技术领域technical field
本发明涉及医疗领域，尤其是一种个性化碳-碳复合材料人工骨的制备方法。The invention relates to the medical field, in particular to a method for preparing a personalized carbon-carbon composite material artificial bone.
背景技术Background technique
人工骨置换手术作为有效的治疗方法在国内外已广泛开展。人的骨骼虽大体形貌一致，但骨骼结构存在较大差异，股骨颈干角可以从110°变化到140°，平均125°，统一的假体不能适用于所有病人。普通的假体柄不能适合每个人的髓腔，使假体与骨之间存在空隙，再受力时会产生微小的晃动，Bowman SM等通过对牛骨小梁的微动实验发现微动会对骨小梁产生疲劳性损伤。假体与骨的紧密结合同时使假体所受的力均匀地传导至骨骼，减少了应力遮挡作用所产生的骨萎缩和骨吸收。所以人工骨假体产品具有极高的个性化特点，标准、系列化的产品往往对一些病人不合适，目前国内使用的人工假体设计参数部分来自欧美人种。因此要设计制造个体化的假体来满足病人骨骼结构的要求，在设计过程中可以人工干预，从而得到最佳人工骨假体。As an effective treatment method, artificial bone replacement surgery has been widely carried out at home and abroad. Although the general appearance of human bones is the same, there are large differences in bone structure. The femoral neck-shaft angle can vary from 110° to 140°, with an average of 125°. A uniform prosthesis cannot be applied to all patients. Ordinary prosthetic stems cannot fit everyone's medullary cavity, so there is a gap between the prosthesis and the bone, and there will be slight shaking when the force is applied again. Bowman SM et al. found that the fretting will be Fatigue damage to trabecular bone. The tight combination of the prosthesis and the bone makes the force of the prosthesis evenly transmitted to the bone, reducing the bone atrophy and bone absorption caused by the stress shielding effect. Therefore, artificial bone prosthesis products have extremely high individual characteristics, and standard and serialized products are often not suitable for some patients. At present, some of the design parameters of artificial prosthesis used in China come from European and American races. Therefore, it is necessary to design and manufacture individualized prostheses to meet the requirements of the patient's bone structure, and manual intervention can be performed during the design process to obtain the best artificial bone prosthesis.
碳是组成有机物质的主要元素之一，更是构成人体的重要元素，碳材料已在心脏瓣膜、骨骼、齿根、血管、肌腱等诸多人工材料方面获得应用和发展。碳/碳复合材料克服了单一碳材料的脆性,具有高强度、高韧性、耐腐蚀、耐高温等优点。碳/碳复合材料是以碳纤维增强碳基体的新型复合材料，弹性模量与人骨相当，具有良好的生物力学相容性。本课题组前期研究认为经过特殊处理的碳/碳复合材料是符合中华人民共和国国家医疗器械生物学安全标准的。而且本课题组通过影像学比较认为：碳/碳复合材料植入物相对于金属植入物在影像学检查上不会产生金属伪影和对射线阻挡作用。碳/碳复合材料是一种极有潜力的新型生物医用材料，个体化碳/碳复合材料人工骨的制备是发展趋势。但是目前个体化碳/碳复合材料人工骨的制备相对于金属植入物来说制造周期长、成本高，制约了碳/碳复合材料人工骨发展。金属修复体一般先通过CT扫描获得二维和三维信息，进行建模后生成模具或模型，再通过铸造获得个体化的人工骨，而碳/碳复合材料人工骨由于需要对碳纤维的排列及热解碳的沉积，因此金属植入物的制造方法对于碳/碳复合材料人工骨的制备是不合适的。Carbon is one of the main elements that make up organic matter, and it is an important element that makes up the human body. Carbon materials have been applied and developed in many artificial materials such as heart valves, bones, tooth roots, blood vessels, and tendons. Carbon/carbon composites overcome the brittleness of single carbon materials, and have the advantages of high strength, high toughness, corrosion resistance, and high temperature resistance. Carbon/carbon composite material is a new type of composite material with carbon fiber reinforced carbon matrix. Its elastic modulus is equivalent to that of human bone and has good biomechanical compatibility. The previous research of this research group concluded that the specially treated carbon/carbon composite material is in line with the national medical device biological safety standards of the People's Republic of China. Moreover, our research group believes through imaging comparison that carbon/carbon composite implants will not produce metal artifacts and ray blocking effects in imaging examination compared with metal implants. Carbon/carbon composite material is a new biomedical material with great potential, and the preparation of individualized carbon/carbon composite artificial bone is a development trend. However, compared with metal implants, the preparation of individualized carbon/carbon composite artificial bones has a long manufacturing cycle and high cost, which restricts the development of carbon/carbon composite artificial bones. Metal restorations generally obtain two-dimensional and three-dimensional information through CT scanning, generate molds or models after modeling, and then obtain individualized artificial bones through casting. The deposition of carbon is decomposed, so the manufacturing method of metal implants is not suitable for the preparation of carbon/carbon composite artificial bone.
