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Número de publicaciónCN102407332 A
Tipo de publicaciónSolicitud
Número de solicitudCN 201110397170
Fecha de publicación11 Abr 2012
Fecha de presentación5 Dic 2011
Fecha de prioridad5 Dic 2011
Número de publicación201110397170.4, CN 102407332 A, CN 102407332A, CN 201110397170, CN-A-102407332, CN102407332 A, CN102407332A, CN201110397170, CN201110397170.4
Inventores刘会群, 易丹青, 王杰恩, 胡海波
Solicitante烟台工程职业技术学院
Exportar citaBiBTeX, EndNote, RefMan
Enlaces externos:  SIPO, Espacenet
Preparation method for porous titanium
CN 102407332 A
Resumen
The invention discloses a preparation method for porous titanium, comprising the following steps of: 1. preparing titanium powder; 2. preparing photosensitive glue; 3. printing and forming in a three-dimensional mode; 4. curing; 5. discharging glue; and 6. sintering. The technical scheme provided by the invention brings the beneficial effect that a workpiece is quick and simple to form by the droplet jetting technology, working efficiency is high, cost is low, raw materials can be recycled, the workpiece with complex shape can be manufactured by computer program control; the forming precision of the workpiece is greatly improved by proper photosensitive adhesive with a proper solidification method; the titanium powder granularity is reduced by adopting the ball-milling technology, the granularity is even, the apertures of the prepared porous titanium product are evenly distributed, and intensity is improved; and the porous titanium products of different porosities can be manufactured by controlling the types of the photosensitive glue and droplet jetting parameters and making different sintering technologies.
Reclamaciones(7)  traducido del chino
1. 一种多孔钛的制备方法,其特征在于,所述制备方法包括以下步骤: 步骤1 :制备粒度适宜的钛粉将粗制钛粉与无水乙醇混合,加入球磨助剂,真空球磨24h后于真空干燥48h,所述粗制钛粉与无水乙醇按质量比4:1混合; 步骤2:制备光敏胶将光敏树脂、光固化单体、有机溶剂、光引发剂及其它活性添加剂按一定配比混合均勻,充分搅拌均勻后制得光敏胶并在室温黑暗环境下保存;所述光敏树脂添加量为质量份20-100 ;所述光固化单体添加量为质量份10-30 ;所述有机溶剂的添加量为质量份5-30 ;所述光引发剂的添加量为质量份0. 5-3 ;所述其它添加剂的添加量为质量分0. 1-1 ; 步骤3 :微滴喷射将步骤1得到的钛粉,平铺于工作台上,将步骤2得到的光敏胶装入喷射腔中,加热喷射腔并通过计算机控制所需喷射图形及喷射参数喷射液态光敏胶; 步骤4:固化将步骤3经液态光敏胶润湿后得到的钛粉在室温下进行紫外光照射,使光敏胶发生聚合反应固化,从而对钛粉起支撑作用; 步骤5 :逐层堆积在已固化的一层钛粉上另铺一层钛粉重复步骤3、步骤4所述过程; 步骤6 :真空排胶及烧结将步骤5中的制件在低温环境下进行干燥一段时间后,于高温真空排胶,保温一段时间后继续升高温度至烧结温度进行烧结,最终制得所需多孔钛。 A method for producing a porous titanium, characterized in that said preparation method comprising the following steps: Step 1: Preparation of titanium powder particle size suitable crude titanium powder was mixed with anhydrous ethanol, added to aid milling, ball milling vacuo 24h after vacuum drying 48h, the crude titanium powder mass ratio with absolute ethanol 4: 1 mixture; Step 2: Preparation of photoresist photosensitive resin, photocurable monomer, organic solvent, active agents and other additives, photoinitiators Press certain proportion mix, stir evenly, photosensitive plastic and stored in the dark at room temperature; the addition amount of the photosensitive resin 20-100 parts by mass; the addition amount of the photo-curable monomers 10-30 parts by weight; parts by mass of the organic solvent is added in an amount of 5-30; the photoinitiator added in an amount by mass of 0. 5-3 parts; the mass fraction of the other additives added in an amount of 0. 