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S0925-8388(16)33125-5
DOI:
10.1016/j.jallcom.2016.10.017
Reference:
JALCOM 39184
To appear in:
1 October 2016
Please cite this article as: Y. Yan, H. Cao, Y. Kang, K. Yu, T. Xiao, J. Luo, Y. Deng, H. Fang, H. Xiong,
Y. Dai, Effects of Zn concentration and heat treatment on the microstructure, mechanical properties and
corrosion behavior of as-extruded Mg-Zn alloys produced by powder metallurgy, Journal of Alloys and
Compounds (2016), doi: 10.1016/j.jallcom.2016.10.017.
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Yang Yan a,b,d, Hanwen Cao b, Yijun Kang c, Kun Yu a,b,d,*, Tao Xiao c, Jie Luo a, Youwen Deng c,
Hongjie Fang a, Hanqing Xiong a,b,d, Yilong Dai a,b,d
a
Department of Materials Science and Engineering, Yantai Nanshan University, Yantai 265713,
School of Materials Science and Engineering, Central South University, Changsha 410083,
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China;
China;
The Second Xiangya Hospital, Central South University, Changsha 410011, China;
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this study, Mg-Zn alloys were fabricated by powder metallurgy and then hot extruded.
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intermetallic phases. Although solid solution treatment could reduce intermetallic
phase amounts, it caused micropores on the surface. And these micropores could
resulted in the pitting corrosion and reduce the corrosion resistance. Notably, aging
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treatment could reduce the segregation of Zn and promote the compactness and
uniformity of corrosion product layer on the surface, leading to the improvement of
corrosion resistance. In addition, the as-extruded Mg-6%Zn alloy (wt. %) aged for
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72h was harmless to L-929 cells in cytotoxicity test. Consequently, the as-extruded
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1.Introduction:
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behavior; Cytocompatibility
In recent years, magnesium and its alloys have been widely studied as
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properties [1-3]. Mg-based implants can be degraded and dissolved in the electrolytic
physiological environment like body fluids, which avoids an additional surgery to
remove these implants after bone tissues have completely healed [4]. The elastic
moduli of Mg-based implants match with those of nature bone, which can decrease
the stress shielding effect induced by a serious mismatch of moduli between natural
bone and other metal implants [5]. Besides, magnesium is one of the major essential
elements in the human body and involves in many metabolic reactions and biological
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mechanisms [6]. So far, there is few report on toxic reactions caused by too much Mg
or Mg2+ [7]. Therefore, the magnesium alloys can be developed to the implants in both
unloaded and loaded applications [8].
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However, magnesium alloys are susceptible to corroded rapidly when they are
contacted abundant aggressive ions as chlorine in body fluids, and the poor corrosion
resistance results in strength loss and limits their practical application for bone tissue
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engineering [9]. Meanwhile, the rapid degradation of magnesium alloys leads to the
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hydrogen bubble accumulation and the local pH value increase, which causes cell
death and tissue inflammation [10]. Unfortunately, most conventional magnesium
alloys with suitable corrosion rates, such as AZ31, AZ91, AM60B, and WE43, were
developed for industry applications, not for biomedical applications [11-13]. These
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alloys contain aluminum, manganese or rare earth elements (REE), which induce
latent toxic and harmful effects in the human body [14, 15]. Therefore, there is an
urgent demand to develop biodegradable magnesium alloys without Al, REE or other
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Zinc is one of the most abundant nutritionally essential elements in human body
and the Zn-containing magnesium alloys have been paid more attention lately [16, 17].
Gu et al. [18] explored the corrosion rates of several magnesium alloys and pointed
out that Zn could be one of appropriate candidates. Cai et al. [19] found that the
corrosion resistance of Mg-Zn alloys could be improved with increasing Zn content in
the range from 1 wt. % to 5 wt. %, but 7 wt. % Zn addition resulted in a network
structure of MgZn intermetallic compounds and accelerated micro-galvanic corrosion.