发明内容Contents of the invention
本发明要解决的技术问题是：为了克服上述中存在的问题，提供一种个性化碳-碳复合材料人工骨的制备方法，其克服了单一碳材料的脆性，具有高强度、高韧性、耐腐蚀性、耐高温的特点。The technical problem to be solved by the present invention is: in order to overcome the above-mentioned problems, provide a method for preparing a personalized carbon-carbon composite artificial bone, which overcomes the brittleness of a single carbon material, and has high strength, high toughness, and durability. Corrosive, high temperature characteristics.
本发明解决其技术问题所采用的技术方案是：一种个性化碳/碳复合材料人工骨的制备方法，具体步骤如下：The technical solution adopted by the present invention to solve the technical problem is: a preparation method of personalized carbon/carbon composite material artificial bone, the specific steps are as follows:
a.选择碳纤维增强碳基体作为原料，碳纤维增强碳基体的弹性模量与人骨相当，具有良好的生物力学相容性；a. Choose carbon fiber reinforced carbon matrix as raw material, the elastic modulus of carbon fiber reinforced carbon matrix is equivalent to that of human bone, and has good biomechanical compatibility;
b.通过CT图像的采集进行人工骨轮廓，采集后的人工骨轮廓转换成非均匀有理B样条曲面的方法对碳/碳复合材料进行处理后形成碳/碳复合材料人工骨，其具体方法如下：(1)轮廓勾画；(2)生成二值体数据；(3)三角网格生成；(4)转换成NURBS曲面；b. Through the acquisition of CT images, the artificial bone outline is converted into a non-uniform rational B-spline surface, and the carbon/carbon composite material is processed to form a carbon/carbon composite artificial bone. The specific method As follows: (1) Outline drawing; (2) Generate binary volume data; (3) Triangular mesh generation; (4) Convert to NURBS surface;
c.将碳纤维增强碳基体放入真空辉光放电室中，在真空辉光放电室中通入氩气进行对碳纤维增强碳基体表面进行等离子预处理，去除碳纤维周围热解碳表面的皱褶、碎片、结合力差的特性，使得羟基磷灰石与碳纤维结合强度提高，真空辉光放电室的直流电源电压、氩气的压力、工作电流、工作时间等参数可调，经过处理后的碳纤维增强碳基体放入酒精溶液中进行超声清洗，清洗氩气轰击下来的热解碳颗粒；c. Put the carbon fiber reinforced carbon matrix into a vacuum glow discharge chamber, and pass argon gas into the vacuum glow discharge chamber to carry out plasma pretreatment on the surface of the carbon fiber reinforced carbon matrix to remove wrinkles on the pyrolytic carbon surface around the carbon fiber, The characteristics of fragments and poor bonding force improve the bonding strength of hydroxyapatite and carbon fiber. The parameters of the DC power supply voltage of the vacuum glow discharge chamber, the pressure of argon gas, the working current, and the working time are adjustable. The treated carbon fiber is reinforced. The carbon matrix is placed in an alcohol solution for ultrasonic cleaning to clean the pyrolytic carbon particles bombarded by argon;
d.对清洗过后的碳纤维增强碳基体表面进行喷涂羟基磷灰石涂层形成成品碳/碳复合材料人工骨，喷等离子喷涂功率为38kw，喷涂距离为110mm，喷枪移动速率为180mm/s，涂层厚度为70um，满足人体对羟基磷灰石图层厚度的要求。d. Spray the hydroxyapatite coating on the surface of the cleaned carbon fiber reinforced carbon matrix to form the finished carbon/carbon composite artificial bone. The thickness of the layer is 70um, which meets the human body's requirement for the thickness of the hydroxyapatite layer.