1-1; Step 3: spray droplets obtained in Step 1 titanium powder, spread on the table, the photoresist obtained in Step 2 into the injection chamber, heated spray chamber and the desired spray pattern and spray liquid photoresist injection parameters by computer control; Step 4: Step 3 by curing the liquid photosensitive adhesive obtained after wetting titanium powder UV irradiation at room temperature, so that a polymerization reaction occurs cured photoresist, and thus play a supportive role titanium powder; Step 5: drill has been deposited in Another layer of solidified titanium powder spread on a titanium powder Repeat steps 3, 4 step process; Step 6: After vacuum debinding and sintering step 5 parts dried at low temperatures for some time, at high temperature latex vacuum, holding the temperature continues to rise after a period of time to the sintering temperature sintering, to obtain the desired final porous titanium.
2.根据权利要求1所述的制备方法,其特征在于,所述步骤1中,所述球磨助剂为硬脂酸,其添加量为钛粉质量1% ;所述球磨工艺参数为球料比1:5,转速300r/min,所述钛粉干燥温度为60°C。 2. The production method according to claim 1, wherein said step 1, the milling aid is stearic acid, which added in an amount of 1% by mass titanium powder; the ball milling process parameters material ratio of 1: 5, speed 300r / min, the titanium powder drying temperature of 60 ° C.
3.根据权利要求1所述的制备方法,其特征在于,所述步骤2中,所述光敏树脂为:环氧丙烯酸酯、环氧丙烯酸缩水甘油酯、甲基丙烯酸环氧树脂、双酚A环氧树脂;所述光固化单体为N-乙烯基吡咯烷酮、N,N-二甲基苄胺、N,N-二甲基乙酰胺;催化剂为三乙醇胺、叔胺;所述有机溶剂包括稀释剂和溶剂,所述稀释剂为苯基丙烯酸乙酯、甲基丙烯酸羟乙酯、 甲基丙烯酸异冰片酯、甲基丙烯酸四氢慷酯、季戊四醇四甲基丙烯酸酯、甲基丙烯酸十六醇酯;所述溶剂为甲苯、乙二醇;所述光引发剂为安息香醚类、二苯甲酮;所述其它添加剂为润湿剂丙三醇、触变剂羟乙基纤维素、阻燃剂对苯二酚、交联剂过氧化苯甲酰。 3. The production method according to claim 1, wherein, in the step 2, the photosensitive resin is: epoxy acrylate, epoxy acrylate, epoxy methacrylate, bisphenol A epoxy resins; the photocurable monomer is N- vinyl pyrrolidone, N, N- dimethylbenzylamine, N, N- dimethylacetamide; catalyst is triethanolamine, tertiary amine; the organic solvent comprises thinners and solvents, the diluent is phenyl ethyl acrylate, methyl acrylate, methyl methacrylate, isobornyl methacrylate, tetrahydro generous, pentaerythritol tetra methacrylate, methacrylate sixteen alcohol ester; the solvent is toluene, ethylene glycol; the photoinitiator is benzoin ethers, benzophenone; the other additives as glycerol wetting agents, thixotropic agents hydroxyethylcellulose, resistance flame retardants hydroquinone, benzoyl peroxide crosslinking agent.
4.根据权利要求1所述的制备方法,其特征在于,所述步骤3中,采用微滴喷射三维打印成形技术,喷射图形为方形、圆形,喷头喷嘴直径为50 μ m,喷射速度为6m/s,标准液滴喷射量为80pl ;所述加热温度为150-300°C。 4. The production method according to claim 1, wherein said step 3, using the spray droplets forming a three-dimensional printing technique, spray pattern square, 50 μ m circular, the nozzle diameter of the nozzle, the ejection velocity 6m / s, the standard droplet ejection amount 80pl; the heating temperature is 150-300 ° C.
5.根据权利要求1所述的制备方法,其特征在于,所述步骤4中,所述固化方法为紫外光固化,固化时间为20-100s。 5. The production method according to claim 1, wherein, in the step 4, the curing method is UV curing, the curing time is 20-100s.
6.根据权利要求1所述的制备方法,其特征在于,所述步骤5中,钛粉逐层堆积厚度为15-25mm。 6. The production method according to claim 1, characterized in that, said step 5, the titanium powder deposited layer by layer thickness 15-25mm.
7.根据权利要求1所述的制备方法,其特征在于,所述步骤6中,干燥温度为100°C干燥时间为12-Mh,真空排胶温度为600°C,加热时间为2-4h,烧结温度为1200°C,保温时间为Ih0 7. The production method according to claim 1, wherein said step 6, the drying temperature is 100 ° C the drying time is 12-Mh, vacuum debinding temperature of 600 ° C, the heating time is 2-4h sintered at 1200 ° C, holding time Ih0
Descripción  traducido del chino

