表面机械研磨对医用钛合金生物活性的影响

doi:10.7503/cjcu20160909

摘要/Abstract

摘要：

采用表面机械研磨(SMAT)法对Ti-25Nb-3Mo-3Zr-2Sn(TLM)钛合金进行了处理, 并考察了SMAT处理前后钛合金样品表面的生物仿生矿化、蛋白吸附及成骨细胞的黏附行为. 表征结果显示, SMAT处理不会改变TLM钛合金样品表面的物相组成及晶粒尺寸, 但会显著改变合金的表面粗糙度、拓扑结构、亲水性及表面不同化学态氧元素的含量. 在模拟体液中浸泡28 d后, 未经SMAT处理的TLM钛合金样品表面没有检测到新化合物的生成, 而经SMAT处理后的合金样品表面已诱导出直径为1~2 μm、钙磷比约为1.58的羟基磷灰石前驱物. 体外实验结果表明, SMAT处理后的钛合金样品表面能从血清中吸附更大数量的蛋白, 且成骨细胞在处理后的样品表面表现出更好的黏附状态. 经SMAT处理后的钛合金样品表面表现出更强的生物矿化、蛋白吸附及促细胞黏附能力, 这与其表面具有更大的表面粗糙度、更好的亲水性及富含更多的基础Ti—OH基团有关.

关键词: 表面机械研磨, 钛合金, 生物矿化, 蛋白吸附, 成骨细胞

Abstract:

Ti-25Nb-3Mo-3Zr-2Sn(TLM) titanium alloy was treated via surface mechanical attrition treatment(SMAT) method in this paper, subsequently the biomineralization, protein adsorption and osteoblast adhesion behaviors of treated and untreated titanium alloy samples were explored. The characteristic results by means of XRD, OM, TEM, AFM, XPS, SEM, EDX and contact angle experiment revealed that SMAT process did not alter the phase composition and grain size of TLM samples, however, it would obviously alter the surface roughness, topography, hydrophilicity and oxygen content of different chemical state of TLM samples. After immersed in the simulated body fluid solutions for 28 d, no new chemical compounds were detected on the untreated surface, nevertheless, hydroxyapatite precursor with a diameter of 1—2 μm and Ca/P ratio of 1.58 was observed on the treated surface. In vitro experimental results showed that the SMAT-treated sample could adsorb more proteins from the serum and osteoblasts exhibited much better adhesion condition on its surface. The SMAT-treated sample possessed superior biomineralization, protein adsorption and cellular adhesion-promoted capacity to the untreated sample, which was related with much larger surface roughness, better hydrophilicity and higher content of basic Ti—OH contained on the SMAT-treated surface.

Key words: Surface mechanical attirion treatment(SMAT), Titanium alloy, Biomineralization, Protein adsorption, Osteoblast

中图分类号:

O614

TrendMD:

黄润, 潘成岭, 张兰. 表面机械研磨对医用钛合金生物活性的影响. 高等学校化学学报, 2017, 38(4): 522.

HUANG Run, PAN Chengling*, ZHANG Lan. Effect of Surface Mechanical Attrition Treatment on Bioactivity of Biomedical Titanium Alloy^†. Chem. J. Chinese Universities, 2017, 38(4): 522.

图/表 13

Table 1 Chemical composition of TLM titanium alloy

Element	Ti	Nb	Mo	Sn	Zr	C	N	H	O	Fe
Content/(%, mass ratio)	66.687	25.1	2.90	2.02	3.08	0.01	0.03	0.003	0.14	0.03

Table 2 Ion concentrations of SBF and human blood plasma[20]

Ion	Ion concentration/(mmol·L^-1)
Ion	Blood	SBF
Na⁺	142.0	142.0
K⁺	5.0	5.0
Mg²⁺	1.5	1.5
Ca²⁺	2.5	2.5
Cl^-	103.0	147.8
HC	27.0	4.2
HP	1.0	1.0
S	0.5	0.5
pH	7.2—7.4	7.40

Fig.1 XRD patterns of TLM(a) and SMAT-TLM(b) samples

Fig.2 Optical microscope picture of the TLM sample(A) and TEM image taken from the

Fig.3 AFM images of the TLM(A) and SMAT-TLM(B) surfaces

Table 3 Surface roughness of different samples

Sample	Surface roughness/nm
Sample	R_a	R_q	R_z
TLM	14.7±1.5	22.9±2.1	51.6±3.8
SMAT-TLM	32.6±2.9	49.2±3.5	98.4±6.8

Fig.4 Water droplet contact angles of the TLM(A) and SMAT-TLM(B) surfaces

Fig.5 O1s XPS spectra of the TLM(a) and SMAT-TLM(b) surfaces

Table 4 Area percent of the O1s peaks at different binding energies

Sample	Area percent of O_1s peak(%)
Sample	530.1 eV	531.3 eV	532.8 eV
SMAT-TLM	59.6	18.7	21.7
TLM	50.4	35.5	14.1

Fig.6 SEM images of the TLM(A) and SMAT-TLM(B) surfaces after immersed in SBF solution for 28 d The inset in (B) is the magnified image of the white dotted square.

Fig.7 EDX spectrum of the point marked with letter I in the inset of Fig.6(B)

Fig.8 Total protein adsorbed onto TLM and SMAT-TLM surfaces after 1, 4 and 24 h of incubation in DMEMData are presented as the mean±SD, n=5, * P<0.05 compared with the TLM surface.

Fig.9 SEM-BSE images of osteoblasts cultured for 4 h on TLM(A) and SMAT-TLM(B) surfaces

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