技术领域technical field
本发明涉及一种块体非晶合金材料，更具体地说，是一种具有优良的生物相容性的生物医用可降解Mg-Zn-Ca-Sr系块体非晶合金及其制备方法。The invention relates to a bulk amorphous alloy material, more specifically, a biomedical degradable Mg-Zn-Ca-Sr bulk amorphous alloy with excellent biocompatibility and a preparation method thereof.
背景技术Background technique
生物医用可降解材料是一种新型生物医用材料，它的广泛使用可以避免不可降解植入材料植入后再取出的二次手术及手术给患者带来的痛苦，其研发和应用对人类健康和医学发展具有重要意义。生物医用可降解镁合金由于①具有较高的腐蚀速率，可以实现体内降解的功能；②较小的弹性模量能够弱化应力遮挡效应；③较高的生物安全性，其腐蚀产物很可能不仅对人体无害反而能起到促进骨愈合的作用而得到迅速发展。但是，镁合金在体内降解过程中通常伴有氢气的产生，这对患者骨骼及组织的愈合是非常不利的。因此控制镁合金的腐蚀速率并减少降解过程中的氢气析出是可降解镁合金设计开发的重要方向之一。Biomedical degradable material is a new type of biomedical material. Its wide use can avoid the pain caused by the secondary operation and operation after the non-degradable implant material is removed after implantation. Its development and application are of great importance to human health and The development of medicine is of great significance. Biomedical degradable magnesium alloys can realize the function of in vivo degradation due to ① high corrosion rate; ② small elastic modulus can weaken the stress shielding effect; Harmless to the human body, it can promote bone healing and develop rapidly. However, the degradation process of magnesium alloys in the body is usually accompanied by the generation of hydrogen gas, which is very detrimental to the healing of patients' bones and tissues. Therefore, controlling the corrosion rate of magnesium alloys and reducing hydrogen evolution during the degradation process is one of the important directions for the design and development of degradable magnesium alloys.
非晶合金是一种在快速冷却条件下，将原子冻结在熔融组态而获得的能在一定温度范围内保持相对稳定的亚稳态物质。非晶合金固态时原子排列呈现出短程有序、长程无序的特征，原子的三维空间呈拓扑无序状的排列。由于其特殊的原子排列结构，非晶合金并不具有晶体材料所具有的晶界与位错等缺陷，也不存在偏析、第二相等成分起伏。正是由于非晶合金这种特殊的原子结构决定了它特殊的物理、化学性能，与传统晶态材料相比非晶合金具有高强度、高硬度、大弹性应变极限、低弹性模量、高耐磨性和高耐腐蚀性能。镁基非晶合金具有优异的非晶形成能力(Mg-Cu-Gd、Mg-Cu-Ag-Gd、Mg-Cu-Ag-Y等非晶合金的尺寸可达厘米级)以及优良的力学和耐腐蚀性能，可以减少降解过程中的氢气析出。因此，镁基非晶合金在生物医用可降解材料方面具有广阔的应用前景。但是，绝大多数具有优良非晶形成能力的镁基非晶合金都含有Cu、Ni等高生物毒性元素，从而限制了镁基非晶合金在生物医用材料上的应用。因此，开发出高非晶形成能力、高强度、低弹性模量、适宜耐腐蚀性且不含有Cu、Ni等高生物毒性元素的镁基块体非晶合金材料，对于生物医用可降解材料的应用及非晶合金材料的发展都具有重要的意义。Amorphous alloy is a kind of metastable substance which can keep relatively stable within a certain temperature range obtained by freezing atoms in a molten configuration under rapid cooling conditions. In the solid state, the atomic arrangement of amorphous alloys presents the characteristics of short-range order and long-range disorder, and the three-dimensional space of atoms is arranged in a topologically disordered manner. Due to its special atomic arrangement structure, amorphous alloys do not have defects such as grain boundaries and dislocations that crystalline materials have, and do not have segregation and second-equivalent composition fluctuations. It is precisely because of the special atomic structure of amorphous alloy that determines its special physical and chemical properties. Compared with traditional crystalline materials, amorphous alloy has high strength, high hardness, large elastic strain limit, low elastic modulus, high Wear resistance and high corrosion resistance. Magnesium-based amorphous alloys have excellent amorphous forming ability (the size of amorphous alloys such as Mg-Cu-Gd, Mg-Cu-Ag-Gd, Mg-Cu-Ag-Y can reach centimeter level) and excellent mechanical and Corrosion resistance, can reduce hydrogen evolution during degradation. Therefore, magnesium-based amorphous alloys have broad application prospects in biomedical degradable materials. However, most Mg-based amorphous alloys with excellent amorphous-forming ability contain highly biotoxic elements such as Cu and Ni, which limits the application of Mg-based amorphous alloys in biomedical materials. Therefore, the development of magnesium-based bulk amorphous alloy materials with high amorphous forming ability, high strength, low elastic modulus, suitable corrosion resistance, and no highly biotoxic elements such as Cu and Ni is suitable for biomedical degradable materials. The application and development of amorphous alloy materials are of great significance.
发明内容Contents of the invention
本发明技术解决问题：为了提高镁基非晶合金的耐腐蚀性、力学性能和生物相容性，本发明公开了一种MgaZnbCacSrd非晶合金。通过向Mg-Zn-Ca系非晶合金中添加微量Sr元素进行合金化，从而提高体系非晶形成能力，提高力学性能，并且在模拟人体溶液中的耐腐蚀性能增强，腐蚀速率降低。The invention technically solves the problem: in order to improve the corrosion resistance, mechanical properties and biocompatibility of the magnesium-based amorphous alloy, the invention discloses a Mga Znb CacSrd amorphous alloy. By adding a small amount of Sr element to the Mg-Zn-Ca series amorphous alloy for alloying, the amorphous formation ability of the system is improved, the mechanical properties are improved, and the corrosion resistance in the simulated human body solution is enhanced and the corrosion rate is reduced.
本发明是一种生物医用可降解镁基块体非晶合金，该合金的化学成分为MgaZnbCacSrd，其中a的原子百分比为60～73，b的原子百分比为22～35，c的原子百分比为2～6，d的原子百分比为0～2，且a+b+c+d＝100。The invention is a biomedical degradable magnesium-based bulk amorphous alloy. The chemical composition of the alloy is Mga Znb CacSrd , wherein the atomic percentage of a is 60-73, and the atomic percentage of b is 22-35 , the atomic percentage of c is 2-6, the atomic percentage of d is 0-2, and a+b+c+d=100.