一种多孔钛的制备方法 Method for preparing a porous titanium

技术领域 Technical Field

[0001] 本发明涉及多孔钛技术领域,特别涉及一种多孔钛紫外光固化及三维打印成型的制备方法,实现了产品精度高的制备。 [0001] The present invention relates to a porous titanium technology, particularly to a porous titanium UV curing and preparation of 3D printing method to achieve a high precision of preparation.

[0002] [0002]

背景技术 Background

[0003] 钛及其合金是一种密度低、生物相容性好、力学相容性好、机械性能优异的金属材料,已被广泛用于医用植入材料。 [0003] The titanium and its alloys is a low density, good biocompatibility, mechanical compatibility, and excellent mechanical properties of metallic materials, has been widely used in medical implants. 多孔钛的组织结构具有三维空间贯通的孔隙结构,不仅可以进一步降低其弹性模量,而且有利于生物组织的生长和体液传输,是一种有深远应用前景的新型医用金属材料。 Organizational structure of the porous titanium having a pore structure through three-dimensional space, not only can further reduce the elastic modulus, but also conducive to the growth of biological tissues and fluids transport, is a far-reaching promising new medical metallic material. 目前,多孔钛及其合金在临床上得到了多方面的应用,如人体关节处应用的多孔钛髋关节以及多孔涂层钛合金、在牙床修复中应用的多孔钛牙种植体、心脏瓣膜替换手术时应用的钛人工心脏瓣膜等[Fujihyashi S, Neo Μ, Kim H Μ, et al, Biomaterials, 2004]。 Currently, porous titanium and its alloys have been many clinical applications, such as human joints applied porous titanium hip and a porous coating of titanium alloy, in the application of gum repair porous titanium dental implants, heart valve replacement surgery the application of titanium artificial heart valves, etc. [Fujihyashi S, Neo Μ, Kim H Μ, et al, Biomaterials, 2004].

