技术领域technical field
本发明涉及一种利用3D打印制备二级多孔钽金属零件的方法，属于3D打印材料设计技术领域。The invention relates to a method for preparing secondary porous tantalum metal parts by 3D printing, which belongs to the technical field of 3D printing material design.
背景技术Background technique
钽有“亲生物”金属之称，它的化学性质十分稳定，耐腐蚀性极强，同时具有优良的生物相容性和生物活性，近年来被广泛的予以重视和大量研究。它应用于医学领域已半世纪余，包括心脏起搏器、颅骨缺损修补、血管夹制造、骨关节假体和手术缝合线等。然而，致密的钽材料由于比重大、弹性模量高并且高昂的原料成本等缺点，限制了它的广泛临床应用。Tantalum is known as a "biophilic" metal. It has very stable chemical properties, strong corrosion resistance, and excellent biocompatibility and biological activity. It has been widely valued and studied in recent years. It has been used in the medical field for more than half a century, including cardiac pacemakers, skull defect repair, vascular clip manufacturing, bone and joint prostheses, and surgical sutures. However, the disadvantages of dense tantalum materials such as high specific gravity, high elastic modulus, and high raw material cost limit its wide clinical application.
近年来，3D打印技术不断发展，由于其在原理上突破了传统机加工对零件外形的限制，并且能打印复杂异性构件和满足个性化定制的需求，3D打印技术被广泛地用于制备医疗领域个性化植入体，特别是多孔结构植入体。在植入体方面，钛合金、钴铬合金已经有较广泛的应用，利用3D打印技术制备多孔钽合金植入体也逐渐得到应用。激光熔融3D打印技术或电子束熔融3D打印技术常被用来成形钽，但是这两种技术在3D打印多孔钽合金植入体方面仍存在一些问题，比如电子束熔融成形钽，可以得到纯度高、无污染的构件，然而电子束成形不够精细，构件的精度以及精细结构受到限制；激光选区熔化虽然成形比较精细，构件精度比较高，然而它只能制备100μm以上的多孔结构，难以得到更微细结构，无法匹配真正的具有100μm以下微结构的骨小梁，不利于骨细胞长入结合。In recent years, 3D printing technology has continued to develop. Because it breaks through the limitations of traditional machining on the shape of parts in principle, and can print complex heterogeneous components and meet the needs of personalized customization, 3D printing technology is widely used in the preparation of medical fields. Personalized implants, especially implants with porous structures. In terms of implants, titanium alloys and cobalt-chromium alloys have been widely used, and the use of 3D printing technology to prepare porous tantalum alloy implants has also been gradually applied. Laser melting 3D printing technology or electron beam melting 3D printing technology are often used to form tantalum, but these two technologies still have some problems in 3D printing porous tantalum alloy implants, such as electron beam melting forming tantalum, which can get high purity , non-polluting components, but the electron beam forming is not fine enough, and the precision and fine structure of the components are limited; although the laser selective melting is finer in forming and the precision of the components is relatively high, it can only prepare porous structures above 100 μm, and it is difficult to obtain finer The structure cannot match the real bone trabecula with a microstructure below 100 μm, which is not conducive to the growth and integration of bone cells.
发明内容Contents of the invention
针对现有技术的不足，本发明的目的在于提供一种利用3D打印制备二级多孔钽金属零件的方法，本发明通过在含钽的混合粉末中配入一定量的水溶性粘结剂；然后通过3D打印制备多孔坯体；最后通过溶解水溶性粘结剂的方式来制备二级多孔钽基材料；所得产品孔隙率可控、通孔率高；且在相同孔隙率的条件下，其所得产品的性能远远优于现有产品。Aiming at the deficiencies in the prior art, the object of the present invention is to provide a method for preparing secondary porous tantalum metal parts by 3D printing. The present invention mixes a certain amount of water-soluble binder in the mixed powder containing tantalum; and then The porous body is prepared by 3D printing; finally, the secondary porous tantalum-based material is prepared by dissolving the water-soluble binder; the porosity of the obtained product is controllable and the through-porosity is high; and under the same porosity, the obtained The performance of the product is far superior to existing products.