所述a的原子百分比为60～65，b的原子百分比为29～35，c的原子百分比为2～6，d的原子百分比为0～2，且a+b+c+d＝100。此成分合金断裂强度高，腐蚀速率较低，适用于老年患者、骨质疏松病患者等所需治愈时间较长的患者。The atomic percentage of a is 60-65, the atomic percentage of b is 29-35, the atomic percentage of c is 2-6, the atomic percentage of d is 0-2, and a+b+c+d=100. This composition alloy has high fracture strength and low corrosion rate, and is suitable for elderly patients, osteoporosis patients and other patients who require a long healing time.
所述a的原子百分比为66～68，b的原子百分比为26～32，c的原子百分比为2～6，d的原子百分比为0～2，且a+b+c+d＝100。此成分合金具有优异的非晶形成能力(4～6mm)。The atomic percentage of a is 66-68, the atomic percentage of b is 26-32, the atomic percentage of c is 2-6, the atomic percentage of d is 0-2, and a+b+c+d=100. This compositional alloy has excellent amorphous-forming ability (4-6mm).
所述a的原子百分比为69～73，b的原子百分比为22～29，c的原子百分比为2～6，d的原子百分比为0～2，且a+b+c+d＝100。此成分合金杨氏模量低，腐蚀速率较快，适用于短期植入使用。The atomic percentage of a is 69-73, the atomic percentage of b is 22-29, the atomic percentage of c is 2-6, the atomic percentage of d is 0-2, and a+b+c+d=100. This composition alloy has a low Young's modulus and a fast corrosion rate, making it suitable for short-term implant use.
制得的MgaZnbCacSrd块体非晶合金的组成元素均为无生物毒性元素，不含高生物毒性的Cu和Ni元素，潜在生物毒性大大降低。The constituent elements of the prepared Mga Znb Cac Srd bulk amorphous alloy are all non-biotoxic elements, and do not contain highly biotoxic Cu and Ni elements, and the potential biotoxicity is greatly reduced.
制得的MgaZnbCacSrd块体非晶合金具有较高的非晶形成能力，非晶形成临界尺寸为6mm。The prepared Mga Znb Cac Srd bulk amorphous alloy has high amorphous formation ability, and the critical size of amorphous formation is 6 mm.
制得的MgaZnbCacSrd块体非晶合金具有较好的力学性能，室温压缩断裂强度为750～900MPa，弹性应变为1.9％，杨氏模量为38～48GPa，比强度为2.75×105～2.9×105Nm/kg。The prepared Mga Znb Cac Srd bulk amorphous alloy has good mechanical properties, the compressive fracture strength at room temperature is 750-900MPa, the elastic strain is 1.9%, the Young's modulus is 38-48GPa, and the specific strength is 2.75×105 to 2.9×105 Nm/kg.
制得的MgaZnbCacSrd块体非晶合金在模拟人体溶液中表现出适宜的腐蚀速率(0.1～1.0mm/year)，和较低的氢气析出量，为0.02～0.15ml/(cm2·d)。The prepared Mga Znb Cac Srd bulk amorphous alloy exhibits a suitable corrosion rate (0.1-1.0mm/year) and a low hydrogen evolution rate of 0.02-0.15ml/year in simulated human body solution (cm2 ·d).
制得的MgaZnbCacSrd块体非晶合金在与鼠成骨细胞共培养实验中表现出低的细胞毒性，细胞贴壁良好，形态健康，细胞有明显伪足，活动能力良好。The prepared Mga Znb Cac Srd bulk amorphous alloy showed low cytotoxicity in the co-culture experiment with mouse osteoblasts, the cells adhered well, the shape was healthy, the cells had obvious pseudopods, and the mobility was good .
本发明采用铜模铸造法制备生物医用可降解MgaZnbCacSrd块体非晶合金，其包括有下列步骤：The present invention adopts copper mold casting method to prepare biomedical degradable Mga Znb Cac Srd bulk amorphous alloy, which includes the following steps:
步骤一：配料Step 1: Ingredients
按MgaZnbCacSrd的名义成分称取各元素，其中，镁(Mg)的质量百分比纯度为99.9％；锌(Zn)的质量百分比纯度为99.9％；钙(Ca)的质量百分比纯度为99.9％；锶(Sr)的质量百分比纯度为99％；Weigh each element according to the nominal composition of Mga Znb Cac Srd , wherein the mass percentage purity of magnesium (Mg) is 99.9%; the mass percentage purity of zinc (Zn) is 99.9%; the mass percentage purity of calcium (Ca) The purity is 99.9%; the mass percent purity of strontium (Sr) is 99%;
步骤二：熔炼制MgaZnbCacSrd母合金Step 2: Melting Mga Znb Cac Srd master alloy
将步骤一称得的所需原料放入真空感应熔炼炉中，调节熔炼炉的真空室的真空度至1×10－2～3×10－2Pa，然后充高纯氩气使真空室的真空度至0.5×105～0.8×105Pa，熔炼温度650～900℃、熔炼10～20min后，随炉冷却，取出，得到第一合金锭；Put the required raw materials weighed in step 1 into the vacuum induction melting furnace, adjust the vacuum degree of the vacuum chamber of the melting furnace to 1×10-2 ~ 3×10-2 Pa, and then fill the high-purity argon to make the vacuum chamber Vacuum to 0.5×105 ~0.8×105 Pa, smelting temperature 650-900°C, smelting for 10-20 minutes, cooling with the furnace, taking out to obtain the first alloy ingot;
翻转第一合金锭，放入真空感应熔炼炉中，调节熔炼炉的真空室的真空度至1×10－2～3×10－2Pa，然后充高纯氩气使真空室的真空度至0.5×105～0.8×105Pa，熔炼温度650～900℃、熔炼10～20min后，随炉冷却，取出，制得MgaZnbCacSrd母合金；Turn over the first alloy ingot, put it into a vacuum induction melting furnace, adjust the vacuum degree of the vacuum chamber of the melting furnace to 1×10-2 ~ 3×10-2 Pa, and then fill it with high-purity argon to make the vacuum degree of the vacuum chamber to 0.5×105 ~0.8×105 Pa, smelting temperature 650~900°C, smelting for 10~20min, cooling with the furnace, taking out, and making Mga Znb Cac Srd master alloy;
步骤三：铜模铸造法制备MgaZnbCacSrd块体非晶合金试样Step 3: Preparation of Mga Znb Cac Srd bulk amorphous alloy sample by copper mold casting method
将步骤二制备得到的MgaZnbCacSrd母合金放入快速凝固感应炉中，调节感应炉的真空室的真空度至7×10－2～2×10－1Pa，然后充高纯氩气使真空室的真空度至0.4×105～0.6×105Pa；Put the Mga Znb Cac Srd master alloy prepared in step 2 into a rapid solidification induction furnace, adjust the vacuum degree of the vacuum chamber of the induction furnace to 7×10-2 ~ 2×10-1Pa , and then fill High-purity argon makes the vacuum of the vacuum chamber to 0.4×105 ~0.6×105 Pa;
调节感应电流至150～250mA，待母合金完全熔化后将熔体喷射入铜模中，并随铜模冷却，即制得MgaZnbCacSrd块体非晶合金试样。Adjust the induction current to 150-250mA. After the master alloy is completely melted, spray the melt into the copper mold and cool it with the copper mold to prepare the Mga Znb Cac Srd bulk amorphous alloy sample.
