PatViewer专利搜索
中国 发明授权 无效

镁合金表面磁控溅射沉积钽膜的制备方法 【EN】Method for preparing tantalum film on surface of magnesium alloy through magnetron sputtering deposition

申请(专利)号:CN201210227668.0国省代码:黑龙江 23
申请(专利权)人:【中文】佳木斯大学【EN】Jiamusi University
温馨提示:Ctrl+D 请注意收藏,详细著录项请登录检索查看。 Please note the collection. For details, please search the home page.

摘要:
【中文】镁合金表面磁控溅射沉积钽膜的制备方法,它涉及镁合金表面钽膜的制备方法,本发明要解决现有的镁合金表面改性技术中存在的镁合金与涂层或膜层间结合力较差、膜层可降解性差、膜层耐磨性差和膜层生物相容性差的问题。本发明通过如下步骤来实现:一、试样的清洗;二、镀膜前的准备;三、镀膜。本发明采用磁控溅射沉积技术在镁合金上制备的钽膜层具有良好的耐蚀性、耐磨性及生物相容性的特点。本发明适用于镁合金表面改性工程领域。 【EN】Paragraph:The invention discloses a method for preparing a tantalum film on the surface of magnesium alloy through magnetron sputtering deposition, and relates to a method for preparing the tantalum film on the surface of the magnesium alloy. The invention aims to solve the problems of relatively poor bonding force between the magnesium alloy and a coating layer or a film layer, poor biodegradablity of the film layer, poor abrasive resistance of the film layer and poor biocompatibility of the film layer in the conventional magnesium alloy surface modification technology. The method is implemented through the following steps of: 1. cleaning a test sample; 2. preparing for coating; and 3. carrying out coating. The tantalum film prepared on the magnesium alloy by the using method provided by the invention through the magnetron sputtering deposition technology has excellent corrosion resistance, abrasive resistance and biocompatibility. The method provided by the invention is suitable for the magnesium alloy surface modification engineering field.Image:201210227668.GIF

主权项:
【中文】镁合金表面磁控溅射沉积钽膜的制备方法,其特征在于它是通过以下步骤实现的: 一、试样的清洗:将镁合金材质的骨固定片状材料先放入丙酮中,在超声功率为150W~180W的条件,清洗30min~45min,然后再放到乙醇中,在超声功率为150W~180W的条件,清洗15min~30min,吹干后装夹在磁控溅射设备的真空室中的样品台上,其中镁合金按质量百分比由93.5%~94.5%的Mg、4.5%~5.5%的Zn、0.4%~0.8%的Zr、0.15%~0.25%的Ca和0.08%~0.1%的Mn组成; 二、镀膜前的准备:将钛硅靶材和钽靶材分别安装在不同的磁控溅射靶上,然后开始抽真空,当真空室气压达到3×10‑3Pa~5×10‑3Pa时,通入氩气并调节真空室内气压至0.8Pa~1.2Pa,开启射频电源及偏压电源,溅射清洗骨固定片状材料15min~20min,完成镀膜前的准备,其中射频电源的加载在磁控溅射靶与样品台之间的电压为1.0kV,电流为0.28A,射频频率为13.56MHz,偏压电源加载在样品台上的电压为‑500V,钛硅靶材和钽靶材的规格尺寸为Φ68mm×6mm,靶基距为60mm~120mm; 三、镀膜:溅射清洗后,将真空室内气压调节到0.4Pa~0.6Pa,开启直流及脉冲复合电源中的直流恒流电源加载在装有钛硅靶材的磁控溅射靶上,预溅射10min~15min,然后拉开挡板,在骨固定片状材料上镀钛硅膜层,镀膜时间为4min~6min,然后关闭加载在装有钛硅靶材的磁控溅射靶上的直流恒流电源,拉上挡板,将真空室内气压调节到0.3Pa~0.9Pa,再将直流及脉冲复合电源加载在装有钽靶材的磁控溅射靶上,预溅射10min~15min后,拉开挡板,在骨固定片状材料上镀钽膜层,镀膜时间为28min~32min,关闭直流及脉冲复合电源,关闭镀膜设备,完成镁合金表面钽膜的制备过程,其中溅射钛硅靶时,直流恒流电源加载在装有钛硅靶材的磁控溅射靶上的电流为0.2A~1A;溅射钽靶时,直流恒流电源加载在装有钽靶材的磁控溅射靶上的电流为0.2A~1A,脉冲电源加载在装有钽靶材的磁控溅射靶上的脉冲电压为300V~800V,脉冲频率为50Hz~150Hz,脉宽为50μs~150μs。  【EN】1. the preparation method of Mg alloy surface magnetron sputtering deposition tantalum film is characterized in that it realizes by following steps: One, the cleaning of sample: by the bone of magnesium alloy material fixedly flaky material first put into acetone, the condition that is 150W~180W at ultrasonic power, clean 30min~45min, and then be put in ethanol, the condition that is 150W~180W at ultrasonic power, clean 15min~30min, dry up on the sample table of rear clamping in the vacuum chamber of magnetron sputtering equipment, wherein magnesium alloy is comprised of 93.5%~94.5% Mg, 4.5%~5.5% Zn, 0.4%~0.8% Zr, 0.15%~0.25% Ca and 0.08%~0.1% Mn by mass percentage; Two, the preparation before plated film: titanium silicon target material and tantalum target are arranged on respectively on different magnetron sputtering targets, then start to vacuumize, when gas pressure in vacuum reaches 3 * 10 pa~5 * 10 during Pa, pass into argon gas and regulate the vacuum chamber internal gas pressure to 0.8Pa~1.2Pa, open radio-frequency power supply and grid bias power supply, the sputter clean bone is flaky material 15min~20min fixedly, complete the front preparation of plated film, wherein the voltage be carried between magnetron sputtering target and sample table of radio-frequency power supply is 1.0kV, electric current is 0.28A, rf frequency is 13.56MHz, the voltage that grid bias power supply is carried on sample table is-500V, the specification of titanium silicon target material and tantalum target is Φ 68mm * 6mm, and target-substrate distance is 60mm~120mm; Three, plated film: after sputter clean, the vacuum chamber internal gas pressure is adjusted to 0.4Pa~0.6Pa, the DC constant flowing power of opening in direct current and pulse composite power source is carried on the magnetron sputtering target that titanium silicon target material is housed, pre-sputtering 10min~15min, then pull open baffle plate, at the fixing titanizing silicon film on flaky material of bone, the plated film time is 4min~6min, then close the DC constant flowing power be carried on the magnetron sputtering target that titanium silicon target material is housed, pull on baffle plate, the vacuum chamber internal gas pressure is adjusted to 0.3Pa~0.9Pa, again direct current and pulse composite power source are carried on the magnetron sputtering target that tantalum target is housed, after pre-sputtering 10min~15min, pull open baffle plate, fixedly on flaky material, plate the tantalum film layer at bone, the plated film time is 28min~32min, close direct current and pulse composite power source, close filming equipment, complete the preparation process of Mg alloy surface tantalum film, wherein during the sputtered titanium silicon target, the electric current that DC constant flowing power is carried on the magnetron sputtering target that titanium silicon target material is housed is 0.2A~1A, during the sputter tantalum target, the electric current that DC constant flowing power is carried on the magnetron sputtering target that tantalum target is housed is 0.2A~1A, the pulsed voltage that the pulse power is carried on the magnetron sputtering target that tantalum target is housed is 300V~800V, and pulse-repetition is 50Hz~150Hz, and pulsewidth is 50 μ s~150 μ s.