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Additionally, Zhang et al. [20] mentioned that the addition of 6 wt. % Zn to
magnesium matrix not only improved its mechanical properties but also decreased the
corrosion rate and exhibited good cytocompatibility. However, there are lack of
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Carboneras et al. [21] found that the pure magnesium prepared by powder metallurgy
has better mechanical properties than those of pure magnesium prepared by casting
due to its finer grain size. Meanwhile, K. Yu et al. [22] found that the mechanical
properties and corrosion behavior of the 5wt. %, 10wt. % and 15wt. %
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related to not only the reinforcement but also the magnesium alloy matrix. Therefore,
it is important to study magnesium alloys prepared by powder metallurgy and the
results will be a basis for the following research on Mg-based composites.
The microstructure generally influences mechanical properties and corrosion
behavior of biodegradable magnesium alloys [23, 24]. It is reported that hot extrusion
can greatly enhance mechanical properties and corrosion resistance of magnesium
alloys through grain refinement and redistribution of second phases [25-27].
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Meanwhile, heat treatments can be effective methods to modify the grain sizes and the
morphology of second phases, resulting to change the mechanical strengths and
corrosion rates of magnesium alloys [24, 28, 29]. It is reasonable to assume the
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suitable heat treatment which can significantly improve the mechanical properties and
corrosion resistance of as-extruded magnesium alloys prepared by powder metallurgy.
According to the Mg-Zn binary phase diagram, the maximum solubility of Zn in
and the alloy reaches a eutectic point at 375
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when the
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content of Zn is 42wt. % [30]. In this study, different Mg/Zn atomic ratios were
chosen and 6wt. %, 14.5wt. %, 25.3wt. % and 40.3wt. % Zn-Mg alloys were prepared
by power metallurgy and then hot extruded. The extruded samples were imparted by
T4, T5 and T6 respectively and a comprehensive investigation of the microstructure,
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mechanical properties and corrosion behavior of the MgZn alloys were studied.
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The Mg-x wt. % Zn (x=6.0, 14.5, 25.3 and 40.3) alloys were prepared by powder
metallurgy and the chemical composition of all experimental alloys was examined by
inductively coupled plasma atomic emission spectrometry (ICP-AES) in this
investigation to ascertain the Zn concentration. The average diameter of the Mg and
Zn powders used in the experiment was about 23.0 m and their purity was greater
than 99.95%.The Mg and Zn powders were mixed together for 8 h and the mixed
powders were cold pressed to billets. And the billets were sintered at 500-550
for 2
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h in a vacuum sinter furnace under argon gas. The exact optimistic sintered
temperature of the Mg-Zn alloys was conducted in this investigation by differential
scanning calorimetry (DSC; WCT-ZA) under a high-purity argon atmosphere and the
, 532
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, 505
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temperature with an extrusion ratio of 15:1 into bars. Finally, the bars were imparted
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by T4, T5 and T6 respectively. The abbreviation of different state alloys were showed
at Table 1. Three samples were tested for each state of alloys in each experiment and
the average values were presented as the results.
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paper, polished using 1 mm diamond paste and etched by the solution consisting of 1g
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oxalic acid, 1ml nitric acid, 1ml acetic acid and 150ml distilled water. The surface
morphology of Mg-Zn alloys before and after immersion was observed using a
Quanta-200 scanning electron microscopy (SEM) equipped with an energy dispersive
X-ray spectrometer (EDS). The phase identification and the corrosion products were
identified by X-ray diffraction (XRD; DMAX-2500X) using CuK radiation with a
wavelength of 1.5406 .
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2.3 Porosity measurement and mechanical properties
The samples for porosity measurement and mechanical properties were a diameter
of 10 mm and thickness of 20mm. The porosity of Mg-Zn alloys was measured using
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Archimedes Principle. The dimensions of the sample were measured using a Vernier
callipers to produce a total volume (V). The dry weight (mdry) measured with an
analytical balance. And then the sample was dipped into in deionized water and
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suspended from an analytical balance to obtain wet weight (mwet). All weights were in
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grams and was the density of deionized water (1 g/cm3). Thus, the porosity () of
the sample was calculated based on the following formula [31]:
= 100[1
mdry mwet
] .........................................................................................Eq1
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The compression tests of the Mg-Zn alloy specimens were measured by MTS810.