为了实现上述目的，本发明采用如下技术方案：In order to achieve the above object, the present invention adopts the following technical solutions:
本发明一种利用3D打印制备二级多孔钽金属零件的方法，包括如下步骤：将钽粉末、其他金属粉末、水溶性粘结剂混合获得混合料，然后将混合料经过3D打印获得多孔坯体，然后将多孔坯体置于浸出液中，溶出水溶性粘结剂后，干燥，得到二级多孔钽金属零件。The present invention is a method for preparing secondary porous tantalum metal parts by 3D printing. , and then place the porous body in the leaching solution, dissolve the water-soluble binder, and dry to obtain a secondary porous tantalum metal part.
本发明的制备方法，在配料过程中引入了水溶性粘结剂，先通过3D打印获得具有一级多孔的坯体，然后再通过浸出水溶性粘结剂，得到孔隙率可控、通孔率高；同时本发明所得产品强度远远高于现有产品的强度。In the preparation method of the present invention, a water-soluble binder is introduced in the batching process, and a first-level porous green body is obtained by 3D printing, and then the water-soluble binder is leached to obtain a controllable porosity, a through-porosity High; simultaneously the strength of the product obtained by the present invention is far higher than that of the existing product.
在现有技术中，3D打印法制备多孔金属材料均加入有机粘结剂以及造孔剂，以其在3D打印时烧结脱除造孔剂和/或有机粘结剂粘结剂，获得多孔，而造孔剂和/或粘结剂在3D打印时一般会分解，虽然有利于造孔，但由于3D打印激光烧结温度高，成型过程快速、造孔剂存在分解不完全等情况，从而在样品中产生气孔、裂纹等缺陷，导致样品力学性能降低。而本发明巧妙的引入在激光烧结时不会分解的水溶性粘结剂，后续通过水或水与有机溶剂的混合溶液浸出，不会在脱出阶段对样品造成影响，从而可以确保所制备多孔钽的强度，并可控的获得二级多孔结构。In the prior art, organic binders and pore-forming agents are added to porous metal materials prepared by 3D printing methods, and the pore-forming agents and/or organic binders are sintered to obtain porous metal materials during 3D printing. The pore-forming agent and/or binder will generally decompose during 3D printing. Although it is beneficial to pore-forming, due to the high sintering temperature of the 3D printing laser, the fast forming process, and the incomplete decomposition of the pore-forming agent, the samples will Defects such as pores and cracks occur in the sample, resulting in a decrease in the mechanical properties of the sample. However, the present invention cleverly introduces a water-soluble binder that will not decompose during laser sintering, and subsequent leaching by water or a mixed solution of water and organic solvent will not affect the sample during the extraction stage, thereby ensuring that the prepared porous tantalum strength, and controllable access to the secondary porous structure.
在本发明中，能获得强度高，且具有二级多控结构多孔钽的很关键的点即采用激光烧结时不会分解的水溶性粘结剂，若采用有机粘结剂，由于沸点较低，在激光烧结时有机粘结剂就会分解挥发，从而使样品性能下降。In the present invention, the very key point of obtaining high strength and porous tantalum with a secondary multi-controlled structure is the use of a water-soluble binder that will not decompose during laser sintering. If an organic binder is used, due to the lower boiling point , the organic binder will decompose and volatilize during laser sintering, thereby degrading the performance of the sample.
优选的方案，所述其他金属粉末中的金属选自镁、铝、钛、铁、锂、铅、锌、锡、钴、金、银、钙、锶、钡、镍、铜、锰、铪、锆中的至少一种，优选为钛、铪、锆中的一种。In a preferred scheme, the metals in the other metal powders are selected from magnesium, aluminum, titanium, iron, lithium, lead, zinc, tin, cobalt, gold, silver, calcium, strontium, barium, nickel, copper, manganese, hafnium, At least one of zirconium, preferably one of titanium, hafnium and zirconium.