说明书

镁合金表面磁控溅射沉积钽膜的制备方法

技术领域


本发明涉及镁合金表面钽膜的制备方法。


背景技术


随着生物医学的发展,生物医用金属材料的应用也越加广泛。具有“21世纪最具发展潜


力和前途的绿色工程材料”之称的镁合金,由于其密度低、比强度和比刚度高、弹性模量与


骨接近、良好的生物相容性和可降解性等突出优点,使其在心血管支架、骨固定材料等方面


具有良好的应用前景。同时,由于镁合金的这些优点,其在航天航空、汽车工业、电子工业


等领域也获得了广泛的应用。然而,镁合金耐蚀性差,腐蚀速度过快,使其进一步的发展和


应用受到了限制。因此,改善镁合金耐蚀性使其在生物医学领域及工业领域获得更广泛的应


用已成为亟待解决的关键问题。


目前解决镁合金耐蚀性差的问题主要采用表面改性技术,主要包括:生物活性涂层法、


阳极氧化膜法、可降解高分子涂层法和化学转化膜法。生物活性涂层法主要存在的问题是涂


层脆性较大,镁合金与涂层间结合力较差;阳极氧化膜法优点是镁合金与膜间结合力较强,


耐蚀性也较强,但氧化膜是否可降解还有待于进一步证实;可降解高分子涂层法与生物活性


涂层法、阳极氧化膜法相比耐磨性较差;化学转化膜法的缺点是:膜层厚度都非常薄,不能


抵抗任何机械损伤,仅能做打底层使用,且其生物相容性还需要进一步证实。


发明内容


本发明是要解决现有的镁合金表面改性技术中存在的镁合金与涂层或膜层间结合力较


差、膜层可降解性差、膜层耐磨性差和膜层生物相容性差的问题而提出镁合金表面磁控溅射


沉积钽及钽复合膜制备方法。


本发明中的镁合金表面磁控溅射沉积钽膜的制备方法按以下步骤进行:


一、试样的清洗:将镁合金材质的骨固定片状材料先放入丙酮中,在超声功率为


150W~180W的条件,清洗30min~45min,然后再放到乙醇中,在超声功率为150W~180W的


条件,清洗15min~30min,吹干后装夹在磁控溅射设备的真空室中的样品台上,其中镁合金


按质量百分比由93.5%~94.5%的Mg、4.5%~5.5%的Zn、0.4%~0.8%的Zr、0.15%~0.25%的


Ca和0.08%~0.1%的Mn组成;


二、镀膜前的准备:将钛硅靶材和钽靶材分别安装在不同的磁控溅射靶上,然后开始抽


真空,当真空室气压达到3×10-3Pa~5×10-3Pa时,通入氩气并调节真空室内气压至0.8Pa~1.2Pa,


开启射频电源及偏压电源,溅射清洗骨固定片状材料15min~20min,完成镀膜前的准备,其


中射频电源的加载在磁控溅射靶与样品台之间的电压为1.0KV,电流为0.28A,射频频率为


13.56MHz,偏压电源加载在样品台上的电压为-500V,钛硅靶材和钽靶材的规格尺寸为


Φ68mm×6mm,靶基距为60mm~120mm;


