path. Laser beam was scanned two times in same
direction. The entire process took place under Argon gas protection.

2.3 Surface Characterization

Morphology was observed by Nikon LV150N optical microscopy (OM) and Hitachi SU8010
scanning electron microscopy (SEM) with energy dispersive spectrometer (EDS). X-ray diffraction
(XRD) was performed with a Rigaku D/max2200PC X ray diffractometer.

2.4 Biocorrosion tests

In vitro corrosion test was conducted at 37 ℃ in Hank's Balanced Salt Solution (HBSS) [23]. The
chemical composition of Hank's solution is shown in Table 1. Corrosion rates of the initial and
modified Mg-Gd-Ca alloy samples were measured by immersion test in HBSS for 2 h, 1 day, 3 days,
7 days and 14 days. After immersion, corrosion product was cleaned in a solution of 15% CrO3 +
1% AgCrO4 in 100 mL water [24]. The weight loss was measured at the end of immersion test and
the corrosion rate was calculated from the weight loss and specimen surface area in mg cm-2. Each
immersion test was performed three times to ensure sufficient statistics.
Electrochemical measurement was carried out at 37 ℃ in HBSS using a CHI660e
electrochemical workstation. A three-electrode system was employed with saturated calomel
electrode as the reference electrode, the specimen as the working electrode with an exposed surface
area of 0.64 cm2, and a carbon electrode as counter electrode. The Tafel curves of as-received and
laser-modified specimens were obtained at a scan rate of 1 mV s-1.

Table 1 Chemical composition of HBSS

Composition (mmol L-1)

3
 Na+ K+ Mg2+ Ca2+ Cl- HCO3- H2PO4- HPO42- SO42-
142 5.8 0.8 2.5 145 4.2 0.4 0.3 0.8

2.5 Cell culture

A mouse embryo osteoblast precursor (MC3T3-E1) cell line was used to investigate the in vitro
biocompatibility of the alloy materials. MC3T3-E1 were cultured in DMEM medium containing
10% fetal bovine serum (FBS). The osteoblast-like cells placed in culture dishes were cultured in
cell incubator with 5% CO2 at 37 ℃.

2.6 Cell viability and cell morphology on specimens

The specimens were exposure to ultraviolet-light radiation for 24h to sterilize. MC3T3-E1 cells
were seeded at a density of 7 × 104 cells per specimen placed into 24-well plate by adding 70 µL cell
suspension onto the surface for cell attachment. After culturing for 2h, 4h and 24h, the cell viability
and morphology were measured. Cell viability was evaluated by CCK-8 assay according to the
reagent instruction. The optical density at 450 nm was detected with a microplate reader. An
average of three measurements was taken for each group. Cell morphology was determined by SEM.
The cell-seeded scaffolds were washed three times with phosphate buffer solution (PBS) and fixed
in paraformaldehyde for 30 min. And then, the samples were rewashed three times with PBS and
dehydrated using graded ethanol. After vacuum-drying, the specimens were sprayed with gold
particles and observed using SEM.

3. Results and discussions

3.1 Microstructure evolution

As shown in Fig. 1 and Fig. 2, as-received microstructure in the substrate mainly consisted of
equiaxed • -Mg matrix and β phase Mg5Gd particles with zonal distribution in extrusion direction
[22,25]. After laser modification, a melted layer was present at the top of specimen with the
thickness of about 360µm, while the solidification microstructure was mainly small columnar grains
of • -Mg phase [26-28]. Mg-Ca eutectic phase was no found either in substrate or melted layer. The
reason could be that Ca content is low in Mg-6Gd-0.6Ca alloy, and it only presents in solid solution
[29]. Quantitative analyses of chemical compositions in the melted layer and substrate were carried
out using EDS, as shown in Table 2. In as-received microstructure, Gd content of β phase was much
higher than that of • -Mg matrix. In laser-modified layer, no Gd-rich area was found, and the
chemical composition in the matrix was in the range of • phase and β phase. It was slightly higher
than the nominal composition of Mg-6Gd-0.6Ca alloy, which may be caused by selective
vaporization of Mg element in laser melting [30]. The uniform element distribution was likely due
to the dissolution of β phase into the laser melted layer.
During laser surface modification process, Mg alloy surface was heated by laser beam and
reached the melting temperature in very short time. After laser beam left, surface temperature of