d中碳/碳复合材料人工骨包括碳/碳复合材料和羟基磷灰石，羟基磷灰石喷涂在碳/碳复合材料表面上。In d, the carbon/carbon composite material artificial bone includes carbon/carbon composite material and hydroxyapatite, and the hydroxyapatite is sprayed on the surface of the carbon/carbon composite material.
本发明的有益效果是，本发明的一种个性化碳-碳复合材料人工骨的制备方法，通过CT图像制备得到的碳/碳复合材料人工骨能够与其被更换的自身骨形状一致；在碳/碳复合材料的表面上喷涂羟基磷灰石涂层，能够提高碳/碳复合材料表面活性，有效地减少碳颗粒的释放；通过等离子体预处理，可以提高羟基磷灰石涂层与碳/碳复合材料之间的结合力；能够使其弹性模量与人骨相当，具有高强度、高韧性、耐腐蚀和耐高温的特性，并且为良好应用前景的人工关节、骨假体材料。The beneficial effect of the present invention is that, according to the preparation method of a personalized carbon-carbon composite artificial bone of the present invention, the carbon/carbon composite artificial bone prepared by CT images can be consistent with the shape of its own bone to be replaced; Spraying hydroxyapatite coating on the surface of carbon/carbon composite material can improve the surface activity of carbon/carbon composite material and effectively reduce the release of carbon particles; through plasma pretreatment, the hydroxyapatite coating and carbon/carbon composite can be improved The bonding force between carbon composite materials can make its elastic modulus comparable to that of human bone, with high strength, high toughness, corrosion resistance and high temperature resistance, and it is an artificial joint and bone prosthesis material with good application prospects.
附图说明Description of drawings
下面结合附图和实施例对本发明进一步说明。The present invention will be further described below in conjunction with the accompanying drawings and embodiments.
图1是本发明的非均匀有理B样条曲面流程图；Fig. 1 is non-uniform rational B-spline surface flow chart of the present invention;
图2是本发明的轮廓勾画的示意图；Fig. 2 is a schematic diagram of outline drawing of the present invention;
图3是本发明的多边形和对应的图像；Figure 3 is a polygon and corresponding image of the present invention;
图4是本发明的等离子处理后的碳/碳复合材料SEM形貌示意图；Fig. 4 is the SEM morphology schematic diagram of the carbon/carbon composite material after plasma treatment of the present invention;
图5是本发明等离子体处理碳/碳复合材料的红外光谱图；Fig. 5 is the infrared spectrogram of plasma treatment carbon/carbon composite material of the present invention;
图6是本发明的羟基磷灰石的涂层SEM形貌和电子能谱示意图；Fig. 6 is the coating SEM morphology and electron energy spectrum schematic diagram of the hydroxyapatite of the present invention;
图7是本发明的羟基磷灰石涂层的红外吸收光谱示意图；Figure 7 is a schematic diagram of the infrared absorption spectrum of the hydroxyapatite coating of the present invention;
图8是本发明的羟基磷灰石涂层的XRD衍射图谱示意图；Figure 8 is a schematic diagram of the XRD diffraction pattern of the hydroxyapatite coating of the present invention;
图9是本发明的划痕试验和SEM形貌示意图。Fig. 9 is a schematic diagram of scratch test and SEM morphology of the present invention.