三、镀膜:溅射清洗后,将真空室内气压调节到0.4Pa~0.6Pa,开启直流及脉冲复合电源


中的直流恒流电源加载在装有钛硅靶材的磁控溅射靶上,预溅射10min~15min,然后拉开挡


板,在骨固定片状材料上镀钛硅膜层,镀膜时间为4min~6min,然后关闭加载在装有钛硅靶


材的磁控溅射靶上的直流恒流电源,拉上挡板,将真空室内气压调节到0.3Pa~0.9Pa,再将直


流及脉冲复合电源加载在装有钽靶材的磁控溅射靶上,预溅射10min~15min后,拉开挡板,


在骨固定片状材料上镀钽膜层,镀膜时间为28min~32min,关闭直流及脉冲复合电源,关闭


镀膜设备,完成镁合金表面钽膜的制备过程,其中溅射钛硅靶时,直流恒流电源加载在装有


钛硅靶材的磁控溅射靶上的电流为0.2A~1A;溅射钽靶时,直流恒流电源加载在装有钽靶材


的磁控溅射靶上的电流为0.2A~1A,脉冲电源加载在装有钽靶材的磁控溅射靶上的脉冲电压


为300V~800V,脉冲频率为50Hz~150Hz,脉宽为50μs~150μs。


本发明的机理是:在表面改性技术中,磁控溅射具有在溅射过程中基材温升低和能实现


“高速”溅射两大典型特点。同时在溅射材料中,钽及钽的氮化物、氧化物以及碳化物都具


有高耐蚀性、高耐磨性和良好生物相容性。鉴于此,本发明提出采用磁控溅射技术在镁合金


表面制备致密且与基体结合良好的钽及钽复合膜,获得具有高耐蚀性、高耐磨性和良好生物


相容性的涂层复合材料。


本发明的有益效果如下:


1、提出一种采用磁控溅射沉积技术,制备出致密且具有生物活性的膜层复合材料;镁合


金钽膜层和基体的结合强度为8MPa~20MPa之间,高于股骨头在人直立的情况下承载的强度


0.5Mpa~1.75Mpa。


2、采用磁控溅射沉积技术在镁合金上制备的钽膜层具有良好的耐蚀性、耐磨性及生物相


容性的特点。


3、本发明采用的磁控溅射沉积技术包括:直流磁控溅射技术、高压注入复合直流磁控溅


射技术和高压注入复合高功率脉冲磁控溅射技术,本技术具有安全、无污染等特点,设备简


单、操作方便,为绿色环保表面处理技术。


附图说明


图1至图4是实验一中4个镁合金圆片表面高功率脉冲复合直流磁控溅射沉积钽膜×2000的


表面形貌;


图5是实验一中4个镁合金圆片表面高功率脉冲复合直流磁控溅射沉积钽膜的XRD图谱。


具体实施方式


本发明技术方案不局限于以下所列举具体实施方式,还包括各具体实施方式间的任意组


合。


具体实施方式一:本实施方式中镁合金表面磁控溅射沉积钽膜的制备方法按以下步骤进


行:


一、试样的清洗:将镁合金材质的骨固定片状材料先放入丙酮中,在超声功率为


150W~180W的条件下,清洗30min~45min,然后再放到乙醇中,在超声功率为150W~180W


的条件下,清洗15min~30min,吹干后装夹在磁控溅射设备的真空室中的样品台上,其中镁


合金按质量百分比由93.5%~94.5%的Mg、4.5%~5.5%的Zn、0.4%~0.8%的Zr、0.15%~0.25%


的Ca和0.08%~0.1%的Mn组成;


二、镀膜前的准备:将钛硅靶材和钽靶材分别安装在不同的磁控溅射靶上,然后开始抽


真空,当真空室气压达到3×10-3Pa~5×10-3Pa时,通入氩气并调节真空室内气压至0.8Pa~1.2Pa,


开启射频电源及偏压电源,溅射清洗骨固定片状材料15min~20min,完成镀膜前的准备,其


中射频电源的加载在磁控溅射靶与样品台之间的电压为1.0KV,电流为0.28A,射频频率为


13.56MHz,偏压电源加载在样品台上的电压为-500V,钛硅靶材和钽靶材的规格尺寸为


Φ68mm×6mm,靶基距为60mm~120mm;


三、镀膜:溅射清洗后,将真空室内气压调节到0.4Pa~0.6Pa,开启直流及脉冲复合电源


中的直流恒流电源加载在装有钛硅靶材的磁控溅射靶上,预溅射10min~15min,然后拉开挡


板,在骨固定片状材料上镀钛硅膜层,镀膜时间为4min~6min,然后关闭加载在装有钛硅靶


材的磁控溅射靶上的直流恒流电源,拉上挡板,将真空室内气压调节到0.3Pa~0.9Pa,再将直


流及脉冲复合电源加载在装有钽靶材的磁控溅射靶上,预溅射10min~15min后,拉开挡板,


在骨固定片状材料上镀钽膜层,镀膜时间为28min~32min,关闭直流及脉冲复合电源,关闭


镀膜设备,完成镁合金表面钽膜的制备过程,其中溅射钛硅靶时,直流恒流电源加载在装有


钛硅靶材的磁控溅射靶上的电流为0.2A~1A;溅射钽靶时,直流恒流电源加载在装有钽靶材


的磁控溅射靶上的电流为0.2A~1A,脉冲电源加载在装有钽靶材的磁控溅射靶上的脉冲电压


为300V~800V,脉冲频率为50Hz~150Hz,脉宽为50μs~150μs。


本发明的机理是:在表面改性技术中,磁控溅射具有在溅射过程中基材温升低和能实现


“高速”溅射两大典型特点。同时在溅射材料中,钽及钽的氮化物、氧化物以及碳化物都具


有高耐蚀性、高耐磨性和良好生物相容性。鉴于此,本发明提出采用磁控溅射技术在镁合金


表面制备致密且与基体结合良好的钽及钽复合膜,获得具有高耐蚀性、高耐磨性和良好生物


相容性的涂层复合材料。


本发明的有益效果如下:


1、提出一种采用磁控溅射沉积技术,制备出致密且具有生物活性的膜层复合材料;镁合


金钽膜层和基体的结合强度为8MPa~20MPa之间,高于股骨头在人直立的情况下承载的强度


0.5Mpa~1.75Mpa。


2、采用磁控溅射沉积技术制备的镁合金钽膜层具有良好的耐蚀性、耐磨性及生物相容性


的特点。


3、本发明采用的磁控溅射沉积技术包括:直流磁控溅射技术、高压注入复合直流磁控溅


射技术和高压注入复合高功率脉冲磁控溅射技术,本技术具有安全、无污染等特点,设备简


单、操作方便,为绿色环保表面处理技术。


具体实施方式二:本实施方式与具体实施方式一不同的是:步骤一中骨固定片状材料先


放入丙酮中,在超声功率为160W~170W的条件下,清洗35min~40min,然后再放到乙醇中,


在超声功率为160W~170W的条件下,清洗20min~25min。其它步骤和参数与具体实施方式一


相同。


具体实施方式三:本实施方式与具体实施方式一不同的是:步骤一中骨固定片状材料先


放入丙酮中,在超声功率为165W的条件下,清洗36min,然后再放到乙醇中,在超声功率为


165W的条件下,清洗24min。其它步骤和参数与具体实施方式一相同。


具体实施方式四:本实施方式与具体实施方式一至三之一不同的是:步骤二中当真空室


气压达到3.5×10-3Pa~4.5×10-3Pa时,通入氩气并调节真空室内气压至0.9Pa~1.1Pa,开启射频


电源及偏压电源,溅射清洗骨固定片状材料16min~19min。其它步骤和参数与具体实施方式


一至三之一相同。


具体实施方式五:本实施方式与具体实施方式一至三之一不同的是:步骤二中当真空室


气压达到4×10-3Pa时,通入氩气并调节真空室内气压至1Pa,开启射频电源及偏压电源,溅


射清洗骨固定片状材料18min。其它步骤和参数与具体实施方式一至三之一相同。


具体实施方式六:本实施方式与具体实施方式一至五之一不同的是:步骤二中靶基距为


70mm~110mm。其它步骤和参数与具体实施方式一至五之一相同。


具体实施方式七:本实施方式与具体实施方式一至六之一不同的是:步骤三中溅射清洗


后,将真空室内气压调节到0.45Pa~0.55Pa,开启直流及脉冲复合电源中的直流恒流电源加载


在装有钛硅靶材的磁控溅射靶上,预溅射11min~14min,然后拉开挡板,在骨固定片状材料


上镀钛硅膜层,镀膜时间为4.5min~5.5min。其它步骤和参数与具体实施方式一至六之一相同。


具体实施方式八:本实施方式与具体实施方式一至六之一不同的是:步骤三中溅射清洗


后,将真空室内气压调节到0.5Pa,开启直流及脉冲复合电源中的直流恒流电源加载在装有钛


硅靶材的磁控溅射靶上,预溅射12min,然后拉开挡板,在骨固定片状材料上镀钛硅膜层,


镀膜时间为5min。其它步骤和参数与具体实施方式一至六之一相同。


具体实施方式九:本实施方式与具体实施方式一至八之一不同的是:步骤三中将真空室


内气压调节到0.4Pa~0.8Pa,再将直流及脉冲复合电源加载在装有钽靶材的磁控溅射靶上,预


溅射11min~14min后,拉开挡板,在骨固定片状材料上镀钽膜层,镀膜时间为29min~31min。


其它步骤和参数与具体实施方式一至八之一相同。


具体实施方式十:本实施方式与具体实施方式一至八之一不同的是:步骤三中将真空室


内气压调节到0.6Pa,再将直流及脉冲复合电源加载在装有钽靶材的磁控溅射靶上,预溅射


12min后,拉开挡板,在骨固定片状材料上镀钽膜层,镀膜时间为30min。其它步骤和参数与


具体实施方式一至八之一相同。


为验证本发明的有益效果进行了以下实验:


实验一:镁合金表面磁控溅射沉积钽膜的制备方法按以下步骤进行:


一、将按质量百分比由94.2%的Mg、5.21%的Zn、0.5%的Zr、0.2%的Ca和0.09%的


Mn组成的镁合金薄板用线切割机切割成4个Ф12mm×1.5mm的镁合金圆片,先后用280#、


500#、800#、1000#和2000#金相砂纸打磨抛光,吹掉表面磨屑;


二、将步骤一中得到的打磨抛光后的4个镁合金圆片先放入丙酮中,在超声功率为165


的条件下,清洗36min,然后再放到乙醇中,在超声功率为165W的条件下,清洗24min,吹


干后装夹在磁控溅射设备的真空室中的样品台上;