本发明与现有技术相比的优点在于：The advantage of the present invention compared with prior art is:
(1)本发明的MgaZnbCacSrd块体非晶合金的组成元素均为无生物毒性元素，不含高生物毒性的Cu和Ni元素，潜在生物毒性大大降低。(1) The constituent elements of the Mga Znb Cac Srd bulk amorphous alloy of the present invention are all non-biotoxic elements, and do not contain highly biotoxic Cu and Ni elements, and the potential biotoxicity is greatly reduced.
(2)本发明的MgaZnbCacSrd块体非晶合金具有较高的非晶形成能力，非晶形成临界尺寸为6mm。(2) The Mga Znb Cac Srd bulk amorphous alloy of the present invention has a relatively high amorphous formation ability, and the critical size of the amorphous formation is 6 mm.
(3)本发明的MgaZnbCacSrd块体非晶合金具有较好的力学性能，室温压缩断裂强度为750～900MPa，弹性应变为1.9％，杨氏模量为38～48GPa，比强度为2.75×105～2.9×105Nm/kg。(3) The Mga Znb Cac Srd bulk amorphous alloy of the present invention has good mechanical properties, the room temperature compressive fracture strength is 750-900 MPa, the elastic strain is 1.9%, and the Young's modulus is 38-48 GPa, The specific strength is 2.75×105 -2.9×105 Nm/kg.
(4)本发明的MgaZnbCacSrd块体非晶合金在模拟人体溶液中表现出适宜的腐蚀速率(0.1～1.0mm/year)，和较低的氢气析出量，为0.02～0.15ml/(cm2·d)。(4) The Mga Znb Cac Srd bulk amorphous alloy of the present invention exhibits a suitable corrosion rate (0.1 to 1.0 mm/year) in a simulated human body solution, and a lower amount of hydrogen evolution, which is 0.02 to 1.0 mm/year. 0.15 ml/(cm2 ·d).
(5)本发明的MgaZnbCacSrd块体非晶合金在与鼠成骨细胞共培养实验中表现出低的细胞毒性，细胞贴壁良好，形态健康，细胞有明显伪足，活动能力良好。(5) The Mga Znb Cac Srd bulk amorphous alloy of the present invention exhibits low cytotoxicity in a co-culture experiment with mouse osteoblasts, the cells adhere well to the wall, the shape is healthy, and the cells have obvious pseudopodia, Good mobility.
附图说明Description of drawings
图1是本发明制得的Mg66Zn30Ca3Sr1块体非晶合金的XRD图谱。Fig. 1 is the XRD spectrum of the Mg66 Zn30 Ca3 Sr1 bulk amorphous alloy prepared in the present invention.
图2是本发明制得的Mg66Zn30Ca3Sr1块体非晶合金的DSC曲线。Fig. 2 is the DSC curve of the Mg66 Zn30 Ca3 Sr1 bulk amorphous alloy prepared in the present invention.
图3是本发明制得的Mg66Zn30Ca3Sr1块体非晶合金的室温压缩应力应变曲线。Fig. 3 is the compressive stress-strain curve at room temperature of the Mg66 Zn30 Ca3 Sr1 bulk amorphous alloy prepared by the present invention.
图4是本发明制得的Mg66Zn30Ca3Sr1块体非晶合金在模拟人体溶液中的氢气析出量随浸泡时间的变化曲线。Fig. 4 is a graph showing the hydrogen evolution of the Mg66 Zn30 Ca3 Sr1 bulk amorphous alloy prepared in the present invention in a simulated human body solution as a function of immersion time.
图5是本发明制得的Mg66Zn30Ca3Sr1块体非晶合金与鼠成骨细胞共培养后，合金表面细胞形态的扫描电镜照片。Fig. 5 is a scanning electron micrograph of cell morphology on the alloy surface after the Mg66 Zn30 Ca3 Sr1 bulk amorphous alloy prepared by the present invention is co-cultured with mouse osteoblasts.
具体实施方式detailed description
下面结合附图及具体实施例详细介绍本发明。但以下的实施例仅限于解释本发明，本发明的保护范围应包括权利要求的全部内容，不仅仅限于本实施例。The present invention will be described in detail below in conjunction with the accompanying drawings and specific embodiments. But the following embodiments are only limited to explain the present invention, and the protection scope of the present invention should include the entire content of the claims, not only limited to the present embodiment.