优选的方案，所述水溶性粘结剂选自卤化物、硅酸盐、硼酸盐、硫酸盐、磷酸盐、硝酸盐、碱金属盐、亚硝酸盐、钾钠盐中的至少一种，优选为碱金属硅酸盐，进一步优选为硅酸钠和/或硅酸钾。本发明所选择的水溶性粘结剂在3D打印时不分解。In a preferred scheme, the water-soluble binder is selected from at least one of halides, silicates, borates, sulfates, phosphates, nitrates, alkali metal salts, nitrites, potassium sodium salts, It is preferably an alkali metal silicate, more preferably sodium silicate and/or potassium silicate. The water-soluble binder selected by the present invention does not decompose during 3D printing.
本发明所优选的硅酸钠、硅酸钾沸点，相比其他水溶性粘结剂具有如下优势：(1)硅酸钠和硅酸钾的沸点都高于2300℃，高于其他的水溶性粘结剂，也大大高于混合料的熔点，很好地满足了打印时的能量束温度要求。(2)硅酸钾和硅酸钠在打印过程中不会分解，且两者都易溶于水，并且在溶解过程中不会产生对零件有影响的杂质。(3)硅酸钠和硅酸钾成本较低，容易获得。The preferred sodium silicate and potassium silicate boiling points of the present invention have the following advantages compared to other water-soluble binders: (1) the boiling points of sodium silicate and potassium silicate are all higher than 2300°C, higher than other water-soluble binders. The binder, also well above the melting point of the compound, satisfies the energy beam temperature requirements for printing well. (2) Potassium silicate and sodium silicate will not decompose during the printing process, and both are easily soluble in water, and will not produce impurities that will affect the part during the dissolution process. (3) Sodium silicate and potassium silicate are relatively cheap and easy to obtain.
优选的方案，所述混合料中，钽粉末的质量分数为30-85％。In a preferred solution, in the mixture, the mass fraction of tantalum powder is 30-85%.
优选的方案，所述混合料中，水溶性粘结剂的质量分数为5-30％。In a preferred solution, in the mixture, the mass fraction of the water-soluble binder is 5-30%.
优选的方案，所述钽粉末和其他金属粉末的粒度≦200μm，优选为1～200μm。In a preferred solution, the particle size of the tantalum powder and other metal powders is ≦200 μm, preferably 1-200 μm.
优选的方案，所述水溶性粘结剂的粒度≦600μm，优选为0.001～600μm，进一步优选为0.001～200μm。In a preferred solution, the particle size of the water-soluble binder is ≦600 μm, preferably 0.001-600 μm, more preferably 0.001-200 μm.
优选的方案，所述混合的方式为球磨，所述球磨的转速为10～500r/min、球磨的时间为1～300h、优选为10～24h。当采用单质金属的粉末作为原料时，可以通过机械合金化得到成分均匀的合金粉末以及混合均匀的备用粉末。In a preferred solution, the mixing method is ball milling, the rotating speed of the ball milling is 10-500r/min, and the time of ball milling is 1-300h, preferably 10-24h. When the powder of elemental metal is used as the raw material, alloy powder with uniform composition and uniformly mixed spare powder can be obtained through mechanical alloying.
在本发明中，通过球磨获得分散均匀的混合料，在此基础上，再通过控制粘结剂的粒度，以及粘结剂在混合料中的质量占比，最终获得100μm的二级多孔，在优选方案中，获得10～50μm的二级多孔。In the present invention, a uniformly dispersed mixture is obtained by ball milling. On this basis, by controlling the particle size of the binder and the mass ratio of the binder in the mixture, a secondary porous of 100 μm is finally obtained. In a preferred solution, secondary pores of 10-50 μm are obtained.
优选的方案，所述3D打印采用选区激光熔融3D打印或电子束熔融3D打印。In a preferred solution, the 3D printing adopts selected area laser fusion 3D printing or electron beam fusion 3D printing.