三、将钛硅靶材和钽靶材分别安装在不同的磁控溅射靶上,然后开始抽真空,当真空室


气压达到4×10-3Pa时,通入氩气并调节真空室内气压至1Pa,开启射频电源及偏压电源,溅


射清洗镁合金圆片18min,完成镀膜前的准备,其中射频电源的加载在磁控溅射靶与样品台


之间的电压为1.0KV,电流为0.28A,射频频率为13.56MHz,偏压电源加载在样品台上的电


压为-500V,钛硅靶材和钽靶材的规格尺寸为Φ68mm×6mm,靶基距为70mm;


四、溅射清洗后,将真空室内气压调节到0.5Pa,开启直流及脉冲复合电源中的直流恒流


电源加载在装有钛硅靶材的磁控溅射靶上,预溅射12min,然后拉开挡板,在骨固定片状材


料上镀钛硅膜层,镀膜时间为5min,然后关闭加载在装有钛硅靶材的磁控溅射靶上的直流恒


流电源,拉上挡板,将真空室内气压调节到0.5Pa,再将直流及脉冲复合电源加载在装有钽靶


材的磁控溅射靶上,预溅射12min后,拉开挡板,在骨固定片状材料上镀钽膜层,镀膜时间


为30min,关闭直流及脉冲复合电源,关闭镀膜设备,完成镁合金表面钽膜的制备过程,其


中溅射钛硅靶时,直流恒流电源加载在装有钛硅靶材的磁控溅射靶上的电流为0.5A;溅射钽


靶时,直流恒流电源加载在装有钽靶材的磁控溅射靶上的电流为0.5A,脉冲电源加载在装有


钽靶材的磁控溅射靶上的脉冲电压为500V,脉冲频率为100Hz,脉宽为100μs。


图1至图4是实验一中4个镁合金圆片表面高功率脉冲复合直流磁控溅射沉积钽膜×2000


的表面形貌,由图1至图4可以看到采用高功率脉冲复合直流磁控溅射沉积的钽膜表面光滑


平整,致密度高,因而膜层具有良好的耐蚀性。图5是实验一中4个镁合金圆片表面高功率


脉冲复合直流磁控溅射沉积钽膜的XRD图谱,由图5可以看到膜层由体心立方α相和四方β


相的混合结构构成,并且以α相为主,因而膜层良好的耐磨性。


【EN】

The preparation method of Mg alloy surface magnetron sputtering deposition tantalum film

Technical field

The present invention relates to the preparation method of Mg alloy surface tantalum film.

Background technology

Along with biomedical development, the application of biomedical metallic material is also all the more extensive.Magnesium alloy with the title of " 21 century tool development potentiality and the green engineering material of future ", because its density is low, specific tenacity and the outstanding advantages such as specific rigidity is high, Young's modulus and bone approach, good biocompatibility and degradability, it is had a good application prospect at aspects such as angiocarpy bracket, bone immobilizing materials.Simultaneously, due to these advantages of magnesium alloy, it also obtains a wide range of applications in fields such as space flight and aviation, automotive industry, electronic industries.Yet corrosion stability of magnesium alloy is poor, corrosion speed is too fast, and its further development and application are restricted.Therefore, improving corrosion stability of magnesium alloy makes it at biomedical sector and industrial circle acquisition application widely, become key issue urgently to be resolved hurrily.

Solve at present the poor problem of corrosion stability of magnesium alloy and mainly adopt process for modifying surface, mainly comprise: bioactive coating method, anodic oxidation embrane method, degradable macromolecule coating and chemical conversion embrane method.The problem that the bioactive coating method mainly exists is that coating fragility is larger, and magnesium alloy is poor with painting interlayer bonding force; Anodic oxidation embrane method advantage is that magnesium alloy and intermembranous bonding force are stronger, and solidity to corrosion is also stronger, but oxide film whether degradable need further to confirm; Degradable macromolecule coating and bioactive coating method, that the anodic oxidation embrane method is compared wear resistance is poor; The shortcoming of chemical conversion embrane method is: thicknesses of layers is all very thin, can not resist any physical abuse, only can do prime coat and use, and its biocompatibility also needs further confirmation.

Summary of the invention

The present invention will solve the problem that between the magnesium alloy that exists in existing Magnesiumalloy surface modifying technology and coating or rete, bonding force is poor, the rete degradability is poor, rete wears no resistance and the rete biocompatibility is poor and propose Mg alloy surface magnetron sputtering deposition tantalum and tantalum composite membrane preparation method.

The preparation method of the Mg alloy surface magnetron sputtering deposition tantalum film in the present invention carries out according to the following steps:

One, the cleaning of sample: by the bone of magnesium alloy material fixedly flaky material first put into acetone, the condition that is 150W~180W at ultrasonic power, clean 30min~45min, and then be put in ethanol, the condition that is 150W~180W at ultrasonic power, clean 15min~30min, dry up on the sample table of rear clamping in the vacuum chamber of magnetron sputtering equipment, wherein magnesium alloy is comprised of 93.5%~94.5% Mg, 4.5%~5.5% Zn, 0.4%~0.8% Zr, 0.15%~0.25% Ca and 0.08%~0.1% Mn by mass percentage;

Two, the preparation before plated film: titanium silicon target material and tantalum target are arranged on respectively on different magnetron sputtering targets, then start to vacuumize, when gas pressure in vacuum reaches 3 * 10