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The immersion tests included weight change testing and hydrogen collection testing.
The samples with 10mm5mm for the immersion tests were ground with 1000 grid
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for 96
hours. The Ringers solution contains 8.6 g of sodium chloride, 0.3 g of potassium
chloride, and 0.33 g of calcium chloride per liter [5]. The temperature of the solution
was controlled with an HTW-10B water bath. The ratio of the solution volume to
sample surface area was 20 ml/cm2 [32]. The original pH value of the Ringers
solution was adjusted to 7.4 to simulate the human body environment. The pH values
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were recorded using a PHSCAN10 pH sensor during the experiment. After immersion,
the samples were washed by distilled water and then dried. The weight change
(remainder) was measured by electronic balance.
up
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soaked samples were collected into a measuring cylinder and the amount of hydrogen
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The samples with dimensions of 10mm5mm and an exposed area of 1cm2 for the
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electrochemical test were ground with 1000 grid SiC sandpaper and cleaned with
ethanol. The electrochemical test was carried out at 37 0.2 C by a standard
three-electrode configuration (platinum mesh as counter, saturated calomel as
and
the
alloy
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reference
as
working
electrode)
with
CHI660C
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measured via indirect contact testing according to ISO 10993-5:1999. The
experimental samples were cultured in Dulbecco modified Eagles medium (DMEM)
with 10% fetal bovine serum in an incubator at 95% relative humidity and 5% CO2 at
10%
dilutions.
The
DMEM
acted
as
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37 0.2 C. The culture medium was replaced by 100% extraction medium or 50% or
negative
control.
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extraction medium was prepared by incubating the samples for 1, 4, and 7 days.
Subsequently, 100 ml of formazan solution was added to each sample, and the optical
density (OD) was measured using a spectrophotometer. The cell relative growth rate
(RGR) was calculated as follows [11]:
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Fig. 1(a), (b), (c) and (d) show the microstructure of the as-extruded Mg-Zn alloys
with different Zn concentrations. E1 (Fig. 1(a)) consisted of fine equiaxed grains and
row elongated grains, which were resulted from partial dynamic recrystallization
during hot extrusion [33]. As Fig. 1(b), (c) and (d) shown, more and larger coarse
intermetallic phases appeared with the increasing Zn concentration.
Fig. 1(a), (e), (f) and (g) show the microstructure of the as-extruded Mg-6%Zn
alloys imparted by different heat treatments. Compared E1, the grain size of E1-T5
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increased slightly after aging treatment and its grain boundaries were much clearer
and more regular (Fig. 1(e)). For E1-T4 and E1-T6, the grain sizes increased
obviously after solid solution treatment and several micropores were found on the
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surfaces (Fig. 1(f) and (g)). During the solid solution treatment, Mg and Zn powers
could violently diffuse at 450C and the volume shrinkage could be produced by the
different diffusion rates of Mg and Zn [34]. However, the samples were in the absence
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of pressure, which was different from the sintered process under full pressure and hot
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extrusion. Therefore, the volume shrinkage could not be reduced and was developed
to micropores with incomplete compaction [35].
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XRD patterns of the as-extruded Mg-Zn alloys are presented in Fig. 2. The XRD
results demonstrated -Mg and MgZn peaks were identified in E1 [20]. When Zn
reached 14.5wt%, MgZn2 and Zn peaks were detected and diffraction intensities of
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MgZn phase increased in E2. With Zn concentration further increasing, MgZn peaks
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decreased and the diffraction intensities of MgZn2 phase and Zn increased in E3 and
E4. Notably, the diffraction intensities of MgZn phase in E1-T5 were higher than
those of E1 due to the more MgZn precipitation during aging treatment. Besides, the
diffraction intensities of MgZn phase in E1-T4 and E1-T6 were significantly lower
than those in E1 and E1-T5, which could be explained that MgZn phase could be
dissolved during solid solution treatment.