进一步的优选，当采用选区激光熔融3D打印时的工艺参数为：Further preferably, the process parameters when using selective laser melting 3D printing are:
激光束斑直径30～100μm，优选为40～100μm，进一步优选为50～80μm；The diameter of the laser beam spot is 30-100 μm, preferably 40-100 μm, more preferably 50-80 μm;
激光能量范围80～450W，优选为200～450W，进一步优选为300～450W；The laser energy range is 80-450W, preferably 200-450W, more preferably 300-450W;
扫描间距20～500μm，优选为50～300μm，进一步优选为80～200μm；The scanning pitch is 20-500 μm, preferably 50-300 μm, more preferably 80-200 μm;
激光扫描速度0.1～6m/s，优选为0.2～4m/s，进一步优选为0.2～2m/s；The laser scanning speed is 0.1-6m/s, preferably 0.2-4m/s, more preferably 0.2-2m/s;
单层铺粉厚度20～100μm，优选为20～80μm，进一步优选为20～50μm。The thickness of a single layer of powder spreading is 20-100 μm, preferably 20-80 μm, more preferably 20-50 μm.
进一步的优选，当采用电子束3D打印时的工艺参数为：Further preferably, the process parameters when using electron beam 3D printing are:
粉末预热温度500～750℃，优选为550～700℃，进一步优选为600～660℃；The powder preheating temperature is 500-750°C, preferably 550-700°C, more preferably 600-660°C;
电子束束斑直径50～500μm，优选为50～200μm，进一步优选为80～150μm；The electron beam spot diameter is 50-500 μm, preferably 50-200 μm, more preferably 80-150 μm;
扫描电流1～10mA，优选为2～8mA，进一步优选为2～6mA，更进一步优先为3～4mA；The scanning current is 1-10mA, preferably 2-8mA, more preferably 2-6mA, more preferably 3-4mA;
扫描速度0.5～1.5m/s、优选为0.8～1m/s；The scanning speed is 0.5-1.5m/s, preferably 0.8-1m/s;
单层铺粉厚度30～500μm，优选50～400μm，进一步优选为50～200μm。The thickness of a single layer of powder spreading is 30-500 μm, preferably 50-400 μm, more preferably 50-200 μm.
在本发明的3D打印过程中，由于要根据混合粉的特性控制激光能量范围，使得激光束或电子束与原料接触点的温度为T；所述T大于等于混合料的熔点，且小于水溶性粘结剂的沸点。In the 3D printing process of the present invention, due to the control of the laser energy range according to the characteristics of the mixed powder, the temperature of the contact point between the laser beam or the electron beam and the raw material is T; The boiling point of the binder.
优选的方案，所述浸出液为水或水与有机溶剂的混合溶液，优选为水。In a preferred solution, the leachate is water or a mixed solution of water and an organic solvent, preferably water.
优选的方案，所述干燥的温度为≤500℃，烘干的时间＜100h、优选为1～180min。In a preferred solution, the drying temperature is ≤500°C, and the drying time is <100h, preferably 1-180min.
优选的方案，所述二级多孔钽金属零件的一级孔尺寸为100～150μm，二级孔尺寸为10～50μm。In a preferred solution, the primary pore size of the secondary porous tantalum metal part is 100-150 μm, and the secondary pore size is 10-50 μm.
原理与优势Principles and advantages
本发明，在配料过程中引入了水溶性粘结剂，在激光3D打印时，通过控制测量束与原料接触点的温度实现坯体成型，然后通过浸出水溶性粘结剂，得到孔隙率可控、通孔率高；同时本发明所得产品强度远远高于现有产品的强度。In the present invention, a water-soluble binder is introduced in the batching process. During laser 3D printing, the green body is formed by controlling the temperature of the contact point between the measurement beam and the raw material, and then the water-soluble binder is leached to obtain a controllable porosity. , High porosity; meanwhile, the strength of the product obtained by the present invention is far higher than that of the existing product.