4
laser irradiated area drops rapidly due to self-quenching, resulting in high temperature gradient and
rapid cooling rate occurred in melted layer. Therefore, there was no β phase precipitated in laser
melted layer. It is reported that higher cooling rate can increase the solid solubility of Gd in Mg,
which was contributed to the reduction of dendritic segregation of the solutes. Because the diffusion
of Gd atom in Mg matrix is slow due to the different atomic radius. The volume fraction of eutectic
could be lower than 0.7%, when the cooling rate was higher than 250K/s [31].
In the laser melting process, the cooling rates of irradiated material could be estimated from a
one-dimensional thermal model by the product of temperature gradient. The transient heat balance
equation is as follows [32]:
𝜕𝜕𝜕𝜕(𝑥𝑥, 𝑡𝑡) 𝑑𝑑 2 𝑇𝑇(𝑥𝑥, 𝑡𝑡)
= 𝐾𝐾 (𝑥𝑥 > 0) (1)
𝜕𝜕𝜕𝜕 𝑑𝑑𝑥𝑥 2
where K is the thermal diffusivity of the material and is equal to k/• Cp; k is the thermal conductivity
of the materials; • is the density of the material and Cp is the specific heat. The initial condition of T
= T0 = 298.15 K was applied at time t = 0. For Mg-Gd-Ca alloy, k ≈ 58.8 W/m K, • ≈ 2.11 g/cm3, Cp
≈ 1000 J/kg K. During cooling process of laser modification, the cooling rate of Mg alloy was
estimated as 104 K/s, which is much higher than 250 K/s. Therefore, under the rapid solidification
and cooling rate, supersaturated solid solution matrix may solidified with little dendritic segregation.
Correspondingly, the melted layers mainly consists of • -Mg phase, and columnar grains forms at
both bottom and boundary of the melting pool [33,34].

Fig.1. M icrostructure analysis of laser modified M g-G d-C a alloy.

Table 2 Chemical composition (wt. %) in positions of Mg-Gd-Ca alloy obtained from EDS analysis.

Elements Mg Gd Ca
• phase 96.4 3.2 0.4
β phase 53.7 42.9 3.4

5
 melted layer 90.2 8.7 1.1

Fig.2. X R D profiles of as-received and laser modified M g-G d-C a alloy surface.

3.2 Effect of laser surface modification on electrochemical behavior and corrosion rates
The polarization curves of as-received and laser modified Mg-Gd-Ca alloy in HBSS are presented in
Fig. 3. The values of corrosion potential (Ecorr), Tafel slope (β c) and the corrosion current density
(icorr) for each curve are listed in Table 3. As shown in Fig. 3, corrosion potential Ecorr of laser
modified Mg-Gd-Ca alloy exhibited less negative value (-1.522 V) than untreated specimen (-1.566
V). It implied less corrosion susceptibility for the laser-modified surface, which is in agreement with
the results of immersion tests (Fig. 4). Furthermore, cathodic current icorr of laser modified Mg-Gd-
Ca was much lower than the as-received, indicating lower corrosion rates.

Fig.3. Potentiodynamic polarization curves for as-received and laser modified Mg-Gd-Ca alloy in HBSS.

6
 Table 3 Ecorr, β c and icorr values for as-received and laser modified Mg-Gd-Ca alloy in HBSS

-2
Specimen E (V) β c(V) I (mA cm )
corr corr

As-received -1.566 0.213 0.0535

Laser modified -1.522 0.188 0.0053

Fig.4 shows the curves of weight loss versus immersion time of the laser-modified and as-received
specimens. All laser-modified specimen with different immersion time showed lower corrosion rate
than the as-received samples. It is known that β -Mg5Gd phase in as-received microstructure acts as a
galvanic cathode accelerating corrosion of matrix [35,36]. After laser surface modification, the
amount of galvanic corrosion reduced significantly due to the dissolution of β phase into the matrix.
As shown in Fig.5, for the laser-modified specimen, corrosion started initially at small pits found
with uniform distribution on the whole surface, resulting in uniform corrosion in • -Mg matrix
surface later. While in the initial 2 h exposure of as-received specimen in HBSS, localized corrosion
occurred in the matrix due to strong galvanic couple at the β phase/magnesium matrix interface.
After immersion for 3 days and 2 weeks, galvanic corrosion accelerated and extended into deeper
corrosion holes, caused higher weigh loss rate than laser-modified specimen. Such results suggest
that laser modification has significant influence on corrosion behavior of the magnesium alloy due
to the dissolution of β phase. This is in agreement with previous finding that the corrosion resistance
was improved with the less micro-segregation structures due to uniform distribution of alloying
elements [29]. The effect could be caused by dissolution of the intermetallic phases following rapid
cooling rate associated with the laser process.