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3.3 SEM images and EDS analysis of the as-extruded Mg-Zn alloys
The SEM images and EDS analysis of the as-extruded Mg-Zn alloys are shown in
Fig. 3. In Fig. 3(a)-(d), plenty of strike-like and coarse intermetallic phases were
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observed along the extrusion direction and their amounts increased with the
increasing Zn concentration. According to the Mg/Zn ratio of EDS analysis in Fig.
3(c), it was showed that transit order of intermetallic phase was -Mg - MgZn -
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the Mg-Zn intermetallic phases were formed at the interface of Mg and Zn due to the
diffusion of Mg and Zn powders [36]. And the diffusion of Zn in hcp Mg is faster than
that of Mg in hcp Zn, because the activation energy for Zn to migrate is less than that
of Mg and the atomic radius of Zn is smaller than that of Mg [37]. Therefore, the
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excess Zn will diffuse towards the Mg side during the sintered process and the Mg-Zn
intermetallic phases toward the Mg matrix showed the less Zn atomic content.
Combining with XRD patterns and EDS analysis, it was confirmed that MgZn
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phase along extrusion direction was the dominant intermetallic phase of E1 and E2
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(Fig. 3(a) and (b)). And MgZn2 phase was found in central of MgZn phase and a small
quantity of Zn was observed in center of strike-like and coarse intermetallic phases in
E2 (Fig. 3(b)). When more Zn added, considerable amount of intermediate phases
were formed in E3 and E4 (Fig. 3(c) and (d)), and MgZn phase decreased and more
MgZn2 phase was formed and more Zn retained. And most intermetallic phases were
MgZn2 phase in E4 (Fig. 3(d)).
The strike-like MgZn phases of E1-T5 (Fig. 1(e)) were reduced after aging
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treatment and some fine intermetallic phases were found as the arrows indicated. It
was demonstrated that aging treatment had two effects on microstructure of the
as-extruded Mg-Zn alloys prepared by powder metallurgy: 1, Reducing the strike-like
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Mg-Zn intermetallic phases; 2, Precipitating the fine intermetallic phases. After solid
solution treatment (Fig. 1(f) and (g)), most of strike-like MgZn phases of E3 and E4
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were decreased completely but some micropores were found (black region).
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higher than those of natural bone, and the elastic moduli and densities were close to
those of natural bone. Compared with E1, E2, E3 and E4, the YS, UCS and elastic
modulus values firstly got an obvious improvement with increasing Zn concentration
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and reached the highest value when Zn concentration got 14.5wt%. And then they
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with Zn concentration no more than 14.5% were more suitable for bone implant
applications.
Compared E1 and E1-T5, the YS, UCS and elastic modulus values could be
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weaken by enlarging the grain size slightly during aging treatment. Thus, the
mechanical properties of the as-extruded Mg-Zn alloys could be modified by
changing aging treatment time for matching strengths and moduli of nature bone. The
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mechanical properties of E1-T4 and E1-T6 exhibited a sharp drop and their porosities
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were obviously higher because the micropores caused by solid solution treatment
could be developed crack sources [35]. It is noted that aging treatment could decrease
porosity and reduce strike-like intermetallic phases to a more homogenous
distribution. The elimination of porosity means the reduction of micropores which
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could act as stress concentrators and be easily developed to the fracture cracks and
reduced the load-bearing capacity of material [35]. Besides, the homogenization of
intermetallic phase could reduce spatial heterogeneity and improve the mechanical
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aging treatment can offer enough mechanical properties for orthopedic applications.
Mg-Zn alloys in simulated body fluid. When immersed in Ringers solution, the
Mg-Zn alloys release H2 gas and are converted by corrosion products such as
Mg(OH)2, according to Eq3 [41].