-3pa~5 * 10

-3during Pa, pass into argon gas and regulate the vacuum chamber internal gas pressure to 0.8Pa~1.2Pa, open radio-frequency power supply and grid bias power supply, the sputter clean bone is flaky material 15min~20min fixedly, complete the front preparation of plated film, wherein the voltage be carried between magnetron sputtering target and sample table of radio-frequency power supply is 1.0KV, electric current is 0.28A, rf frequency is 13.56MHz, the voltage that grid bias power supply is carried on sample table is-500V, the specification of titanium silicon target material and tantalum target is Φ 68mm * 6mm, and target-substrate distance is 60mm~120mm;

Three, plated film: after sputter clean, the vacuum chamber internal gas pressure is adjusted to 0.4Pa~0.6Pa, the DC constant flowing power of opening in direct current and pulse composite power source is carried on the magnetron sputtering target that titanium silicon target material is housed, pre-sputtering 10min~15min, then pull open baffle plate, at the fixing titanizing silicon film on flaky material of bone, the plated film time is 4min~6min, then close the DC constant flowing power be carried on the magnetron sputtering target that titanium silicon target material is housed, pull on baffle plate, the vacuum chamber internal gas pressure is adjusted to 0.3Pa~0.9Pa, again direct current and pulse composite power source are carried on the magnetron sputtering target that tantalum target is housed, after pre-sputtering 10min~15min, pull open baffle plate, fixedly on flaky material, plate the tantalum film layer at bone, the plated film time is 28min~32min, close direct current and pulse composite power source, close filming equipment, complete the preparation process of Mg alloy surface tantalum film, wherein during the sputtered titanium silicon target, the electric current that DC constant flowing power is carried on the magnetron sputtering target that titanium silicon target material is housed is 0.2A~1A, during the sputter tantalum target, the electric current that DC constant flowing power is carried on the magnetron sputtering target that tantalum target is housed is 0.2A~1A, the pulsed voltage that the pulse power is carried on the magnetron sputtering target that tantalum target is housed is 300V~800V, and pulse-repetition is 50Hz~150Hz, and pulsewidth is 50 μ s~150 μ s.

Mechanism of the present invention is: in process for modifying surface, magnetron sputtering has base material temperature rise in sputter procedure and hangs down and can realize the large typical feature of " at a high speed " sputter two.In sputter material, the nitride of tantalum and tantalum, oxide compound and carbide all have high anti-corrosion, high-wearing feature and good biocompatibility simultaneously.Given this, the present invention proposes to adopt magnetron sputtering technique fine and close and be combined good tantalum and tantalum composite membrane with matrix in Mg alloy surface preparation, obtains the coating composite material with high anti-corrosion, high-wearing feature and good biocompatibility.

Beneficial effect of the present invention is as follows:

1, propose a kind of employing magnetron sputtered deposition technology, prepare densification and there is bioactive rete matrix material; The bonding strength of magnesium alloy tantalum film layer and matrix is between 8MPa~20MPa, higher than femoral head in the situation that the upright intensity 0.5Mpa carried of people~1.75Mpa.

2, the tantalum film layer that adopts magnetron sputtered deposition technology to prepare on magnesium alloy has the characteristics of good solidity to corrosion, wear resistance and biocompatibility.

3, the magnetron sputtered deposition technology that the present invention adopts comprises: magnetically controlled DC sputtering technology, high pressure inject compound direct current magnetron sputtering technique and high pressure injects compound high-power impulse magnetron sputtering technology, present technique has the characteristics such as safe, pollution-free, equipment is simple, easy to operate, is the environmental protection process for treating surface.

The accompanying drawing explanation

Fig. 1 to Fig. 4 is the surface topography of 4 the compound Deposited By Dc Magnetron Sputtering tantalum film of magnesium alloy disk surfaces high power pulse * 2000 in experiment one;

Fig. 5 is the XRD figure spectrum of 4 compound Deposited By Dc Magnetron Sputtering tantalum films of magnesium alloy disk surfaces high power pulse in experiment one.

Embodiment

Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.

Embodiment one: in present embodiment, the preparation method of Mg alloy surface magnetron sputtering deposition tantalum film carries out according to the following steps:

One, the cleaning of sample: by the bone of magnesium alloy material fixedly flaky material first put into acetone, under the condition that is 150W~180W at ultrasonic power, clean 30min~45min, and then be put in ethanol, under the condition that is 150W~180W at ultrasonic power, clean 15min~30min, dry up on the sample table of rear clamping in the vacuum chamber of magnetron sputtering equipment, wherein magnesium alloy is comprised of 93.5%~94.5% Mg, 4.5%~5.5% Zn, 0.4%~0.8% Zr, 0.15%~0.25% Ca and 0.08%~0.1% Mn by mass percentage;

Two, the preparation before plated film: titanium silicon target material and tantalum target are arranged on respectively on different magnetron sputtering targets, then start to vacuumize, when gas pressure in vacuum reaches 3 * 10

-3pa~5 * 10

-3during Pa, pass into argon gas and regulate the vacuum chamber internal gas pressure to 0.8Pa~1.2Pa, open radio-frequency power supply and grid bias power supply, the sputter clean bone is flaky material 15min~20min fixedly, complete the front preparation of plated film, wherein the voltage be carried between magnetron sputtering target and sample table of radio-frequency power supply is 1.0KV, electric current is 0.28A, rf frequency is 13.56MHz, the voltage that grid bias power supply is carried on sample table is-500V, the specification of titanium silicon target material and tantalum target is Φ 68mm * 6mm, and target-substrate distance is 60mm~120mm;