Fig.4. C orrosion rate for as-received and laser-modified specimens in H B S S as a function of exposure time.

7
 (a)

(b)
Fig.5. (a) S E M showing corroded surfaces of laser-modified and as-received specimens, in H B S S after
exposure for 2 hours, 3 days, 14 days. (b) area A marked in (a).

3.3 In vitro biocompatibility

The cytotoxicity evaluation of Mg alloys is essential for their applications in biomedical
engineering. The result of cell viability was shown in Fig. 6. After 2 h of seeding, the average
optical density (OD) value of the laser-modified group was 4 times higher than that of the as-
received group. At each incubation time-point, OD quantity of as-received group maintained low
value. While the laser-modified specimens promoted the proliferation of MC3T3-E1 cells with the
increase of incubation time. As shown in Fig.7, there were no cells survived on the surface of as-
received specimen during the detection periods. After culturing for 24h, the corrosion was
aggravated and rod-like crystals formed on the surface. On the contrary, MC3T3-E1 cells exhibited
a good adhesion behavior, spreading performance and proliferation capacity on the laser-modified
group. After being incubated for 2h, the cells had already started to extended filiform pseudopodia

8
and retained spherical morphology at the same time. Cells spread with a flattened spindle shape on
the surface of laser-modified samples at 4h. After 24h of culture, the cells proliferated and covered
over the entire specimen surface. The enhanced cell behavior might be due to the reduced
degradation rate. The high pH value and high Mg2+ ion concentration caused by rapid corrosion rate
of as-received samples might be the major contributing factor to influence the viability of MC3T3-
E1 cells [37-39].

Fig.6. MC3T3-E1 cell proliferation on surfaces of different samples evaluated by CCK-8 test.

** indicates significant differences of P < 0.01.

Fig.7. SEM morphology of MC3T3-E1 cells cultured on laser-modified and as-received specimens.

9
4. Conclusions
Microstructure evolution, corrosion behavior and biocompatibility of Mg-6Gd-0.6Ca alloy after
laser surface modification was carefully examined. The main findings may be summarized as
follows:
1. As-received microstructure mainly consisted of equiaxed • -Mg phase as the matrix and β -
Mg5Gd phase particles distributed in the matrix along extrusion direction. After laser surface
modification, solidification microstructure was changed to • -Mg phase, and no β phase grains
precipitated along grain boundaries. The thickness laser-modified layer was about 360µm.
2. For as-received specimen, initial galvanic corrosion occurred preferentially in a-Mg matrix
around β phase and extended into deep corrosion holes. After laser surface modification,
dissolution of β phase in the melted region led to uniform corrosion in the laser-modified
specimens. Therefore, the amount of galvanic couples was decreased significantly, and the
corrosion rate was much lower than that of as-received materials.
3. Due to high degradation rate, as-received specimen showed cytotoxicity of MC3T3-E1 cells.
No cells survived on the surface during the culturing periods. With enhanced corrosion
resistance, laser-modified specimens exhibited good biocompatibility. In vitro cell culture
showed that MC3T3-E1 cells survived on the surface of laser-modified specimens, and
significant improvements were illustrated by good adhesion property, spreading performance
and proliferation capacity.

Acknowledgments
Support by the National Program of Key Research in Additive Manufacturing and Laser
Manufacturing of China with grant number 2016YFB1102503, National Key Basic Research
Program of China with grant number 2015CB059900, Beijing Natural Science Foundation with
grant number 3162019, Fundamental Research Funds for the Central Universities from Beihang
University with project code 74003401.

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 Highlights
• One-stop laser method for corrosion resistance and biocompatibility enhancement of
Mg alloy was developed.
• No secondary phase precipitated in laser-modified layer with thickness of 360µm was
investigated.
• Both secondary phase dissolution and galvanic corrosion reduction took place at laser-
modified surfaces.
• In vitro cells were survived successfully at laser-modified surfaces, while cytotoxicity
occurred at as-received surface.
• Biocompatibility enhancement were caused by good adhesion, spreading and
proliferation.

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