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MgMg2+ + 2e- (anodic reaction)
2H2O +2eH2 + 2OH- (cathodic reaction)
Mg+2H2OH2 + Mg (OH)2 (overall reaction).........................................................Eq3
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Zn can be oxidized into Zn2+ (Eq4) and Mg is able to remove some Zn2+ (Eq5)
because Mg is more active than Zn, then Zn2+ react with OH- to form Zn(OH)2 near
the sample surface (Eq6) [42-44].
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ZnZn2++2e-.............................................................................................................Eq4
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Mg+Zn2+Mg2++Zn................................................................................................Eq5
Zn+2H2OH2 + Zn (OH)2.......................................................................................Eq6
Though the metal hydroxides can be precipitate on the surface and from the
protective film, chloride ions in the Ringers solution dissolve them and transform
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into soluble MgCl2 or Zn2+ [1]. Compared with Mg(OH)2, the solubility of Zn(OH)2
are much lower than Mg(OH)2, moreover Zn(OH)2 can be changed to stable ZnO,
which can enhance the protectiveness of the passive film[43, 45].
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Zn(OH)2ZnO+H2O................................................................................................Eq7
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more corrosion products adhered on the surface and reduced the reaction area with
Ringers solution, resulting the corrosion rate reduction [47]. Finally, the formation of
corrosion product and the dissolution of corrosion product caused by chloride ions
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reached the dynamic balance and pH value was stable [3]. The sequence of the
stability pH values at 40h was E1-T5 < E1 < E1-T6 < E1-T4 < E2 < E3 < E4.
However, the excessively high pH value can lead to cell death and bone tissue
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inflammation [11, 48]. Therefore, E1 and E1-T5 with lower stability pH values are
Fig. 5 shows the hydrogen evolution of the as-extruded Mg-Zn alloys during 96
hours of immersion. The hydrogen volume increased with immersion time prolonging
and hydrogen evolution rate during 96 hours of immersion increased in the order of
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E1-T5 < E1 < E1-T6 < E1-T4 < E2 < E3 < E4, which revealed corrosion rates.
Fig. 6 demonstrates the weight change (remainder) of the as-extruded Mg-Zn alloys
Eq8
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in Ringers solution for 168 h of immersion. The weight change was determined by
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C= (m1-m0)/m0...........................................................................................................Eq8
where C is the remainder, m1 is the weight with different immersion time and m0 is
the original weight. In this experiment, the samples were dried and weighed without
removing corrosion product. In this case, the sample remainder could more clearly
reflect the integrity, and a higher remainder meant a better integrity and a lower
strengths loss. At 96h, the remainder of E1-T4, E1-T6, E2, E3 and E4 dropped faster
than that of E1 and E1-T5. Consequentially, the immersion test results showed E1-T5
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had the highest corrosion resistance.
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Fig. 7 shows the XRD patterns of the as-extruded Mg-Zn alloys after immersion in
Ringers solution for 72 h. The Mg, Mg(OH)2 and ZnO peaks were observed. The
Mg(OH)2 was the main corrosion product and the Mg(OH)2 peak values displayed
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concentration was more than 14.5 and the higher ZnO peak values also were showed
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Fig. 8 shows the surface morphology of the as-extruded Mg-Zn alloys after
immersion in Ringers solution for 72h. Some strike-like Mg(OH)2 was adhered on
the surface of E1 along the extrusion direction (Fig. 8(a)). It was because that
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magnesium matrix around the intermetallic phases was preferentially attacked due to
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micro-galvanic corrosion and corrosion products were attached [49]. However, the
Mg(OH)2 layer could not cover the whole of alloy matrix completely and the surface
exposed to Ringers solution would be further corroded. The surfaces of E2, E3 and
E4 (Fig. 8(b), (c) and (d)) were covered with plenty of corrosion products and some
deep corrosion pits were found. The depth and number of corrosion pits increased
with the increasing Zn concentration. The enlarged views of the corrosion pits showed
that corrosion cracks existed on the pit walls where Ringers solution could permeate
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through the corrosion product layer and react with the fresh alloy matrix [47]. The
more Zn concentration caused more large-size intermetallic phases which accelerated
micro-galvanic corrosion and reduced the corrosion resistance [49, 50]. And the EDS
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was compact and almost no crack was found, which indicated the corrosion product
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layer could effectively provide alloy matrix from Ringers solution and reduce the
further corrosion. The uneven corrosion product layer with the large-sized peeling
were observed on the surface of E3 and E4 (Fig. 8(f) and (g)). It could be explained
that the micropores prepared by solid solution treatment promoted the accumulation
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of Cl- and resulted in the severe pitting corrosion and localized corrosion.