[0004] 多孔钛传统制备方法有粉末冶金法、浆料发泡法Rarrett R, Abhay P, Dimitrios PA, Biomaterials,2006]。 [0004] The traditional preparation methods of porous titanium powder metallurgy, pulp foaming Rarrett R, Abhay P, Dimitrios PA, Biomaterials, 2006]. Oh IH [Oh IH, Nomura N, Masahashi N, et al, Scripta Materialia, 2003]等采用粉末冶金法制备出孔隙度为30%的多孔钛,其杨氏模量和抗弯强度分别为12_25GI^和115MPa。 Oh IH [Oh IH, Nomura N, Masahashi N, et al, Scripta Materialia, 2003], etc. prepared by powder metallurgy a porosity of 30% of the porous titanium, Young's modulus and flexural strength were 12_25GI ^ and 115MPa. 李虎[李虎,虞奇峰,张波等,稀有金属与工程,2006]使用双氧水作为浆料发泡剂,得到孔隙度为58%、杨氏模量为4. 15GPa、压缩强度190. 7MPa的多孔钛。 Li Hu [Li Hu, Yu Qifeng, Zhang Bo and other rare metals and engineering, 2006] use of hydrogen peroxide as a slurry foaming agent to obtain a porosity of 58%, a Young's modulus of 4. 15GPa, compressive strength of 190. 7MPa porous titanium. 三维打印成形(3DP)技术也称粉末材料选择性粘结,是近年来发展起来的一种新型快速原型制造技术,三维打印技术是相对于二维平面打印而提出的概念,最早由美国麻省理工学院的Mchs EM和Cima MJ等人于1991年申请了关于三维打印的专利[sachs E, Cima M, Williams P, et al. Three dimensional printing: rapid tooling and prototypes directly from a CAD model. Journal of Engineering for Industry, 1992,114 (4) : 481-488.],基于这个专利开发的三维打印成形是采用惠普热气泡喷头喷射粘接材料使粉末粘接成型。 Three Dimensional Printing (3DP) technology, also known as selective bonding powder materials, rapid prototyping is a new technology developed in recent years, the concept of three-dimensional printing technology is a two-dimensional plane with respect to the print and raised first by Massachusetts Tech Mchs EM and Cima MJ et al applied for a patent on 3D printing [sachs E in 1991, Cima M, Williams P, et al Three dimensional printing:. rapid tooling and prototypes directly from a CAD model Journal of Engineering. for Industry, 1992,114 (4):. 481-488], based on this patent developed 3D printing using HP thermal bubble formation is ejecting the adhesive bonding the powder molding. 3DP的工作原理类似于喷墨打印,是一种基于液滴喷射原理的快速成形技术,即在数字信号的激励下,使喷嘴工作腔内的液体在瞬间形成液滴,并以一定的速度和频率从喷嘴喷出,喷射图形CAD软件绘制,胶黏剂固化后逐层堆积, 得至丨J成形零件[Dimitrov D. , Schrevez K. , de Beer N. , et al. Three dimensional printing in the South African industrial environment[J]. South African Journal of Industrial Engineering, 2008,19 (1): 195-213·]。 3DP works like an ink-jet printing, is based on the principle of droplet ejection rapid prototyping technology, namely in the excitation of the digital signal, the working chamber of the nozzle to form droplets of liquid in an instant, and to a certain speed and frequency from the nozzle, spray pattern CAD software rendering, layer by layer stacked after curing the adhesive, have to 丨 J molded parts [Dimitrov D., Schrevez K., de Beer N., et al. Three dimensional printing in the South African industrial environment [J] South African Journal of Industrial Engineering, 2008,19 (1):. 195-213 ·]. 3DP 快速成形技术是目前快速成形中最具有生命力的技术,该技术无需激光系统,仅需选择合适的胶黏剂便可制得各种不同类型的多孔钛制件,它具有设备操作简单、成形速度快、成形过程无污染、成形件的精度高,可在办公室环境使用等优点。 3DP rapid prototyping technology is the rapid prototyping technology is currently the most viable, the technology without laser system, simply select the appropriate adhesive can be prepared by a variety of different types of porous titanium parts, it has a simple device, forming speed, forming process without pollution, high precision molded parts, can use in an office environment and other advantages. 因此,3DP是目前快速成形技术研究的热点之一,特别适合我国的市场需求[李晓燕,伍永辉,张曙.三维打印成形技术的新进展.机械制造, 2005,43 (496) : 62-64.],其应用前景广阔。 Therefore, 3DP is one of the hot rapid prototyping technology research, especially for China's market demand [Li Xiaoyan, Wu Yonghui, Zhang Shu new three dimensional printing technology in machinery manufacturing, 2005, 43 (496): 62-64. ], its broad application prospects.

[0005] 在实现本发明的过程中,发明人发现现有技术至少存在以下问题:基于三维打印成形技术制备的多孔钛制件表面形貌较差,而且强度较之其他成形方法较低。 [0005] In the process of implementing the present invention, the inventors have found that the prior art at least has the following problems: poor print-based three-dimensional shaped porous titanium surface topography prepared parts, and lower intensity than other molding method. 发明内容 DISCLOSURE

[0006] 本发明提供了一种多孔钛的制备方法,此制备方法能够使用微米级钛粉为原料, 通过3DP技术能够快速获得精度较高的成形制件,通过选用合适光敏胶黏剂、将光固化手段与烧结工艺相结合能够获得不同孔隙率的多孔钛制件并显著增加制备得到的多孔钛的强度和硬度,降低其热导率,且用此方法制备的多孔钛制品形状精度高,孔径分布均勻,孔隙率可调,通过合适表面处理产品纯度较高。 [0006] The present invention provides a method for preparing porous titanium, this production method micron titanium powder can be used as raw material by 3DP technology to quickly obtain high precision molding parts, by appropriate choice of the photosensitive adhesive, the Light curing means and sintering process of combining different porosity can be obtained porous titanium parts and significantly increases the production of the resulting porous titanium strength and hardness, lower thermal conductivity, and high precision shape porous titanium products prepared by this method, pore size distribution, porosity adjustable high purity by a suitable surface treatment products.