实施例1：Example 1:
采用铜模铸造法制备直径为2mm的Mg66Zn30Ca3Sr1块体非晶合金Mg66 Zn30 Ca3 Sr1 Bulk Amorphous Alloy with a Diameter of 2mm Prepared by Copper Die Casting
步骤一：配料Step 1: Ingredients
按Mg66Zn30Ca3Sr1的名义成分称取各元素，其中，镁(Mg)的质量百分比纯度为99.9％；锌(Zn)的质量百分比纯度为99.9％；钙(Ca)的质量百分比纯度为99.9％；锶(Sr)的质量百分比纯度为99％；Weigh each element according to the nominal composition of Mg66 Zn30 Ca3 Sr1 , wherein the mass percent purity of magnesium (Mg) is 99.9%; the mass percent purity of zinc (Zn) is 99.9%; the mass percent purity of calcium (Ca) The purity is 99.9%; the mass percent purity of strontium (Sr) is 99%;
步骤二：熔炼制Mg66Zn30Ca3Sr1母合金Step 2: Melting Mg66 Zn30 Ca3 Sr1 Master Alloy
将步骤一称得的所需原料放入真空感应熔炼炉中，调节熔炼炉的真空室的真空度至2×10－2Pa，然后充高纯氩气使真空室的真空度至0.8×105Pa，熔炼温度800℃、熔炼15min后，随炉冷却，取出，得到第一合金锭；Put the required raw materials weighed in step 1 into the vacuum induction melting furnace, adjust the vacuum degree of the vacuum chamber of the melting furnace to 2×10-2 Pa, and then fill the high-purity argon to make the vacuum degree of the vacuum chamber to 0.8×105 Pa, melting temperature 800°C, smelting for 15 minutes, cooling with the furnace, taking out, and obtaining the first alloy ingot;
翻转第一合金锭，放入真空感应熔炼炉中，调节熔炼炉的真空室的真空度至2×10－2Pa，然后充高纯氩气使真空室的真空度至0.8×105Pa，熔炼温度750℃、熔炼15min后，随炉冷却，取出，制得Mg66Zn30Ca3Sr1母合金；Turn over the first alloy ingot, put it into a vacuum induction melting furnace, adjust the vacuum degree of the vacuum chamber of the melting furnace to 2×10-2 Pa, and then fill it with high-purity argon to make the vacuum degree of the vacuum chamber to 0.8×105 Pa, After smelting at 750°C for 15 minutes, cool with the furnace and take it out to obtain Mg66 Zn30 Ca3 Sr1 master alloy;
步骤三：铜模铸造法制备直径为2mm的Mg66Zn30Ca3Sr1块体非晶合金Step 3: Mg66 Zn30 Ca3 Sr1 bulk amorphous alloy with a diameter of 2 mm prepared by copper mold casting
将步骤二制备得到的Mg66Zn30Ca3Sr1母合金放入快速凝固感应炉中，调节感应炉的真空室的真空度至2×10－1Pa，然后充高纯氩气使真空室的真空度至0.5×105Pa；Put the Mg66 Zn30 Ca3 Sr1 master alloy prepared in step 2 into a rapid solidification induction furnace, adjust the vacuum degree of the vacuum chamber of the induction furnace to 2×10-1 Pa, and then fill the vacuum chamber with high-purity argon to make the vacuum chamber The vacuum degree is up to 0.5×105 Pa;
调节感应电流至200mA，待母合金完全熔化后将熔体喷射入铜模中，并随铜模冷却，即制得直径为2mm的Mg66Zn30Ca3Sr1块体非晶合金试样。Adjust the induction current to 200mA, spray the melt into the copper mold after the master alloy is completely melted, and cool it with the copper mold to prepare a Mg66 Zn30 Ca3 Sr1 bulk amorphous alloy sample with a diameter of 2mm.
对实施例1制得的Mg66Zn30Ca3Sr1块体非晶合金试样取其纵剖面，进行X射线衍射测试，其X射线衍射图谱如图1所示。图中横坐标为2θ角度，纵坐标为衍射强度；从衍射图谱中可以看出该样品没有明显的晶化峰，为非晶结构。The longitudinal section of the Mg66 Zn30 Ca3 Sr1 bulk amorphous alloy sample obtained in Example 1 was taken for X-ray diffraction test. The X-ray diffraction pattern is shown in FIG. 1 . The abscissa in the figure is the 2θ angle, and the ordinate is the diffraction intensity; it can be seen from the diffraction pattern that the sample has no obvious crystallization peak and is an amorphous structure.
对实施例1制得的Mg66Zn30Ca3Sr1块体非晶合金试样截取其心部小块区域，用差示扫描量热仪(DSC)对其进行热分析测试，得到其热力学参数，其DSC曲线如图2所示。图中横坐标为温度，纵坐标为热量，向下方向为放热；从图中可以看出其玻璃转化温度(Tg)为96.2℃，晶化温度(Tx)为109.6℃，过冷液相区(ΔTx＝Tx-Tg)宽度为13.4℃。For the Mg66 Zn30 Ca3 Sr1 bulk amorphous alloy sample obtained in Example 1, a small area in the center was cut, and a thermal analysis test was carried out with a differential scanning calorimeter (DSC), to obtain its thermodynamic parameters, and its DSC curve is shown in Figure 2. The abscissa in the figure is temperature, the ordinate is heat, and the downward direction is heat release; it can be seen from the figure that the glass transition temperature (Tg ) is 96.2 °C, and the crystallization temperature (Tx ) is 109.6 °C, supercooled The width of the liquid phase region (ΔTx =Tx -Tg ) is 13.4°C.
对实施例1制得的Mg66Zn30Ca3Sr1块体非晶合金试样用力学性能试验机测试其室温压缩力学性能，其压缩过程的应力应变曲线如图3所示。图中横坐标为压缩应变，纵坐标为压缩应力，可以看出该合金断裂强度为848MPa，弹性应变为1.9％，杨氏模量为44.6GPa，比强度为2.86×105Nm/kg。The room temperature compression mechanical properties of the Mg66 Zn30 Ca3 Sr1 bulk amorphous alloy sample prepared in Example 1 were tested by a mechanical property testing machine, and the stress-strain curve of the compression process is shown in FIG. 3 . The abscissa in the figure is the compressive strain, and the ordinate is the compressive stress. It can be seen that the fracture strength of the alloy is 848MPa, the elastic strain is 1.9%, the Young's modulus is 44.6GPa, and the specific strength is 2.86×105 Nm/kg.
对实施例1制得的Mg66Zn30Ca3Sr1块体非晶合金试样用静态浸泡法测试其在模拟人体溶液中的腐蚀速率。结果表明，其在模拟人体溶液中的腐蚀速率为0.145mm/year。所使用的模拟人体溶液(溶剂为去离子水)由8.011g/L的氯化钠(NaCl)、0.2g/L的氯化钾(KCl)、1.153g/L的磷酸一氢钠(Na2HPO4)和0.2g/L的磷酸二氢钾(KH2PO4)组成。The corrosion rate of the Mg66 Zn30 Ca3 Sr1 bulk amorphous alloy sample prepared in Example 1 was tested by static soaking method in simulated human body solution. The results show that its corrosion rate in simulated human body solution is 0.145mm/year. The used simulated human body solution (solvent is deionized water) consists of 8.011g/L sodium chloride (NaCl), 0.2g/L potassium chloride (KCl), 1.153g/L sodium monohydrogen phosphate (Na2 HPO4 ) and 0.2g/L potassium dihydrogen phosphate (KH2 PO4 ).
对实施例1制得的Mg66Zn30Ca3Sr1块体非晶合金试样用静态浸泡收集氢气法测试其氢气析出量，所采用溶液为模拟人体溶液，其氢气析出量随浸泡时间的变化曲线如图4所示。图中横坐标为浸泡时间，纵坐标为氢气析出量；可以看出该合金在模拟人体溶液中的氢气析出速率随浸泡时间的增加而减小，240小时氢气析出总量为0.363ml/cm2。The Mg66 Zn30 Ca3 Sr1 bulk amorphous alloy sample obtained in Example 1 is tested for its hydrogen evolution by static immersion to collect hydrogen. The solution used is a simulated human body solution. The change curve is shown in Figure 4. The abscissa in the figure is the immersion time, and the ordinate is the amount of hydrogen evolution; it can be seen that the hydrogen evolution rate of the alloy in the simulated human body solution decreases with the increase of the immersion time, and the total amount of hydrogen evolution in 240 hours is 0.363ml/cm2 .