In order to further the study corrosion behavior of the as-extruded Mg-Zn alloys,
the sample surfaces with corrosion products removed are showed in Fig. 9. The
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corrosion products were removed using a boiling 20% chromic acid +1% AgNO3
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solution and cleaned by absolute ethanol. The same strike-like corrosion pits on the
surface of E1 and E1-T5 were found (Fig. 9(a) and (e)). And the corrosion product
layer of E1-T5 with shallower corrosion pits was flatter and more uniform, and the
localized corrosion was more difficult to occur [28]. As Fig. 9(b), (c) and (d) shown,
the area of Zn and Mg-Zn intermetallic phases retained but the magnesium matrix
disappeared, which proved that their galvanic corrosion was serious. E1-T4 and
E1-T6 were attacked severe local corrosion (Fig. 10(f) and (g)). Solid solution
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treatment reduced the amount of intermetallic phases and micro-galvanic corrosion,
however, micropores were caused at the same time and decrease their corrosion
resistance.
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The results indicated that lower Zn concentration and aging treatment enhanced
corrosion resistance of the as-extruded Mg-Zn alloys by impart their microstructure.
E1-T5 with fine grain and more uniform intermetallic phase distribution showed the
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Mg-Zn alloys presented passivize stages due to the presence of protective layer on the
surface [51]. And the cathodic polarization curves were associated with hydrogen
evolution reactions [52]. Ecorr values of the as-extruded Mg-Zn alloys with different
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Zn concentrations increased in the following order: E1 < E2 < E3 < E4, which
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indicated the adding Zn more than 6% had a positive influence on Ecorr [53]. Besides,
Icorr values increased and Rp values decreased with the increasing Zn concentration
and E1 presented better corrosion resistance because more adding Zn resulted in more
intermetallic phases and Zn particles that acted as a cathode during the micro-galvanic
corrosion and caused more severe corrosion [54, 55].
The Ecorr of E1-T4 and E1-T6 were more positive than that of E1, but the Icorr was
higher and Rp was much lower. It was because that solid solution treatment reduced
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the intermetallic phase amount and enhanced corrosion potential, however, the
micropores formed during the solid solution treatment increased the corrosion current
density and decreased the corrosion resistance. Compared E1 and E1-T5, it could be
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found that aging treatment could enhanced Ecorr, which was agree with previous
results [56]. And E1-T5 showed the lowest Icorr and the highest Rp of all as-extruded
Mg-Zn alloys because aging treatment could reduce strike-like intermetallic phases
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are shown in Fig. 11. The results showed that no significant differences could be
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detected between the RGRs of the cells in the extracts and those in the negative
control. According to the ISO 10993-5:1999 standard, the cytotoxicity of these
extracts of E-T5 was grade 01. Thus, the as-extruded Mg-6%Zn alloy imparted by
aging treatment was innocuous and was suitable for cellular applications.
Conclusions
1. The as-extruded MgZn alloys prepared by powder metallurgy consisted of fine
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equiaxed grains and row elongated grains. With the increasing Zn concentration, more
strike-like and coarse intermetallic phases were found. When adding Zn was 6%
(wt. %) and 14.5%, MgZn phases were the dominant intermetallic phases and when
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the addition of Zn reached 25.3% and 40.3%, plenty of MgZn2 phases and Zn were
formed. From Mg matrix to the central of Zn particle, transit order of intermetallic
phase was -Mg - MgZn - MgZn2 - Zn, which demonstrated the diffusion between Mg
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and Zn. The solid solution treatment could increase grain size obviously and decrease
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most strike-like intermetallic phases, but it also caused micropores on the surface due
to Kirkendall effect. The aging treatment had two effects on microstructure of the
as-extruded Mg-Zn alloys: 1, Reducing the strike-like intermetallic phases; 2,
Precipitating the fine intermetallic phases.