[0007] 为了实现上述发明目的,本发明的技术方案如下: 一种多孔钛的制备方法,所述制备方法包括以下步骤: 步骤1 :制备粒度小,粒径分布窄的钛粉 [0007] To achieve the above object of the invention, the technical solution of the present invention is as follows: Method for preparing porous titanium, said process comprising the following steps: Step 1: Preparation of small particle size, a narrow particle size distribution of the titanium powder

将粗制钛粉与无水乙醇混合,加入球磨助剂,真空球磨24h后于真空干燥48h,所述粗制钛粉与无水乙醇按质量比4:1混合; 步骤2:制备光敏胶 The crude titanium powder was mixed with anhydrous ethanol, added to aid milling, ball milling in vacuo and dried under vacuum after 24h 48h, the crude titanium powder mass with absolute ethanol to 4: 1 mixing; Step 2: Preparation of photoresist

在黑暗环境下,将光敏树脂、光固化单体、有机溶剂、其它活性添加剂按一定质量比混合均勻,在20-60°C条件下,经机械搅拌30-120min后添加光引发剂,继续搅拌10-30min,制得光敏胶; In the dark, the light-sensitive resin, photo-curable monomers, organic solvents, other active additives were mixed to homogeneity by a certain quality, at 20-60 ° C conditions, by mechanical agitation add light after 30-120min initiator and continue stirring 10-30min, to prepare the photoresist;

所述光敏树脂添加量为质量份20-100 ;所述光固化单体添加量为质量份10-30 ;所述有机溶剂的添加量为质量份5-30 ;所述光引发剂的添加量为质量份0. 5-3 ;所述其它添加剂的添加量为质量分0. 1-1 ; The addition amount of the photosensitive resin 20-100 parts by mass; the photocurable 10-30 parts by mass of the monomer addition amount; parts by mass of the organic solvent is added in an amount of 5-30; addition amount of the photoinitiator agent 0. 5-3 parts by mass; the addition amount of quality additives other points 0. 1-1;

所述有机溶剂包括稀释剂和溶剂; The organic solvents include diluents and solvents;

稀释剂和溶剂从本质上来说相同,稀释剂为了降低体系黏度,改善体系及产物性能的填充物,可以是传统的有机溶剂,也可以是其它一类有机物,溶剂是指传统概念上的常用“有机溶剂”,它相当于对稀释剂的“稀释”效果做增强,如果在加入稀释剂后体系流动性仍较差,这时加入一点溶剂; Diluents and solvents are essentially the same as diluents to reduce the viscosity of the system, improve system performance and product fillers may be conventional organic solvents, it can be a class of other organic compounds, solvents commonly refers to the traditional concept of " The organic solvent ", which is equivalent to a diluent" dilution "effect do enhanced if liquidity remains poor after the addition of a diluent, then add a little solvent;

步骤3 :微滴喷射(即三维打印成型) Step 3: droplet ejection (ie 3D Printing)

将步骤1得到的钛粉,平铺于工作台上,将步骤2得到的光敏胶装入喷射腔中,加热喷射腔并通过计算机控制所需喷射图形及喷射参数喷射液态光敏胶; 步骤4:固化 The titanium powder obtained in the step 1, the tile on the table, the photosensitive adhesive obtained in step 2 is loaded in the injection chamber, the heating chamber and the injection spray pattern and the desired injection parameters ejection liquid photoresist by computer control; Step 4: solidify

将步骤3经液态光敏胶润湿后得到的钛粉在室温下进行紫外光照射,使光敏胶发生聚合反应固化,从而对钛粉起支撑作用; 步骤5 :逐层堆积 Step 3 wetted by the liquid photoresist obtained after the titanium powder UV irradiation at room temperature, so that a polymerization reaction occurs cured photoresist, and thus play a supportive role titanium powder; Step 5: stacking drill

在已固化的一层钛粉上另铺一层钛粉重复步骤3、步骤4所述过程; 步骤6 :真空排胶及烧结 Cured layer on another layer of titanium powder, titanium powder Repeat steps 4 3 step process; Step 6: vacuum debinding and sintering

将步骤5中的制件在低温环境下进行干燥一段时间后,于高温真空排胶,保温一段时间后继续升高温度至烧结温度进行烧结,最终制得所需多孔钛。 After step 5 parts dried at low temperatures for some time, at high temperature and vacuum exhaust glue, holding the temperature continues to rise after a period of time to the sintering temperature sintering, to obtain the desired final porous titanium.