在本发明中，金属混合粉和粘结剂的热膨胀系数是不相等的，而且在本发明的优选方案中，其二者的比例是在一定范围内；在优选方案所限定范围内，当金属混合粉和粘结剂的热膨胀系数不相等时，有利于细微裂纹的形成；细微裂纹的形成有利于后续浸出。这就可以确保粘接剂被完全浸出；同时，这也确保了产品的通孔率可以保持在较高值以上。本发明中，所产生的细微裂纹的尺寸和数目远远小于造孔剂在3D打印过程中分解所导致成品产生裂纹的数目和尺寸，这也是为什么本发明所得产品的力学性能优于同孔隙率下同类产品力学能的原因之一。In the present invention, the thermal expansion coefficients of the metal mixed powder and the binder are not equal, and in the preferred version of the present invention, the ratio of the two is within a certain range; within the limited range of the preferred version, when the metal When the thermal expansion coefficients of the mixed powder and the binder are not equal, it is beneficial to the formation of fine cracks; the formation of fine cracks is beneficial to the subsequent leaching. This ensures that the adhesive is fully leached; at the same time, it also ensures that the through-porosity of the product can be kept above a high value. In the present invention, the size and number of fine cracks produced are far smaller than the number and size of cracks in the finished product caused by the decomposition of the pore-forming agent during the 3D printing process, which is why the mechanical properties of the product obtained in the present invention are better than those with the same porosity One of the reasons for the mechanical performance of similar products.
本发明所开发的二级多孔钽金属零件，通过3D打印直接成型所得钽材料的孔隙度范围广，产品的孔隙率最高可达90％。本发明通过3D打印直接成型，避免了模具的使用，同时还能制备出结构复杂、精密、更利于骨长入的多级多孔钽金属医用植入体材料。由于其可以直接采用3D打印成型，这在很大程度上降低了多级多孔钽金属医用植入体的制造成本。The two-stage porous tantalum metal part developed by the present invention has a wide range of porosity in the tantalum material directly formed by 3D printing, and the porosity of the product can reach up to 90%. The present invention is directly shaped by 3D printing, avoids the use of molds, and can also prepare multi-level porous tantalum metal medical implant materials with complex structure, precision, and better bone ingrowth. Since it can be directly formed by 3D printing, this greatly reduces the manufacturing cost of multi-level porous tantalum metal medical implants.
具体实施方式Detailed ways
实施例1：Example 1:
实施例1中所用钽粉粒度范围为25～64μm、D50为45μm，商业钛粉粒度范围为15～50μm、D50为40μm，商业硅酸钠粉的粒度范围为38～53μm、D50为45μm。The particle size range of tantalum powder used in Example 1 is 25-64 μm, D50 is 45 μm, the particle size range of commercial titanium powder is 15-50 μm, D50 is 40 μm, the particle size range of commercial sodium silicate powder is 38-53 μm, D50 is 45 μm.
以Ta粉、商业钛粉和商业硅酸钠粉为原料，称重Ta粉17kg、商业钛粉2kg、商业硅酸钠粉1kg，加入氧化锆球，在滚筒球磨机中以60rpm的转速球磨12小时，得到氧含量为0.5wt％粉体。然后将球磨好的粉体放置于华曙高科生产的选区激光熔融设备的供粉缸中，选用50μm直径的激光束斑、300W的激光能量、0.8m/s的扫描速度、80μm的扫描间距、30μm的单层铺粉层厚度，在氩气的保护气氛下激光熔融钽金属。激光加工完成之后，把样品放在室温条件下的水中溶解10分钟，然后在120℃温度条件下烘干20分钟，并对样品进行喷砂处理和必要的打磨，从而获得所需的个性化二级多孔钽钛金属构件。所述钽钛构件的强度为61.2MPa、孔隙率为15.3％，其中，一级孔尺寸为100-123μm，二级孔尺寸为38-56μm。Using Ta powder, commercial titanium powder and commercial sodium silicate powder as raw materials, weigh 17kg of Ta powder, 2kg of commercial titanium powder, and 1kg of commercial sodium silicate powder, add zirconia balls, and mill in a roller mill at a speed of 60rpm for 12 hours , to obtain a powder with an oxygen content of 0.5 wt%. Then place the ball-milled powder in the powder supply cylinder of the selective laser melting equipment produced by Farsoon Hi-Tech, choose a laser beam spot with a diameter of 50 μm, a laser energy of 300 W, a scanning speed of 0.8 m/s, and a scanning distance of 80 μm. The thickness of the single-layer powder layer is 30μm, and the tantalum metal is laser-melted under the protective atmosphere of argon. After the laser processing is completed, the sample is dissolved in water at room temperature for 10 minutes, then dried at 120°C for 20 minutes, and the sample is sandblasted and polished as necessary to obtain the desired personalized second. Porous tantalum-titanium metal components. The strength of the tantalum-titanium member is 61.2 MPa, and the porosity is 15.3%, wherein the primary pore size is 100-123 μm, and the secondary pore size is 38-56 μm.