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2. The compressive strengths of the as-extruded Mg-Zn alloys were much higher
than those of natural bone and the elastic moduli were close to that of natural bone.
When Zn concentration got 14.5wt%, the YS, UCS and modulus values reached the
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the large-sized strike-like and coarse intermetallic phases could easily be developed
crack sources during the compression test. The micropores caused by solid solution
treatment leaded to a sharp drop in mechanical properties and an oblivious increase of
porosity. The aging treatment could decrease porosity and reduce strike-like
intermetallic phases, resulting in the improvement of mechanical properties.
3. The more Zn concentration caused more large-size intermetallic phases and
resulted more severe micro-galvanic corrosion. The micropores caused by solid
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solution treatment could promote the accumulation of Cl- and result in the severe
pitting corrosion and localized corrosion. The as-extruded Mg-6%Zn alloy imparted
by aging treatment with fine grain, a small quantity of strike-like intermetallic phases
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and more uniform Zn distribution showed a better ability to keep the sample integrity
and the best corrosion resistance. The Mg(OH)2 was the main composition of
corrosion products and ZnO appeared with more Zn concentration.
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alloy imparted by aging treatment showed that the cells were normal and healthy in
different extracts, which demonstrated its good biosafety. And the as-extruded
Mg-6%Zn alloy imparted by aging treatment can be considered for further
Acknowledgements
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The authors acknowledge the Project (81472058) supported by the National Natural
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Science Foundation of China and The financial support of the 2015 ShanDong
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Table 1. The abbreviation of different state Mg-Zn alloys
Design component (wt. %)
State
E1
Mg-6%Zn
as-extruded
E2
Mg-14.5%Zn
as-extruded
E3
Mg-25.3%Zn
as-extruded
E4
Mg-40.3%Zn
as-extruded
E1-T4
Mg-6%Zn
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Abbreviation
for 12h
E1-T6
Mg-6%Zn
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Mg-6%Zn
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E1-T5
for 24h
for 24h
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Table 2. Porosity and mechanical properties of the as-extruded Mg-Zn alloys
Porosity(%)
Density(g/cm3)
YS(MPa)
UCS(MPa)
Modulus(GPa)
Elongation(%)
E1
1.5
1.81
220.6
373.5
40.8
11.7
E1-T5
0.6
1.82
213.7
365.5
39.6
10.6
E1-T4
9.2
1.66
185.3
342.5
E1-T6
8.7
1.67
176.5
337.2
E2
1.8
1.92
239.5
396.3
E3
2.1
2.07
218.9
E4
2.4
2.60
bone[38,39]
Ti alloy[38,39]
7.68.3
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steel[38]
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Stainless
4.44.5
8.8
36.1
8.2
43.1
10.4
41.3
11.5
354.6
38.6
12.5
130180
320
1.072.10
7581117
110117
480834
70230
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36.7
371.7
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Natural
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Material
206.4
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Table 3. The corrosion parameters of the as-extruded Mg-Zn alloys from polarization curves
Sample
E4
E3
E2
E1-T4
E1-T6
E1
E1-T5
-1.464
-1.484
-1.501
-1.530
-1.523
-1.557
-1.542
Icorr (Acm-2)
132.2
80.3
54.2
19.9
17.3
15.9
9.3
Rp (kcm2)
37.3
55.4
86.2
217
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259.2
272.1
414.4
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a
row elongated grains
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250m
250m
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250m
250m
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micropores
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250m
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Fig.1. Optical micrographs of the as-extruded Mg-Zn alloys: (a) E1, (b) E2, (c) E3, (d) E4, (e)
E1-T5, (f) E1-T4 and (g) E1-T6
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a
MgZn
MgZn