[0008] 上述制备方法中,步骤3是通过计算机控制喷头绘制的图形、喷头的喷射速度、喷射量,先在平台上喷一层粉然后按所需形状按设定的喷射参数喷射胶黏剂,分别制备柱体和长方体样品,微滴喷射就是通过加热喷射腔,液态光敏胶以小液滴的形式喷射到钛粉层上,通过润湿作用在粉末间扩散,通过调整其喷射速度、喷射量来调整这种润湿效果,通过改变加热温度来改变液滴的形成大小。 [0008] The preparation method described above, step 3 is controlled by a computer graphics drawing nozzles, nozzle jet speed, injection quantity, first spray a layer of powder on the platform and press the desired shape by setting adhesive spray injection parameters , cylindrical and rectangular samples were prepared, droplet ejection is heated spray chamber, liquid photoresist in the form of small droplets sprayed onto the titanium powder layer by diffusion between the powder wetting, by adjusting the injection rate, injection to adjust the amount of this wetting, the heating temperature is changed by changing the size of the droplets formed. 步骤3、4、5综合起来为三维打印成型技术,在制备一个样品时,其中步骤3是喷射光敏胶、步骤4是固化光敏胶、步骤5是重复3、4的步骤至所需的样品厚度,重复过程中3、4步骤条件不做任何改变。 Step 3,4,5 together for the 3D printing technology in the preparation of a sample when, where step 3 is spray the photoresist, photoresist curing step 4, step 5 was repeated 3 and 4 to the desired thickness of the sample Repeat steps 3 and 4 process conditions without any change.

[0009] 进一步地,所述步骤1中,所述球磨助剂为硬脂酸,其添加量为钛粉质量1% ;所述球磨工艺参数为球料比1 : 5,转速300r/min,所述钛粉干燥温度为60°C。 [0009] Further, the step 1, the milling aid is stearic acid, added in an amount of 1% by mass of titanium powder; the ball milling process parameters feed ratio of 1: 5, speed 300r / min, The titanium powder drying temperature of 60 ° C. 球料比指的是球磨时用的钢球和钛粉的质量比。 Ball feed ratio refers to the ratio of quality when using ball milling and titanium powder.

[0010] 进一步地,所述步骤2中,所述光敏树脂为:环氧丙烯酸酯、环氧丙烯酸缩水甘油酯、甲基丙烯酸环氧树脂、双酚A环氧树脂;所述光固化单体为N-乙烯基吡咯烷酮、N,N- 二甲基苄胺、N,N-二甲基乙酰胺;催化剂为三乙醇胺、叔胺;所述稀释剂为苯基丙烯酸乙酯、 甲基丙烯酸羟乙酯、甲基丙烯酸异冰片酯、甲基丙烯酸四氢慷酯、季戊四醇四甲基丙烯酸酯、甲基丙烯酸十六醇酯;所述溶剂为甲苯、乙二醇;所述光引发剂为安息香醚类、二苯甲酮;所述其它添加剂为润湿剂丙三醇、触变剂羟乙基纤维素、阻燃剂对苯二酚、交联剂过氧化苯甲酰。 [0010] Further, in the step 2, the photosensitive resin is: epoxy acrylate, epoxy acrylate, glycidyl methacrylate, epoxy resins, bisphenol A epoxy resin; a photocurable monomer as N- vinyl pyrrolidone, N, N- dimethylbenzylamine, N, N- dimethylacetamide; catalyst is triethanolamine, tertiary amines; the diluent is phenyl acrylate, hydroxyethyl methacrylate, ethyl methacrylate, isobornyl methacrylate, tetrahydro Kang, pentaerythritol tetra methacrylate, cetyl alcohol esters of methacrylic acid; the solvent is toluene, ethylene glycol; the photoinitiator is benzoin ethers, benzophenone; the other additives as glycerol wetting agents, thixotropic agents hydroxyethylcellulose, flame retardants hydroquinone, benzoyl peroxide crosslinking agent.