实施例2：Example 2:
实施例2中所用钽粉粒度范围为25～64μm、D50为45μm，商业钛粉粒度范围为15～50μm、D50为40μm，商业硅酸钠粉的粒度范围为38～53μm、D50为45μm。The particle size range of the tantalum powder used in Example 2 is 25-64 μm, D50 is 45 μm, the particle size range of the commercial titanium powder is 15-50 μm, the D50 is 40 μm, the particle size range of the commercial sodium silicate powder is 38-53 μm, and the D50 is 45 μm.
以Ta粉、商业钛粉和商业硅酸钠粉为原料，称重Ta粉17kg、商业钛粉2kg、商业硅酸钠粉1kg，加入氧化锆球，在滚筒球磨机中以70rpm的转速球磨10小时，得到氧含量为0.8wt％粉体。然后将球磨好的粉体放置于西安塞隆生产的电子束熔融设备中。将粉末预热到700℃，选用120μm直径的电子束束斑、3mA的扫描电流、1m/s的扫描速度、120μm的单层铺粉层厚度，在10-4Pa的真空条件下熔融合金。最后利用线切割设备将样品从基板上切割下来，并对样品进行喷砂处理和必要的打磨，从而获得所需的二级多孔钽钛金属构件。所述钽钛金属构件的强度为64.1MPa，孔隙率为16.7％，其中，一级孔尺寸为102-124μm，二级孔尺寸为38-61μm。Using Ta powder, commercial titanium powder and commercial sodium silicate powder as raw materials, weigh 17kg of Ta powder, 2kg of commercial titanium powder, and 1kg of commercial sodium silicate powder, add zirconia balls, and ball mill at a speed of 70rpm for 10 hours in a roller ball mill , to obtain a powder with an oxygen content of 0.8wt%. Then the ball-milled powder is placed in the electron beam melting equipment produced by Xi'an Sailong. Preheat the powder to 700°C, select an electron beam spot with a diameter of 120μm, a scanning current of 3mA, a scanning speed of 1m/s, and a single-layer powder layer thickness of 120μm, and melt the alloy under a vacuum of 10-4Pa. Finally, the sample is cut from the substrate by wire cutting equipment, and the sample is subjected to sandblasting and necessary grinding, so as to obtain the required secondary porous tantalum-titanium metal component. The strength of the tantalum-titanium metal component is 64.1 MPa, and the porosity is 16.7%, wherein, the primary pore size is 102-124 μm, and the secondary pore size is 38-61 μm.
实施例3：Example 3:
实施例3中所用的钽粉粒度范围为25～64μm、D50为45μm，商业钛粉粒度范围为15～50μm、D50为40μm，商业锆粉粒度范围为15～60μm、D50为35μm，商业铪粉粒度范围为20～50μm，D50为35μm，商业硅酸钠粉的粒度范围为38～53μm、D50为45μm。The particle size range of the tantalum powder used in Example 3 is 25-64 μm, D50 is 45 μm, the particle size range of commercial titanium powder is 15-50 μm, D50 is 40 μm, the particle size range of commercial zirconium powder is 15-60 μm, D50 is 35 μm, commercial hafnium powder The particle size range is 20-50 μm, and the D50 is 35 μm. The particle size range of commercial sodium silicate powder is 38-53 μm, and the D50 is 45 μm.