B
C
A
F
G
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MgZn2
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MgZn
MgZn
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MgZn2
MgZn2
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B
Element
Wt%
At%
MgK
28.44
52.40
ZnK
71.56
47.60
Element
Wt%
At%
MgK
27.76
50.81
ZnK
72.24
49.19
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Wt%
MgK
16.43
ZnK
83.57
At%
Element
Wt%
At%
34.58
MgK
93.59
97.52
65.42
ZnK
06.41
02.48
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Element
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Element
Wt%
At%
Element
Wt%
At%
MgK
29.18
52.56
MgK
17.33
36.05
ZnK
70.82
47.44
ZnK
82.67
63.95
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Element
Wt%
At%
ZnK
100.00
100.00
Element
Wt%
At%
MgK
16.96
35.45
ZnK
83.04
64.55
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At%
MgK
00.25
00.67
ZnK
99.75
99.33
Element
Wt%
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Wt%
At%
MgK
30.90
53.87
ZnK
69.10
46.13
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Element
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Fig.3. SEM micrographs and EDS analysis of the as-extruded Mg-Zn alloys: (a) E1, (b) E2,
(c) E3, (d) E4, (e) E1-T5, (f) E1-T4 and (g) E1-T6
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11.6
11.2
10.8
10.0
9.6
9.2
E4
E3
E2
E1
E1-T5
E1-T4
E1-T6
8.8
8.4
8.0
20
40
60
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pH Value
10.4
80
100
Immersion time(h)
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Fig.4. pH value variation of the as-extruded Mg-Zn alloys in Ringers solution for 96 hours
180
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160
120
100
80
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E4
E3
E2
E1
E1-T5
E1-T4
E1-T6
140
60
40
20
40
60
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20
80
100
Immersion time(h)
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Fig.5. Hydrogen evolution of the as-extruded Mg-Zn alloys in Ringers solution for 96 hours
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1.1
1.0
0.8
E4
E3
E2
E1
E1-T5
E1-T4
E1-T6
0.7
0.6
0.5
0.4
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Remainder(%)
0.9
0.3
0.1
20
40
60
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0.2
80
100
Immersion time(h)
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Fig.6. Remainder of the as-extruded Mg-Zn alloys in Ringers solution for 96 hours
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Mg
Mg(OH)2
ZnO
3200
E4
2400
E3
Intensity(A.U.)
2800
2000
E2
E1
1200
E1-T5
800
E1-T4
400
E1-T6
0
20
30
40
50
2(degree)
60
70
80
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Fig.7. XRD patterns of the as-extruded Mg-Zn alloys after 72 h of immersion in Ringers
solution
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a
b
A
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Wt%
At%
OK
48.65
59.77
MgK
48.48
39.11
ClK
01.02
00.56
ZnK
01.85
00.56
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Element
Wt%
At%
OK
MgK
42.17
45.86
55.73
39.86
ClK
01.99
01.19
ZnK
09.98
03.23
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Fig.9. SEM micrographs of the as-extruded Mg-Zn alloys with corrosion product removed
after 72 h of immersion: (a) E1, (b) E2, (c) E3, (d) E4, (e) E1-T5, (f) E1-T4 and (g) E1-T6
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-2
Log i(A/cm )
-1
-3
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E4
E3
E2
E1
E1-T5
E1-T4
E1-T6
-4
-5
-7
-1.8
-1.7
-1.6
-1.5
Potential(Vsce)
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-1.4
-1.3
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140
Negative
10% extract
50% extract
100% extract
120
80
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RGR(%)
100
60
40
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20
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Fig.11. RGRs of the L-929 cells cultured in different extracts of E1-T5. P < 0.05
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Highlights
The Mg-Zn alloys are prepared by powder metallurgy and then hot extruded.
The mechanical properties of the Mg-Zn alloys are suitable for bone implants.
The Mg-6%Zn alloy imparted by aging treatment shows the best corrosion
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resistance.