对实施例1制得的Mg66Zn30Ca3Sr1块体非晶合金试样用体外细胞共培养实验法测试其生物相容性，所采用的细胞为鼠成骨细胞(MC3T3-E1)，12小时共培养后合金表面扫描电镜照片如图5所示。可以看出该合金表面细胞贴壁良好，形态健康，细胞有明显伪足，活动能力良好。The biocompatibility of the Mg66 Zn30 Ca3 Sr1 bulk amorphous alloy sample prepared in Example 1 was tested by an in vitro cell co-culture experiment, and the cells used were mouse osteoblasts (MC3T3-E1) , after 12 hours of co-cultivation, the scanning electron micrographs of the alloy surface are shown in Figure 5. It can be seen that the cells on the surface of the alloy are well adhered to the wall, the shape is healthy, the cells have obvious pseudopodia, and the mobility is good.
采用实施例1的制备方法制得下表所列化学成分为MgaZnbCacSrd块体非晶合金的临界尺寸、热力学参数和力学性能参数：Adopt the preparation method of embodiment 1 to make the chemical composition listed in the table below be the critical size, thermodynamic parameter and mechanical performance parameter of Mga Znb Cac Srd bulk amorphous alloy:
实施例2：Example 2:
采用铜模铸造法制备直径为2mm的Mg66Zn30Ca2.5Sr1.5块体非晶合金Mg66 Zn30 Ca2.5 Sr1.5 Bulk Amorphous Alloy with a Diameter of 2mm Prepared by Copper Die Casting
步骤一：配料Step 1: Ingredients
按Mg66Zn30Ca2.5Sr1.5的名义成分称取各元素，其中，镁(Mg)的质量百分比纯度为99.9％；锌(Zn)的质量百分比纯度为99.9％；钙(Ca)的质量百分比纯度为99.9％；锶(Sr)的质量百分比纯度为99％；Weigh each element according to the nominal composition of Mg66 Zn30 Ca2.5 Sr1.5 , wherein the mass percent purity of magnesium (Mg) is 99.9%; the mass percent purity of zinc (Zn) is 99.9%; the mass percent purity of calcium (Ca) The purity is 99.9%; the mass percent purity of strontium (Sr) is 99%;
步骤二：熔炼制Mg66Zn30Ca2.5Sr1.5母合金Step 2: Melting Mg66 Zn30 Ca2.5 Sr1.5 Master Alloy
将步骤一称得的所需原料放入真空感应熔炼炉中，调节熔炼炉的真空室的真空度至2×10－2Pa，然后充高纯氩气使真空室的真空度至0.8×105Pa，熔炼温度800℃、熔炼15min后，随炉冷却，取出，得到第一合金锭；Put the required raw materials weighed in step 1 into the vacuum induction melting furnace, adjust the vacuum degree of the vacuum chamber of the melting furnace to 2×10-2 Pa, and then fill the high-purity argon to make the vacuum degree of the vacuum chamber to 0.8×105 Pa, melting temperature 800°C, smelting for 15 minutes, cooling with the furnace, taking out, and obtaining the first alloy ingot;
翻转第一合金锭，放入真空感应熔炼炉中，调节熔炼炉的真空室的真空度至2×10－2Pa，然后充高纯氩气使真空室的真空度至0.8×105Pa，熔炼温度750℃、熔炼15min后，随炉冷却，取出，制得Mg66Zn30Ca2.5Sr1.5母合金；Turn over the first alloy ingot, put it into the vacuum induction melting furnace, adjust the vacuum degree of the vacuum chamber of the melting furnace to 2×10-2 Pa, and then fill the high-purity argon to make the vacuum degree of the vacuum chamber to 0.8×105Pa , after smelting at 750°C for 15 minutes, cool with the furnace, take out, and make Mg66 Zn30 Ca2.5 Sr1.5 master alloy;
步骤三：铜模铸造法制备直径为2mm的Mg66Zn30Ca2.5Sr1.5块体非晶合金Step 3: Mg66 Zn30 Ca2.5 Sr1.5 bulk amorphous alloy with a diameter of 2 mm prepared by copper mold casting
将步骤二制备得到的Mg66Zn30Ca2.5Sr1.5母合金放入快速凝固感应炉中，调节感应炉的真空室的真空度至2×10－1Pa，然后充高纯氩气使真空室的真空度至0.5×105Pa；Put the Mg66 Zn30 Ca2.5 Sr1.5 master alloy prepared in step 2 into a rapid solidification induction furnace, adjust the vacuum degree of the vacuum chamber of the induction furnace to 2×10-1 Pa, and then fill the vacuum chamber with high-purity argon to make the vacuum chamber The vacuum degree is up to 0.5×105 Pa;
调节感应电流至200mA，待母合金完全熔化后将熔体喷射入铜模中，并随铜模冷却，即制得直径为2mm的Mg66Zn30Ca2.5Sr1.5块体非晶合金试样。Adjust the induction current to 200mA, spray the melt into the copper mold after the master alloy is completely melted, and cool it with the copper mold to prepare a Mg66 Zn30 Ca2.5 Sr1.5 bulk amorphous alloy sample with a diameter of 2mm.
对实施例2制得的Mg66Zn30Ca2.5Sr1.5块体非晶合金试样取其纵剖面，进行X射线衍射测试，得到其衍射图谱。可以看出该样品没有明显的晶化峰，为非晶结构。The longitudinal section of the Mg66 Zn30 Ca2.5 Sr1.5 bulk amorphous alloy sample obtained in Example 2 was taken for X-ray diffraction test to obtain its diffraction pattern. It can be seen that the sample has no obvious crystallization peak and has an amorphous structure.
对实施例2制得的Mg66Zn30Ca2.5Sr1.5块体非晶合金试样截取其心部小块区域，用差示扫描量热仪(DSC)对其进行热分析测试，得到其热力学参数。可以看出该合金玻璃转化温度(Tg)为95.7℃，晶化温度(Tx)为113.0℃，过冷液相区(ΔTx)宽度为17.3℃。For the Mg66 Zn30 Ca2.5 Sr1.5 bulk amorphous alloy sample prepared in Example 2, cut out the small area of its core, and use a differential scanning calorimeter (DSC) to perform a thermal analysis test on it to obtain its thermodynamic parameter. It can be seen that the glass transition temperature (Tg ) of the alloy is 95.7°C, the crystallization temperature (Tx ) is 113.0°C, and the width of the supercooled liquid phase region (ΔTx ) is 17.3°C.