以钽粉、商业钛粉、商业锆粉、商业铪粉和商业硅酸钠粉为原料，称重钽粉12.1kg、钛粉6.1kg、锆粉1.56kg、铪粉0.24kg、商业硅酸钠粉2kg，加入氧化锆球，在滚筒球磨机中以60rpm的转速球磨12小时，得到氧含量为0.5wt％粉体。然后将球磨好的粉体放置于华曙高科生产的选区激光熔融设备的供粉缸中，选用50μm直径的激光束斑、350W的激光能量、0.8m/s的扫描速度、80μm的扫描间距、30μm的单层铺粉层厚度，在氩气的保护气氛下激光熔融钽金属。激光加工完成之后，把样品放在室温条件下的水中溶解10分钟，然后在120℃温度条件下烘干20分钟，并对样品进行喷砂处理和必要的打磨，从而获得所需的个性化二级多孔钽铪锆钛金属构件。所述钽基构件的强度为106.2MPa、孔隙率为21.8％，其中，一级孔尺寸为100-126μm，二级孔尺寸为38-58μm。Using tantalum powder, commercial titanium powder, commercial zirconium powder, commercial hafnium powder and commercial sodium silicate powder as raw materials, weigh 12.1kg of tantalum powder, 6.1kg of titanium powder, 1.56kg of zirconium powder, 0.24kg of hafnium powder, and commercial sodium silicate powder 2 kg of powder was added with zirconia balls, and ball milled for 12 hours at a speed of 60 rpm in a roller ball mill to obtain a powder with an oxygen content of 0.5 wt%. Then place the ball-milled powder in the powder supply cylinder of the selective laser melting equipment produced by Farsoon Hi-Tech, choose a laser beam spot with a diameter of 50 μm, a laser energy of 350 W, a scanning speed of 0.8 m/s, and a scanning distance of 80 μm. The thickness of the single-layer powder layer is 30μm, and the tantalum metal is laser-melted under the protective atmosphere of argon. After the laser processing is completed, the sample is dissolved in water at room temperature for 10 minutes, then dried at 120°C for 20 minutes, and the sample is sandblasted and polished as necessary to obtain the desired personalized second. Level porous tantalum hafnium zirconium titanium metal components. The strength of the tantalum-based component is 106.2 MPa, and the porosity is 21.8%, wherein the primary pore size is 100-126 μm, and the secondary pore size is 38-58 μm.
对比例1：Comparative example 1:
实施例1中所用钽粉的粒度范围为25～64μm、D50为45μm，商业钛粉粒度范围为15～50μm、D50为40μm。The particle size range of the tantalum powder used in Example 1 is 25-64 μm, the D50 is 45 μm, the particle size range of the commercial titanium powder is 15-50 μm, and the D50 is 40 μm.
以Ta粉和商业钛粉为原料，称重Ta粉17kg、商业钛粉2kg，加入氧化锆球，在滚筒球磨机中以60rpm的转速球磨12小时，得到氧含量为0.5wt％粉体。然后将球磨好的粉体放置于华曙高科生产的选区激光熔融设备的供粉缸中，选用50μm直径的激光束斑、350W的激光能量、0.8m/s的扫描速度、80μm的扫描间距、30μm的单层铺粉层厚度，在氩气的保护气氛下激光熔融钽金属。激光加工完成之后，把样品放在室温条件下的水中溶解10分钟，然后在120℃温度条件下烘干20分钟，并对样品进行喷砂处理和必要的打磨，从而获得所需的个性化多孔钽金属构件。所述钽构件的强度为65.4MPa、孔隙率为9.6％。Using Ta powder and commercial titanium powder as raw materials, weigh 17kg of Ta powder and 2kg of commercial titanium powder, add zirconia balls, and mill in a roller mill at a speed of 60rpm for 12 hours to obtain a powder with an oxygen content of 0.5wt%. Then place the ball-milled powder in the powder supply cylinder of the selective laser melting equipment produced by Farsoon Hi-Tech, choose a laser beam spot with a diameter of 50 μm, a laser energy of 350 W, a scanning speed of 0.8 m/s, and a scanning distance of 80 μm. The thickness of the single-layer powder layer is 30μm, and the tantalum metal is laser-melted under the protective atmosphere of argon. After the laser processing is completed, the sample is dissolved in water at room temperature for 10 minutes, then dried at 120°C for 20 minutes, and the sample is sandblasted and polished as necessary to obtain the desired personalized porosity. Tantalum metal components. The tantalum member has a strength of 65.4 MPa and a porosity of 9.6%.