Three, plated film: after sputter clean, the vacuum chamber internal gas pressure is adjusted to 0.4Pa~0.6Pa, the DC constant flowing power of opening in direct current and pulse composite power source is carried on the magnetron sputtering target that titanium silicon target material is housed, pre-sputtering 10min~15min, then pull open baffle plate, at the fixing titanizing silicon film on flaky material of bone, the plated film time is 4min~6min, then close the DC constant flowing power be carried on the magnetron sputtering target that titanium silicon target material is housed, pull on baffle plate, the vacuum chamber internal gas pressure is adjusted to 0.3Pa~0.9Pa, again direct current and pulse composite power source are carried on the magnetron sputtering target that tantalum target is housed, after pre-sputtering 10min~15min, pull open baffle plate, fixedly on flaky material, plate the tantalum film layer at bone, the plated film time is 28min~32min, close direct current and pulse composite power source, close filming equipment, complete the preparation process of Mg alloy surface tantalum film, wherein during the sputtered titanium silicon target, the electric current that DC constant flowing power is carried on the magnetron sputtering target that titanium silicon target material is housed is 0.2A~1A, during the sputter tantalum target, the electric current that DC constant flowing power is carried on the magnetron sputtering target that tantalum target is housed is 0.2A~1A, the pulsed voltage that the pulse power is carried on the magnetron sputtering target that tantalum target is housed is 300V~800V, and pulse-repetition is 50Hz~150Hz, and pulsewidth is 50 μ s~150 μ s.

Mechanism of the present invention is: in process for modifying surface, magnetron sputtering has base material temperature rise in sputter procedure and hangs down and can realize the large typical feature of " at a high speed " sputter two.In sputter material, the nitride of tantalum and tantalum, oxide compound and carbide all have high anti-corrosion, high-wearing feature and good biocompatibility simultaneously.Given this, the present invention proposes to adopt magnetron sputtering technique fine and close and be combined good tantalum and tantalum composite membrane with matrix in Mg alloy surface preparation, obtains the coating composite material with high anti-corrosion, high-wearing feature and good biocompatibility.

Beneficial effect of the present invention is as follows:

1, propose a kind of employing magnetron sputtered deposition technology, prepare densification and there is bioactive rete matrix material; The bonding strength of magnesium alloy tantalum film layer and matrix is between 8MPa~20MPa, higher than femoral head in the situation that the upright intensity 0.5Mpa carried of people~1.75Mpa.

2, the magnesium alloy tantalum film layer that adopts magnetron sputtered deposition technology to prepare has the characteristics of good solidity to corrosion, wear resistance and biocompatibility.

3, the magnetron sputtered deposition technology that the present invention adopts comprises: magnetically controlled DC sputtering technology, high pressure inject compound direct current magnetron sputtering technique and high pressure injects compound high-power impulse magnetron sputtering technology, present technique has the characteristics such as safe, pollution-free, equipment is simple, easy to operate, is the environmental protection process for treating surface.

Embodiment two: present embodiment is different from embodiment one: in step 1 bone fixedly flaky material first put into acetone, under the condition that is 160W~170W at ultrasonic power, clean 35min~40min, and then be put in ethanol, under the condition that is 160W~170W at ultrasonic power, clean 20min~25min.Other step and parameter are identical with embodiment one.

Embodiment three: present embodiment is different from embodiment one: in step 1 bone fixedly flaky material first put into acetone, under the condition that is 165W at ultrasonic power, clean 36min, and then be put in ethanol, under the condition that is 165W at ultrasonic power, clean 24min.Other step and parameter are identical with embodiment one.

Embodiment four: present embodiment is different from one of embodiment one to three: work as gas pressure in vacuum in step 2 and reach 3.5 * 10

-3pa~4.5 * 10

-3during Pa, pass into argon gas and regulate the vacuum chamber internal gas pressure to 0.9Pa~1.1Pa, open radio-frequency power supply and grid bias power supply, the sputter clean bone is flaky material 16min~19min fixedly.Other step and parameter are identical with one of embodiment one to three.

Embodiment five: present embodiment is different from one of embodiment one to three: work as gas pressure in vacuum in step 2 and reach 4 * 10

-3during Pa, pass into argon gas and regulate the vacuum chamber internal gas pressure to 1Pa, open radio-frequency power supply and grid bias power supply, the sputter clean bone is flaky material 18min fixedly.Other step and parameter are identical with one of embodiment one to three.

Embodiment six: present embodiment is different from one of embodiment one to five: in step 2, target-substrate distance is 70mm~110mm.Other step and parameter are identical with one of embodiment one to five.

Embodiment seven: present embodiment is different from one of embodiment one to six: in step 3 after sputter clean, the vacuum chamber internal gas pressure is adjusted to 0.45Pa~0.55Pa, the DC constant flowing power of opening in direct current and pulse composite power source is carried on the magnetron sputtering target that titanium silicon target material is housed, pre-sputtering 11min~14min, then pull open baffle plate, at the fixing titanizing silicon film on flaky material of bone, the plated film time is 4.5min~5.5min.Other step and parameter are identical with one of embodiment one to six.