具体实施方式Detailed ways
现在结合附图对本发明作进一步详细的说明。这些附图均为简化的示意图，仅以示意方式说明本发明的基本结构，因此其仅显示与本发明有关的构成。The present invention is described in further detail now in conjunction with accompanying drawing. These drawings are all simplified schematic diagrams, which only illustrate the basic structure of the present invention in a schematic manner, so they only show the configurations related to the present invention.
一种个性化碳-碳复合材料人工骨的制备方法，具体步骤如下：a.选择碳纤维增强碳基体作为原料；A method for preparing a personalized carbon-carbon composite material artificial bone, the specific steps are as follows: a. Selecting a carbon fiber reinforced carbon matrix as a raw material;
b.通过CT图像的采集进行人工骨轮廓，采集后的人工骨轮廓转换成非均匀有理B样条曲面(如图1)的方法对碳/碳复合材料进行处理后形成碳/碳复合材料人工骨，其具体方法如下：(1)轮廓勾画：在DICOM RT上通过RT struct模块自动和手动相结合勾画骨轮廓，自动勾画可以较快的勾画轮廓，手动勾画相对准确但费时。自动勾画采用auto-by-threshold技术，即把CT灰度分为128等级，再转换成红色的64灰阶等级图，如图2(a)所示，利用公式b. Carry out the artificial bone outline through the acquisition of CT images, and convert the acquired artificial bone outline into a non-uniform rational B-spline surface (as shown in Figure 1) to process the carbon/carbon composite material to form a carbon/carbon composite material artificial Bone, the specific method is as follows: (1) Contour delineation: On DICOM RT, the RT struct module is used to delineate the bone contour automatically and manually. Automatic delineation can delineate the contour quickly, while manual delineation is relatively accurate but time-consuming. The auto-outline adopts the auto-by-threshold technology, that is, the CT gray scale is divided into 128 levels, and then converted into a red 64 gray scale map, as shown in Figure 2(a), using the formula
计算得到每个灰阶所代表的像素值，选取其中 Calculate the pixel value represented by each gray scale, select one of
某一点状区域等级色图为参考值，这相同灰阶等级的区域为轮廓，调节CT的窗宽、窗位，可以得到较满意的轮廓图，但是对于相邻的两个骨组织调节窗值不能很好的区分，只有通过手动区分。图2(b)为人工肱骨头的轮廓，人工肱骨头的假体柄的轮廓略小于右侧肱骨骨髓腔的轮廓，以保证该假体柄能够顺利地插入到髓腔中；图2(c)为多层轮廓叠加人工肱骨头的结果；(2)生成二值体数据：把提取出来的多边形画到一个体(volume)数据中。Volume为二值体数据，多边形内部用0表示，多边形外部用1表示。这样就由多边形数据生成了一个volume数据，如图3所示；(3)三角网格生成：上述步骤生成的二值体数据中0和1之间的过渡面即为骨骼的表面。本文使用marching cubes算法提取上述体数据中值为0.5的等值面，得到一个表面三角形网格。三角形网格足以描述一个三维物体的表面信息；(4)转换成NURBS曲面：机械加工所使用的数据模型大多采用非均匀有理B样条来表示。因此，若要所建立的模型能方便地进行机械加工，需要将其转换为NURBS表示的模型。本文工作使用GeomagicStudio12软件把三角网格转换成非均匀有理B样条曲面，使用网格医生来分析和修复多边形网格，通过轮廓线与边界线生成曲面片结构，再修理曲面片防止曲面错误，构造格栅，拟合曲面生存一个NURBS曲面，保存为iges模型文件；The level color map of a point-shaped area is a reference value, and the area with the same gray scale level is a contour. Adjusting the window width and window level of CT can obtain a satisfactory contour map, but adjust the window value for two adjacent bone tissues It cannot be distinguished very well, only by manual distinction. Figure 2(b) is the outline of the artificial humeral head. The outline of the prosthetic stem of the artificial humeral head is slightly smaller than the outline of the medullary cavity of the right humerus to ensure that the prosthetic stem can be smoothly inserted into the medullary cavity; Figure 2(c ) The result of superimposing the artificial humeral head for the multi-layer contour; (2) Generate binary volume data: draw the extracted polygon into a volume data. Volume