对实施例2制得的Mg66Zn30Ca2.5Sr1.5块体非晶合金试样用力学性能试验机测试其室温压缩力学性能，得到其压缩过程的应力应变曲线。可以看出该合金断裂强度为841MPa，弹性应变为1.9％，杨氏模量为44.3GPa，比强度为2.82×105Nm/kg。The room temperature compression mechanical properties of the Mg66 Zn30 Ca2.5 Sr1.5 bulk amorphous alloy sample prepared in Example 2 were tested by a mechanical property testing machine, and the stress-strain curve of the compression process was obtained. It can be seen that the fracture strength of the alloy is 841MPa, the elastic strain is 1.9%, the Young's modulus is 44.3GPa, and the specific strength is 2.82×105 Nm/kg.
对实施例2制得的Mg66Zn30Ca2.5Sr1.5块体非晶合金试样用静态浸泡法测试其在模拟人体溶液中的腐蚀速率。结果表明，其在模拟人体溶液中的腐蚀速率为0.245mm/year。The corrosion rate of the Mg66 Zn30 Ca2.5 Sr1.5 bulk amorphous alloy sample prepared in Example 2 was tested by static soaking method in simulated human body solution. The results show that its corrosion rate in simulated human body solution is 0.245mm/year.
对实施例2制得的Mg66Zn30Ca2.5Sr1.5块体非晶合金试样用静态浸泡收集氢气法测试其氢气析出量，得到其氢气析出量随浸泡时间的变化曲线，所采用溶液为模拟人体溶液。可以看出该合金在模拟人体溶液中的氢气析出速率随浸泡时间的增加而减小，240小时氢气析出总量为0.462ml/cm2。The Mg66 Zn30 Ca2.5 Sr1.5 bulk amorphous alloy sample obtained in Example 2 is tested for its hydrogen evolution by static immersion to collect hydrogen, and obtains a curve of its hydrogen evolution with soaking time. The solution used is Simulated human body solution. It can be seen that the hydrogen evolution rate of the alloy in the simulated human body solution decreases with the increase of immersion time, and the total amount of hydrogen evolution in 240 hours is 0.462ml/cm2 .
对实施例2制得的Mg66Zn30Ca2.5Sr1.5块体非晶合金试样用体外细胞共培养实验法测试其生物相容性，所采用的细胞为鼠成骨细胞(MC3T3-E1)，12小时共培养后通过扫描电镜观察合金表面，发现该合金表面细胞贴壁良好，形态健康，细胞有明显伪足，活动能力良好。The biocompatibility of the Mg66 Zn30 Ca2.5 Sr1.5 bulk amorphous alloy sample obtained in Example 2 was tested by an in vitro cell co-culture experiment, and the cells used were mouse osteoblasts (MC3T3-E1) , After 12 hours of co-cultivation, the surface of the alloy was observed by scanning electron microscopy, and it was found that the cells on the surface of the alloy adhered well, the shape was healthy, the cells had obvious pseudopodia, and the activity was good.
实施例3：Example 3:
采用铜模铸造法制备直径为2mm的Mg73Zn23Ca3.5Sr0.5块体非晶合金Mg73 Zn23 Ca3.5 Sr0.5 Bulk Amorphous Alloy with a Diameter of 2mm Prepared by Copper Die Casting
步骤一：配料Step 1: Ingredients
按Mg73Zn23Ca3.5Sr0.5的名义成分称取各元素，其中，镁(Mg)的质量百分比纯度为99.9％；锌(Zn)的质量百分比纯度为99.9％；钙(Ca)的质量百分比纯度为99.9％；锶(Sr)的质量百分比纯度为99％；Weigh each element according to the nominal composition of Mg73 Zn23 Ca3.5 Sr0.5 , wherein the mass percent purity of magnesium (Mg) is 99.9%; the mass percent purity of zinc (Zn) is 99.9%; the mass percent purity of calcium (Ca) The purity is 99.9%; the mass percent purity of strontium (Sr) is 99%;
步骤二：熔炼制Mg73Zn23Ca3.5Sr0.5母合金Step 2: Melting Mg73 Zn23 Ca3.5 Sr0.5 Master Alloy
将步骤一称得的所需原料放入真空感应熔炼炉中，调节熔炼炉的真空室的真空度至2×10－2Pa，然后充高纯氩气使真空室的真空度至0.8×105Pa，熔炼温度850℃、熔炼15min后，随炉冷却，取出，得到第一合金锭；Put the required raw materials weighed in step 1 into the vacuum induction melting furnace, adjust the vacuum degree of the vacuum chamber of the melting furnace to 2×10-2 Pa, and then fill the high-purity argon to make the vacuum degree of the vacuum chamber to 0.8×105 Pa, melting temperature 850°C, smelting for 15 minutes, cooling with the furnace, taking out to obtain the first alloy ingot;
翻转第一合金锭，放入真空感应熔炼炉中，调节熔炼炉的真空室的真空度至2×10－2Pa，然后充高纯氩气使真空室的真空度至0.8×105Pa，熔炼温度800℃、熔炼15min后，随炉冷却，取出，制得Mg73Zn23Ca3.5Sr0.5母合金；Turn over the first alloy ingot, put it into a vacuum induction melting furnace, adjust the vacuum degree of the vacuum chamber of the melting furnace to 2×10-2 Pa, and then fill it with high-purity argon to make the vacuum degree of the vacuum chamber to 0.8×105 Pa, After smelting at 800°C for 15 minutes, cool with the furnace and take it out to obtain Mg73 Zn23 Ca3.5 Sr0.5 master alloy;
步骤三：铜模铸造法制备直径为2mm的Mg73Zn23Ca3.5Sr0.5块体非晶合金Step 3: Mg73 Zn23 Ca3.5 Sr0.5 bulk amorphous alloy with a diameter of 2 mm prepared by copper mold casting
将步骤二制备得到的Mg73Zn23Ca3.5Sr0.5母合金放入快速凝固感应炉中，调节感应炉的真空室的真空度至8×10－2Pa，然后充高纯氩气使真空室的真空度至0.5×105Pa；Put the Mg73 Zn23 Ca3.5 Sr0.5 master alloy prepared in step 2 into a rapid solidification induction furnace, adjust the vacuum degree of the vacuum chamber of the induction furnace to 8×10-2 Pa, and then fill the vacuum chamber with high-purity argon to The vacuum degree is up to 0.5×105 Pa;
调节感应电流至200mA，待母合金完全熔化后将熔体喷射入铜模中，并随铜模冷却，即制得直径为2mm的Mg73Zn23Ca3.5Sr0.5块体非晶合金试样。Adjust the induction current to 200mA, spray the melt into the copper mold after the master alloy is completely melted, and cool with the copper mold, and then make a Mg73 Zn23 Ca3.5 Sr0.5 bulk amorphous alloy sample with a diameter of 2mm.