由于没有添加硅酸钠粉，导致3D打印成形的钽零件孔隙率较低。Due to the absence of sodium silicate powder, the porosity of 3D printed tantalum parts is low.
对比例2：Comparative example 2:
实施例1中所用钽粉粒度范围为25～64μm、D50为45μm，商业钛粉粒度范围为15～50μm、D50为40μm，商业硅酸钠粉的粒度范围为38～53μm、D50为45μm。The particle size range of tantalum powder used in Example 1 is 25-64 μm, D50 is 45 μm, the particle size range of commercial titanium powder is 15-50 μm, D50 is 40 μm, the particle size range of commercial sodium silicate powder is 38-53 μm, D50 is 45 μm.
以Ta粉、商业钛粉和商业硅酸钠粉为原料，称重Ta粉17kg、商业钛粉2kg、商业硅酸钠粉1kg，加入氧化锆球，在滚筒球磨机中以60rpm的转速球磨12小时，得到氧含量为0.5wt％粉体。然后将球磨好的粉体放置于华曙高科生产的选区激光熔融设备的供粉缸中，选用50μm直径的激光束斑、50W的激光能量、0.8m/s的扫描速度、80μm的扫描间距、30μm的单层铺粉层厚度，在氩气的保护气氛下激光熔融钽金属。激光加工完成之后，把样品放在室温条件下的水中溶解10分钟，然后在120℃温度条件下烘干20分钟，并对样品进行喷砂处理和必要的打磨，从而获得所需的个性化二级多孔钽钛金属构件。所述钽钛构件的强度为32.8MPa、孔隙率为17.5％。Using Ta powder, commercial titanium powder and commercial sodium silicate powder as raw materials, weigh 17kg of Ta powder, 2kg of commercial titanium powder, and 1kg of commercial sodium silicate powder, add zirconia balls, and mill in a roller mill at a speed of 60rpm for 12 hours , to obtain a powder with an oxygen content of 0.5 wt%. Then place the ball-milled powder in the powder supply cylinder of the selective laser melting equipment produced by Farsoon Hi-Tech, choose a laser beam spot with a diameter of 50 μm, a laser energy of 50 W, a scanning speed of 0.8 m/s, and a scanning distance of 80 μm. The thickness of the single-layer powder layer is 30μm, and the tantalum metal is laser-melted under the protective atmosphere of argon. After the laser processing is completed, the sample is dissolved in water at room temperature for 10 minutes, then dried at 120°C for 20 minutes, and the sample is sandblasted and polished as necessary to obtain the desired personalized second. Porous tantalum-titanium metal components. The strength of the tantalum-titanium member is 32.8 MPa and the porosity is 17.5%.
由于所用激光能量不在本发明的范围，导致3D打印成形的钽基零件性能差。Since the laser energy used is outside the scope of the present invention, 3D printed tantalum-based parts have poor performance.
对比例3：Comparative example 3:
其他条件均与实施例1一致，不同的之处在于采用500W的激光能量；由于温度过高，远远超过硅酸钠的沸点，实验失败。Other conditions are consistent with Example 1, except that the laser energy of 500W is used; because the temperature is too high, far exceeding the boiling point of sodium silicate, the experiment fails.
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| CN202210289117.0ACN114749659B (en) | 2022-03-23 | 2022-03-23 | Method for preparing secondary porous tantalum metal part by 3D printing |
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| CN108213408B (en)* | 2018-01-11 | 2020-03-13 | 中南大学 | Method for preparing porous metal part with complex structure by using 3D printing technology |
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| TWI877173B (en)* | 2019-07-19 | 2025-03-21 | 美商環球高級金屬美國公司 | Spherical tantalum-titanium alloy powder, products containing the same, and methods of making the same |
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