is binary data, which is represented by 0 inside the polygon and 1 outside the polygon. In this way, a volume data is generated from the polygon data, as shown in Figure 3; (3) Triangular mesh generation: the transition surface between 0 and 1 in the binary volume data generated in the above steps is the surface of the bone. In this paper, the marching cubes algorithm is used to extract the isosurface with a value of 0.5 in the above volume data, and a surface triangular mesh is obtained. Triangular mesh is enough to describe the surface information of a three-dimensional object; (4) Convert to NURBS surface: Most of the data models used in machining are represented by non-uniform rational B-splines. Therefore, if the established model can be conveniently machined, it needs to be converted into a model represented by NURBS. This work uses GeomagicStudio12 software to convert the triangular mesh into a non-uniform rational B-spline surface, uses the grid doctor to analyze and repair the polygonal mesh, generates the surface patch structure through the contour lines and boundary lines, and then repairs the surface patch to prevent surface errors. Construct the grid, fit the surface to save a NURBS surface, and save it as an iges model file;
c.将碳纤维增强碳基体放入真空辉光放电室中，直流电源电压600v、工作时间20min、氩气的压力60Pa，在真空辉光放电室中通入氩气进行对碳纤维增强碳基体表面进行等离子预处理，该条件下热解碳表面光滑，而过高的电压和过长的工作时间将使表面形貌再一次得到腐蚀，过低的电压、较短的工作时间对等离子预处理碳/碳复合材料形貌影响不大，如图4(a)为经500v、20min、30Pa等离子处理条件处理的碳/碳复合材料的碳纤维形貌，与未经等离子处理的碳/碳复合材料的原始碳纤维形貌相似，碳纤维表面有明显的凸起的条状皱褶，这是热解碳沉积造成的，图4(b)为经600v、20min、60Pa等离子处理条件处理的碳/碳复合材料的碳纤维形貌，碳纤维表面相对光滑，没有凸起皱褶，说明等离子处理碳/碳复合材料的碳纤维是有效的，但是在更高放大倍数电镜下观察，碳纤维表面观察到有刻蚀凹坑形成，图4(c)为经700v、20min、60Pa等离子处理条件处理的碳/碳复合材料的碳纤维形貌，碳纤维表面有明显的腐蚀凹坑形成。经过等离子体处理后，在碳/碳复合材料表面引入了羰基、羟基等活性基团，如图5(a)红外光谱图所示，图5(b)为未经等离子体处理的碳/碳复合材料红外光谱图，经过处理后的碳纤维增强碳基体放入酒精溶液中进行超声清洗，清洗氩气轰击下来的热解碳颗粒；c. Put the carbon fiber reinforced carbon matrix into the vacuum glow discharge chamber, the DC power supply voltage is 600v, the working time is 20min, and the pressure of argon gas is 60Pa. Plasma pretreatment, under this condition, the surface of pyrolytic carbon is smooth, while excessively high voltage and long working time will corrode the surface morphology again, too low voltage and short working time will affect the plasma pretreatment of carbon/ The morphology of carbon composites has little effect. Figure 4(a) shows the carbon fiber morphology of carbon/carbon composites treated with plasma treatment conditions of 500v, 20min, and 30Pa, which is different from that of the original carbon/carbon composites without plasma treatment. The morphology of carbon fibers is similar, and there are obvious raised stripes on the surface of carbon fibers, which are caused by pyrolytic carbon deposition. Figure 4(b) shows the carbon/carbon composite material treated by 600v, 20min, 60Pa plasma treatment conditions The carbon fiber morphology, the surface of the carbon fiber is relatively smooth, and there are no raised wrinkles, indicating that the plasma treatment of the carbon fiber of the carbon/carbon composite material is effective, but under a higher magnification electron microscope, the