对实施例3制得的Mg73Zn23Ca3.5Sr0.5块体非晶合金试样取其纵剖面，进行X射线衍射测试，得到其衍射图谱。可以看出该样品没有明显的晶化峰，为非晶结构。The longitudinal section of the Mg73 Zn23 Ca3.5 Sr0.5 bulk amorphous alloy sample obtained in Example 3 was taken for X-ray diffraction test to obtain its diffraction pattern. It can be seen that the sample has no obvious crystallization peak and has an amorphous structure.
对实施例3制得的Mg73Zn23Ca3.5Sr0.5块体非晶合金试样截取其心部小块区域，用差示扫描量热仪(DSC)对其进行热分析测试，得到其热力学参数。可以看出该合金玻璃转化温度(Tg)为91.4℃，晶化温度(Tx)为106.0℃，过冷液相区(ΔTx)宽度为14.6℃。For the Mg73 Zn23 Ca3.5 Sr0.5 bulk amorphous alloy sample prepared in Example 3, the small block area of the center is cut off, and a thermal analysis test is carried out with a differential scanning calorimeter (DSC) to obtain its thermodynamic parameter. It can be seen that the glass transition temperature (Tg ) of the alloy is 91.4°C, the crystallization temperature (Tx ) is 106.0°C, and the width of the supercooled liquid phase region (ΔTx ) is 14.6°C.
对实施例3制得的Mg73Zn23Ca3.5Sr0.5块体非晶合金试样用力学性能试验机测试其室温压缩力学性能，得到其压缩过程的应力应变曲线。可以看出该合金断裂强度为751MPa，弹性应变为1.9％，杨氏模量为39.5GPa，比强度为2.81×105Nm/kg。The room temperature compression mechanical properties of the Mg73 Zn23 Ca3.5 Sr0.5 bulk amorphous alloy sample prepared in Example 3 were tested by a mechanical property testing machine, and the stress-strain curve of the compression process was obtained. It can be seen that the fracture strength of the alloy is 751MPa, the elastic strain is 1.9%, the Young's modulus is 39.5GPa, and the specific strength is 2.81×105 Nm/kg.
对实施例3制得的Mg73Zn23Ca3.5Sr0.5块体非晶合金试样用静态浸泡法测试其在模拟人体溶液中的腐蚀速率。结果表明，其在模拟人体溶液中的腐蚀速率为0.936mm/year。The corrosion rate of the Mg73 Zn23 Ca3.5 Sr0.5 bulk amorphous alloy sample prepared in Example 3 was tested by the static immersion method in a simulated human body solution. The results show that its corrosion rate in simulated human body solution is 0.936mm/year.
对实施例3制得的Mg73Zn23Ca3.5Sr0.5块体非晶合金试样用静态浸泡收集氢气法测试其氢气析出量，得到其氢气析出量随浸泡时间的变化曲线，所采用溶液为模拟人体溶液。可以看出该合金在模拟人体溶液中的氢气析出速率随浸泡时间的增加而减小，240小时氢气析出总量为1.386ml/cm2。The Mg73 Zn23 Ca3.5 Sr0.5 bulk amorphous alloy sample obtained in Example 3 is tested for its hydrogen evolution by static immersion to collect hydrogen, and obtains a curve of its hydrogen evolution with soaking time. The solution used is Simulated human body solution. It can be seen that the hydrogen evolution rate of the alloy in the simulated human body solution decreases with the increase of immersion time, and the total amount of hydrogen evolution in 240 hours is 1.386ml/cm2 .
对实施例3制得的Mg73Zn23Ca3.5Sr0.5块体非晶合金试样用体外细胞共培养实验法测试其生物相容性，所采用的细胞为鼠成骨细胞(MC3T3-E1)，12小时共培养后通过扫描电镜观察合金表面，发现该合金表面细胞贴壁良好，形态健康，细胞有明显伪足，活动能力良好。The biocompatibility of the Mg73 Zn23 Ca3.5 Sr0.5 bulk amorphous alloy sample prepared in Example 3 was tested by an in vitro cell co-culture experiment, and the cells used were mouse osteoblasts (MC3T3-E1) , After 12 hours of co-cultivation, the surface of the alloy was observed by scanning electron microscopy, and it was found that the cells on the surface of the alloy adhered well, the shape was healthy, the cells had obvious pseudopodia, and the activity was good.
实施例4：Example 4:
采用铜模铸造法制备直径为2mm的Mg61Zn34Ca4Sr1块体非晶合金Mg61 Zn34 Ca4 Sr1 Bulk Amorphous Alloy with a Diameter of 2mm Prepared by Copper Mold Casting
步骤一：配料Step 1: Ingredients
按Mg61Zn34Ca4Sr1的名义成分称取各元素，其中，镁(Mg)的质量百分比纯度为99.9％；锌(Zn)的质量百分比纯度为99.9％；钙(Ca)的质量百分比纯度为99.9％；锶(Sr)的质量百分比纯度为99％；Weigh each element according to the nominal composition of Mg61 Zn34 Ca4 Sr1 , wherein the mass percentage purity of magnesium (Mg) is 99.9%; the mass percentage purity of zinc (Zn) is 99.9%; the mass percentage purity of calcium (Ca) The purity is 99.9%; the mass percent purity of strontium (Sr) is 99%;
步骤二：熔炼制Mg61Zn34Ca4Sr1母合金Step 2: Melting Mg61 Zn34 Ca4 Sr1 Master Alloy
将步骤一称得的所需原料放入真空感应熔炼炉中，调节熔炼炉的真空室的真空度至2×10－2Pa，然后充高纯氩气使真空室的真空度至0.8×105Pa，熔炼温度750℃、熔炼15min后，随炉冷却，取出，得到第一合金锭；Put the required raw materials weighed in step 1 into the vacuum induction melting furnace, adjust the vacuum degree of the vacuum chamber of the melting furnace to 2×10-2 Pa, and then fill the high-purity argon to make the vacuum degree of the vacuum chamber to 0.8×105 Pa, smelting temperature 750°C, smelting for 15 minutes, cooling with the furnace, taking out, and obtaining the first alloy ingot;
翻转第一合金锭，放入真空感应熔炼炉中，调节熔炼炉的真空室的真空度至2×10－2Pa，然后充高纯氩气使真空室的真空度至0.8×105Pa，熔炼温度700℃、熔炼15min后，随炉冷却，取出，制得Mg61Zn34Ca4Sr1母合金；Turn over the first alloy ingot, put it into a vacuum induction melting furnace, adjust the vacuum degree of the vacuum chamber of the melting furnace to 2×10-2 Pa, and then fill it with high-purity argon to make the vacuum degree of the vacuum chamber to 0.8×105 Pa, After smelting at 700°C for 15 minutes, cool with the furnace and take it out to obtain Mg61 Zn34 Ca4 Sr1 master alloy;
步骤三：铜模铸造法制备直径为2mm的Mg61Zn34Ca4Sr1块体非晶合金Step 3: Mg61 Zn34 Ca4 Sr1 bulk amorphous alloy with a diameter of 2 mm prepared by copper mold casting
将步骤二制备得到的Mg61Zn34Ca4Sr1母合金放入快速凝固感应炉中，调节感应炉的真空室的真空度至8×10－2Pa，然后充高纯氩气使真空室的真空度至0.5×105Pa；Put the Mg61 Zn34 Ca4 Sr1 master alloy prepared in step 2 into a rapid solidification induction furnace, adjust the vacuum degree of the vacuum chamber of the induction furnace to 8×10-2 Pa, and then fill the vacuum chamber with high-purity argon The vacuum degree is up to 0.5×105 Pa;
调节感应电流至200mA，待母合金完全熔化后将熔体喷射入铜模中，并随铜模冷却，即制得直径为2mm的Mg61Zn34Ca4Sr1块体非晶合金试样。Adjust the induction current to 200mA, spray the melt into the copper mold after the master alloy is completely melted, and cool it with the copper mold to prepare a Mg61 Zn34 Ca4 Sr1 bulk amorphous alloy sample with a diameter of 2mm.