Embodiment eight: present embodiment is different from one of embodiment one to six: in step 3 after sputter clean, the vacuum chamber internal gas pressure is adjusted to 0.5Pa, the DC constant flowing power of opening in direct current and pulse composite power source is carried on the magnetron sputtering target that titanium silicon target material is housed, pre-sputtering 12min, then pull open baffle plate, at the fixing titanizing silicon film on flaky material of bone, the plated film time is 5min.Other step and parameter are identical with one of embodiment one to six.

Embodiment nine: present embodiment is different from one of embodiment one to eight: in step 3, the vacuum chamber internal gas pressure is adjusted to 0.4Pa~0.8Pa, again direct current and pulse composite power source are carried on the magnetron sputtering target that tantalum target is housed, after pre-sputtering 11min~14min, pull open baffle plate, fixedly on flaky material, plate the tantalum film layer at bone, the plated film time is 29min~31min.Other step and parameter are identical with one of embodiment one to eight.

Embodiment ten: present embodiment is different from one of embodiment one to eight: in step 3, the vacuum chamber internal gas pressure is adjusted to 0.6Pa, again direct current and pulse composite power source are carried on the magnetron sputtering target that tantalum target is housed, after pre-sputtering 12min, pull open baffle plate, fixedly on flaky material, plate the tantalum film layer at bone, the plated film time is 30min.Other step and parameter are identical with one of embodiment one to eight.

For verifying that beneficial effect of the present invention has carried out following experiment:

Experiment one: the preparation method of Mg alloy surface magnetron sputtering deposition tantalum film carries out according to the following steps:

One, the magnesium alloy sheet will be by mass percentage be comprised of the Mn of 94.2% Mg, 5.21% Zn, 0.5% Zr, 0.2% Ca and 0.09% cuts into the magnesium alloy disk of 4 Ф 12mm * 1.5mm with wire cutting machine, successively, with 280#, 500#, 800#, 1000# and 2000# abrasive paper for metallograph sanding and polishing, blow surperficial abrasive dust off;

Two, 4 magnesium alloy disks after the sanding and polishing obtained in step 1 are first put into to acetone, under the condition that is 165 at ultrasonic power, clean 36min, and then be put in ethanol, under the condition that is 165W at ultrasonic power, clean 24min, dry up on the sample table of rear clamping in the vacuum chamber of magnetron sputtering equipment;

Three, titanium silicon target material and tantalum target are arranged on respectively on different magnetron sputtering targets, then start to vacuumize, when gas pressure in vacuum reaches 4 * 10

-3during Pa, pass into argon gas and regulate the vacuum chamber internal gas pressure to 1Pa, open radio-frequency power supply and grid bias power supply, sputter clean magnesium alloy disk 18min, complete the front preparation of plated film, wherein the voltage be carried between magnetron sputtering target and sample table of radio-frequency power supply is 1.0KV, electric current is 0.28A, and rf frequency is 13.56MHz, and the voltage that grid bias power supply is carried on sample table is-500V, the specification of titanium silicon target material and tantalum target is Φ 68mm * 6mm, and target-substrate distance is 70mm;

Four, after sputter clean, the vacuum chamber internal gas pressure is adjusted to 0.5Pa, the DC constant flowing power of opening in direct current and pulse composite power source is carried on the magnetron sputtering target that titanium silicon target material is housed, pre-sputtering 12min, then pull open baffle plate, at the fixing titanizing silicon film on flaky material of bone, the plated film time is 5min, then close the DC constant flowing power be carried on the magnetron sputtering target that titanium silicon target material is housed, pull on baffle plate, the vacuum chamber internal gas pressure is adjusted to 0.5Pa, again direct current and pulse composite power source are carried on the magnetron sputtering target that tantalum target is housed, after pre-sputtering 12min, pull open baffle plate, fixedly on flaky material, plate the tantalum film layer at bone, the plated film time is 30min, close direct current and pulse composite power source, close filming equipment, complete the preparation process of Mg alloy surface tantalum film, wherein during the sputtered titanium silicon target, the electric current that DC constant flowing power is carried on the magnetron sputtering target that titanium silicon target material is housed is 0.5A, during the sputter tantalum target, the electric current that DC constant flowing power is carried on the magnetron sputtering target that tantalum target is housed is 0.5A, and the pulsed voltage that the pulse power is carried on the magnetron sputtering target that tantalum target is housed is 500V, and pulse-repetition is 100Hz, and pulsewidth is 100 μ s.

Fig. 1 to Fig. 4 is the surface topography of 4 the compound Deposited By Dc Magnetron Sputtering tantalum film of magnesium alloy disk surfaces high power pulse * 2000 in experiment one, the tantalum film smooth surface that can be seen the compound Deposited By Dc Magnetron Sputtering of employing high power pulse by Fig. 1 to Fig. 4 is smooth, density is high, thereby rete has good solidity to corrosion.Fig. 5 is the XRD figure spectrum of 4 compound Deposited By Dc Magnetron Sputtering tantalum films of magnesium alloy disk surfaces high power pulse in experiment one, can see that by Fig. 5 rete consists of the mixed structure of body-centered cubic α phase and cubic β phase, and take α mutually as main, thereby the good wear resistance of rete.

图1
PatViewer知识产权搜索   专利、商标、地理标志、集成电路
©2018 IPPH.cn  主办单位:国家知识产权局知识产权出版社  咨询热线:01082000860-8588
浏览器:火狐、谷歌、opera、ie9及以上等  京ICP备09007110号 京公网安备 11010802026659号 开放平台