carbon fiber surface is observed to have etching pits, Figure 4(c) shows the carbon fiber morphology of the carbon/carbon composite material treated with plasma treatment conditions of 700v, 20min, and 60Pa. There are obvious corrosion pits on the surface of the carbon fiber. After plasma treatment, active groups such as carbonyl and hydroxyl groups were introduced on the surface of carbon/carbon composites, as shown in Figure 5(a) infrared spectrum, and Figure 5(b) is the carbon/carbon without plasma treatment Infrared spectrogram of the composite material, the treated carbon fiber reinforced carbon matrix is placed in an alcohol solution for ultrasonic cleaning, and the pyrolytic carbon particles bombarded by argon gas are cleaned;
d.对清洗过后的碳纤维增强碳基体表面进行喷涂羟基磷灰石涂层形成成品碳/碳复合材料人工骨，对经600v、20min、60Pa等离子处理条件处理的碳/碳复合材料、及未进行等离子处理的碳/碳复合材料进行等离子喷涂，由图6(a)、图6(b)看到羟基磷灰石涂层主要由溶化了羟基磷灰石的大小不等的颗粒组成，表面不平整且有空隙存在，有利于人体组织细胞的攀附生长，与不用等离子预处理碳/碳复合材料形成的羟基磷灰石涂层形貌基本一致，通过两者电子能谱(EDS)图6(c)、图6(d)发现两种方法得到的涂层都含有Ca，P，C，O等成分，O来自基体,观察由600v、20min、60Pa等离子处理条件处理的碳/碳复合材料、及未进行等离子处理的碳/碳复合材料HA涂层的红外吸收光谱，如图7,2500cm-1～3200cm-1的宽而散的峰为C-H伸缩振动,1654cm-1和3447cm-1为羟基的吸收峰,而在3582cm-1HA的特征吸收峰可能被羟基吸收峰掩盖，P-O的伸缩振动出现在1090cm-1、1048cm-1,而602cm-1、569cm-1、473cm-1则是P-O弯曲振动的吸收峰[16]。进行等离子预处理的碳/碳复合材料HA涂层的P-O的伸缩振动和弯曲振动的吸收峰的强度和宽度比等离子未处理的碳/碳复合材料HA涂层增强，从XRD图谱中发现，如图8所示，HA涂层的图谱中出现了HA晶面特征衍射峰((100)、(201)、(211)、(112)、(300)、(222)、(213))以及磷酸钙、氧化钙的部分衍射峰，图谱中也出现了其他杂质的衍射峰，可能与等离子喷涂枪清洗不干净存在其他喷涂材料有关；d. Spray hydroxyapatite coating on the surface of the cleaned carbon fiber reinforced carbon matrix to form a finished carbon/carbon composite artificial bone. Plasma-treated carbon/carbon composites are sprayed by plasma. From Fig. 6(a) and Fig. 6(b), it can be seen that the hydroxyapatite coating is mainly composed of particles of different sizes dissolved in hydroxyapatite, and the surface is not It is flat and has gaps, which is conducive to the growth of human tissue cells. It is basically consistent with the morphology of the hydroxyapatite coating formed without plasma pretreatment of carbon/carbon composites. Through the electron spectroscopy (EDS) of the two, Figure 6 ( c), Figure 6(d) found that the coatings obtained by both methods contain Ca, P, C, O and other components, and O comes from the matrix. Observe the carbon/carbon composite material treated by 600v, 20min, 60Pa plasma treatment conditions, And the infrared absorption spectrum of the carbon/carbon composite HA coating without plasma treatment, as shown in Figure 7, the broad and scattered peaks from 2500cm-1 to 3200cm-1 are CH stretching vibrations, and 1654cm-1 and 3447cm-1 are hydroxyl The absorption peak of HA, while the characteristic absorption peak of HA at 3582cm-1 may be covered by the absorption peak of hydroxyl group, the stretching vibration of PO appears at 1090cm-1 , 1048cm-1 , while 602cm-1 , 569cm-1 , 473cm-1 are PO Absorption peaks of bending vibrations[16] . The intensity and width of the absorption peaks of stretching vibration and bending vibration of PO of the carbon/carbon composite HA coating subjected to plasma pretreatment were enhanced than those of the plasma-untreated carbon/carbon composite HA coating, as found from the XRD patterns, as As shown in Figure 8, the characteristic diffraction peaks of HA crystal planes ((100), (201), (211), (112), (300), (222), (213)) and phosphoric acid Part of the diffraction peaks of calcium and calcium oxide, and other impurities also appear in the spectrum, which may be related to the presence of other spray materials if the plasma spray gun is not cleaned cleanly;