对实施例4制得的Mg61Zn34Ca4Sr1块体非晶合金试样取其纵剖面，进行X射线衍射测试，得到其衍射图谱。从衍射图谱中可以看出该样品没有明显的晶化峰，为非晶结构。The longitudinal section of the Mg61 Zn34 Ca4 Sr1 bulk amorphous alloy sample obtained in Example 4 was taken for X-ray diffraction test to obtain its diffraction pattern. It can be seen from the diffraction pattern that the sample has no obvious crystallization peak and is an amorphous structure.
对实施例4制得的Mg61Zn34Ca4Sr1块体非晶合金试样截取其心部小块区域，用差示扫描量热仪(DSC)对其进行热分析测试，得到其热力学参数。可以看出该合金玻璃转化温度(Tg)为101.6℃，晶化温度(Tx)为115.3℃，过冷液相区(ΔTx)宽度为13.7℃。For the Mg61 Zn34 Ca4 Sr1 bulk amorphous alloy sample obtained in Example 4, a small area in the center was cut, and a thermal analysis test was carried out with a differential scanning calorimeter (DSC), to obtain its thermodynamic parameter. It can be seen that the glass transition temperature (Tg ) of the alloy is 101.6°C, the crystallization temperature (Tx ) is 115.3°C, and the width of the supercooled liquid phase region (ΔTx ) is 13.7°C.
对实施例4制得的Mg61Zn34Ca4Sr1块体非晶合金试样用力学性能试验机测试其室温压缩力学性能，得到其压缩过程的应力应变曲线。可以看出该合金断裂强度为878MPa，弹性应变为1.9％，杨氏模量为46.2GPa，比强度为2.81×105Nm/kg。The Mg61 Zn34 Ca4 Sr1 bulk amorphous alloy sample prepared in Example 4 was tested for its room-temperature compression mechanical properties with a mechanical property testing machine, and its stress-strain curve during compression was obtained. It can be seen that the fracture strength of the alloy is 878MPa, the elastic strain is 1.9%, the Young's modulus is 46.2GPa, and the specific strength is 2.81×105 Nm/kg.
对实施例4制得的Mg61Zn34Ca4Sr1块体非晶合金试样用静态浸泡法测试其在模拟人体溶液中的腐蚀速率。结果表明，其在模拟人体溶液中的腐蚀速率为0.112mm/year。The corrosion rate of the Mg61 Zn34 Ca4 Sr1 bulk amorphous alloy sample prepared in Example 4 was tested by static soaking method in simulated human body solution. The results show that its corrosion rate in simulated human body solution is 0.112mm/year.
对实施例4制得的Mg61Zn34Ca4Sr1块体非晶合金试样用静态浸泡收集氢气法测试其氢气析出量，得到其氢气析出量随浸泡时间的变化曲线，所采用溶液为模拟人体溶液。可以看出该合金在模拟人体溶液中的氢气析出速率随浸泡时间的增加而减小，240小时氢气析出总量为0.236ml/cm2。The Mg61 Zn34 Ca4 Sr1 bulk amorphous alloy sample obtained in Example 4 is tested for its hydrogen evolution by static immersion to collect hydrogen, and the curve of its hydrogen evolution with soaking time is obtained. The solution used is Simulated human body solution. It can be seen that the hydrogen evolution rate of the alloy in the simulated human body solution decreases with the increase of immersion time, and the total amount of hydrogen evolution in 240 hours is 0.236ml/cm2 .
对实施例4制得的Mg61Zn34Ca4Sr1块体非晶合金试样用体外细胞共培养实验法测试其生物相容性，所采用的细胞为鼠成骨细胞(MC3T3-E1)，12小时共培养后通过扫描电镜观察合金表面，发现该合金表面细胞贴壁良好，形态健康，细胞有明显伪足，活动能力良好。The biocompatibility of the Mg61 Zn34 Ca4 Sr1 bulk amorphous alloy sample obtained in Example 4 was tested by an in vitro cell co-culture experiment, and the cells used were mouse osteoblasts (MC3T3-E1) , After 12 hours of co-cultivation, the surface of the alloy was observed by scanning electron microscopy, and it was found that the cells on the surface of the alloy adhered well, the shape was healthy, the cells had obvious pseudopodia, and the activity was good.
需要说明的是，按照本发明上述各实施例，本领域技术人员是完全可以实现本发明独立权利要求及从属权利的全部范围的，实现过程及方法同上述各实施例；且本发明未详细阐述部分属于本领域公知技术。It should be noted that, according to the above-mentioned embodiments of the present invention, those skilled in the art can fully realize the full scope of the independent claims and dependent rights of the present invention, and the implementation process and method are the same as the above-mentioned embodiments; and the present invention is not elaborated Some of them belong to well-known technologies in the art.
以上所述，仅为本发明部分具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本领域的人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。The above are only some specific implementations of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be covered within the protection scope of the present invention.
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