喷涂后的碳/碳复合材料需要进行划痕测试，读取划痕仪的数据并结合SEM划痕图片，如图9所示，得到采用或不采用等离子预处理碳∕碳复合材料HA涂层临界载荷分别为14.0N、8.9N，前者比后者临界载荷提高了57.3％，根据公式HS为基体硬度，LC为临界压力，R为加载压头金刚石的尖端半经，采用或不采用等离子处理碳∕碳复合材料HA涂层两者的剪切强度分别为63.3MPa、50.5MPa。采用等离子处理碳∕碳复合材料HA涂层失效前划痕光滑平整，在失效后，涂层剥离，露出基体，基体处可见有少量的涂层残留，这部分残留主要是位于碳/碳复合材料孔隙中的涂层所致。而未用等离子处理碳∕碳复合材料HA涂层失效后大块涂层剥落，涂层的结合力不强。The carbon/carbon composite material after spraying needs to be tested for scratches. Read the data of the scratch instrument and combine the SEM scratch picture, as shown in Figure 9, to obtain the carbon/carbon composite material HA coating with or without plasma pretreatment The critical loads are 14.0N and 8.9N respectively, the former is 57.3% higher than the latter critical load, according to the formula HS is the hardness of the matrix, LC is the critical pressure, R is the tip half-warp of the loading indenter diamond, and the shear strength of the carbon/carbon composite HA coating with or without plasma treatment is 63.3MPa and 50.5MPa respectively . Plasma treatment of carbon/carbon composite material HA coating before the failure of the scratch is smooth and flat, after failure, the coating peels off, exposing the substrate, a small amount of coating residue can be seen on the substrate, this part of the residue is mainly located in the carbon/carbon composite material Caused by coating in pores. However, after the HA coating of the carbon/carbon composite material without plasma treatment fails, large pieces of the coating peel off, and the bonding force of the coating is not strong.
采用比不采用等离子预处理碳∕碳复合材料HA涂层临界载荷提高的机理如下：氩离子高速轰击碳/碳复合材料，去除碳纤维周围热解碳表面的缺陷如皱褶、碎片等，皱褶等与基体及羟基磷灰石的结合力差、易脱落，去除皱褶等热解碳表面缺陷能提高碳∕碳复合材料的HA涂层的临界载荷。The mechanism of the critical load improvement of the carbon/carbon composite material HA coating is as follows: argon ions bombard the carbon/carbon composite material at high speed, and remove the defects on the pyrolytic carbon surface around the carbon fiber, such as wrinkles, debris, etc., wrinkles Poor bonding with the matrix and hydroxyapatite, easy to fall off, removal of pyrolytic carbon surface defects such as wrinkles can increase the critical load of the HA coating of carbon/carbon composites.
以上述依据本发明的理想实施例为启示，通过上述的说明内容，相关工作人员完全可以在不偏离本项发明技术思想的范围内，进行多样的变更以及修改。本项发明的技术性范围并不局限于说明书上的内容，必须要根据权利要求范围来确定其技术性范围。Inspired by the above-mentioned ideal embodiment according to the present invention, through the above-mentioned description content, relevant workers can make various changes and modifications within the scope of not departing from the technical idea of the present invention. The technical scope of the present invention is not limited to the content in the specification, but must be determined according to the scope of the claims.
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| CN201210261732.7ACN102764453B (en) | 2012-07-26 | 2012-07-26 | A preparation method of personalized carbon-carbon composite artificial bone |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103920186A (en)* | 2014-04-17 | 2014-07-16 | 倪昕晔 | Magnesium-containing hydroxyapatite coating on the surface of medical materials and preparation method thereof |
| CN104587527B (en)* | 2015-01-16 | 2017-03-08 | 中国石油大学(华东) | A kind of carbon/carbon compound material of biological functional and preparation method thereof |
| CN105908155B (en)* | 2016-06-16 | 2018-10-19 | 常州市第二人民医院 | Preparation method of magnesium-containing hydroxyapatite coating on surface of carbon/carbon composite material |
| CN107518962B (en) | 2017-08-23 | 2019-01-08 | 湖南碳康生物科技有限公司 | A kind of carbon fibre composite artificial bone and preparation method thereof |
| CN110680559B (en)* | 2019-09-27 | 2022-02-15 | 长沙晟天新材料有限公司 | Chest lock integrated piece and preparation method thereof |
| CN110841114B (en)* | 2019-09-27 | 2021-12-14 | 长沙晟天新材料有限公司 | Carbon fiber composite material artificial bone and preparation method thereof |
| CN111925226B (en)* | 2020-01-19 | 2022-04-08 | 湖南碳康生物科技有限公司 | Carbon fiber composite skull patch and preparation method thereof |
| CN112370569B (en)* | 2021-01-15 | 2021-04-02 | 湖南碳康生物科技有限公司 | Carbon fiber composite material artificial rib and preparation method thereof |
| CN112843340B (en)* | 2021-01-18 | 2022-08-09 | 湖南碳康生物科技有限公司 | Carbon-based composite material artificial rib and preparation method thereof |
| CN112876269B (en)* | 2021-01-18 | 2023-04-28 | 湖南碳康生物科技有限公司 | Length-adjustable carbon fiber composite artificial rib and preparation method thereof |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1561927A (en)* | 2004-04-02 | 2005-01-12 | 清华大学 | CT assisted bone imitated producing artificial bone method |
| CN101991879A (en)* | 2010-11-11 | 2011-03-30 | 奇瑞汽车股份有限公司 | Preparation method of carbon-carbon composite material/hydroxyapatite/polylactic acid biological material |
| CN102429746A (en)* | 2011-10-24 | 2012-05-02 | 晓健科技（大连）有限公司 | Novel carbon fiber artificial joint |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9339387B2 (en)* | 2010-10-13 | 2016-05-17 | Cibor, Inc. | Synthetic bone grafts constructed from carbon foam materials |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1561927A (en)* | 2004-04-02 | 2005-01-12 | 清华大学 | CT assisted bone imitated producing artificial bone method |
| CN101991879A (en)* | 2010-11-11 | 2011-03-30 | 奇瑞汽车股份有限公司 | Preparation method of carbon-carbon composite material/hydroxyapatite/polylactic acid biological material |
| CN102429746A (en)* | 2011-10-24 | 2012-05-02 | 晓健科技（大连）有限公司 | Novel carbon fiber artificial joint |
| Title |
|---|
| 吴庆等.碳纤维的表面处理.《化工新型材料》.中国化工信息中心,2000,第28卷(第3期), |
| 碳纤维的表面处理;吴庆等;《化工新型材料》;中国化工信息中心;20000331;第28卷(第3期);全文* |
| Publication number | Publication date |
|---|---|
| CN102764453A (en) | 2012-11-07 |
| Publication | Publication Date | Title |
|---|---|---|
| CN102764453B (en) | A preparation method of personalized carbon-carbon composite artificial bone | |
| Chehroudi et al. | The effects of micromachined surfaces on formation of bonelike tissue on subcutaneous implants as assessed by radiography and computer image processing | |
| Zhao et al. | Corrosion resistance characteristics of a Ti-6Al-4V alloy scaffold that is fabricated by electron beam melting and selective laser melting for implantation in vivo | |
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| US20180014936A1 (en) | Bioactive material | |
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| Zabala et al. | Quantification of dental implant surface wear and topographical modification generated during insertion | |
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| Ji et al. | Structure optimization of porous dental implant based on 3D printing |
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