[0011] 所述步骤3中,采用微滴喷射三维打印成形技术,喷射图形为方形、圆形,喷头喷嘴直径为50 μ m,喷射速度为6m/s,标准液滴喷射量为SOpl ;所述加热温度为150-300°C。 [0011] In the step 3, the use of spray droplets forming a three-dimensional printing technique, spray pattern square, round, the nozzle of the nozzle 50 μ m in diameter, jet velocity of 6m / s, the standard droplet ejection amount SOpl; the said heating temperature is 150-300 ° C.

[0012] 将步骤2得到的光敏胶在150-300°C加热10-30min后,转变为液体,液体经喷头以微滴形式喷射于钛粉层上,经充分润湿后,在室温下紫外光固化20-100S,使颗粒之间粘结成具有所需形状的制件; After the [0012] The photoresist obtained in Step 2 was heated at 150-300 ° C 10-30min, into a liquid, the liquid through the spray nozzle to form droplets on the titanium powder layer, after thoroughly wetted UV at room temperature light curing 20-100S, the adhesive between the particles have a desired shape parts;

三维打印成形:用计算机绘图软件绘制所需多孔钛制件图形,编辑程序,将步骤1得到的钛粉平铺于工作台上,将步骤2得到的光敏胶加入喷射腔中,加热喷射枪,并以一定速率按所需图形喷射光敏胶液滴,液滴充分润湿钛粉后以紫外光照射固化成形,完全固化后在第一层钛粉上铺加新一层钛粉,并重复以上步骤。 Three Dimensional Printing: Using computer graphics software porous titanium parts needed for drawing graphics editing program, the titanium powder obtained in step 1 tile on the table, the photoresist obtained in Step 2 into a jet chamber, heated spray gun, and at a rate according to a desired pattern photoresist droplet ejection, after a droplet titanium powder sufficiently wetted to ultraviolet light curable molding, a first layer of fully cured capped add a new layer of titanium powder titanium powder, and repeat step.

[0013] 所述步骤4中,所述固化方法为紫外光固化,固化时间为20-100S。 [0013] In the step 4, the curing method for the curing, the curing time is 20-100S.

[0014] 所述步骤5中,钛粉逐层堆积厚度为15_25mm。 [0014] In the step 5, the titanium powder deposited layer by layer thickness 15_25mm.

[0015] 所述步骤6中,干燥温度为100°C干燥时间为12_24h,真空排胶温度为600°C,加热时间为2-4h,烧结温度为1200°C,保温时间为lh。 [0015] In the step 6, the drying temperature is 100 ° C drying time 12_24h, vacuum debinding temperature of 600 ° C, the heating time is 2-4h, the sintering temperature is 1200 ° C, holding time lh.

[0016] 真空排胶时,将固态制件放置于干燥箱中于100°C干燥1214h,将干燥后的制件放置于真空炉中以600°C排胶2-4h。 [0016] When the vacuum exhaust glue, the solid parts placed in the oven at 100 ° C and dried 1214h, the parts dried and placed in a vacuum furnace at 600 ° C latex 2-4h.

[0017] 本发明提供的技术方案带来的有益效果是:(1)采用微滴喷射技术,使得制件成形快速简单,工作效率高,成本低,原料可回收利用,通过计算机程序控制可制得复杂形状的制件;(2)通过选用合适的光敏胶黏剂,并采取适宜的固化方法,极大的提高了制件的成形精度;(3)采用球磨工艺,使得钛粉粒度较小,粒度分布均勻,制备的多孔钛制品孔径分布均勻,强度提高,通过控制光敏胶种类和微滴喷射参数以及制定不同烧结工艺能制得不同孔隙率大小的多孔钛制件。 [0017] The aspect of the present invention provides the beneficial effect that: (1) using a droplet ejection technology, making parts forming fast and simple, high efficiency, low cost, recyclable material, can be prepared by a computer program control too complex shape of the workpiece; (2) the appropriate choice of light-sensitive adhesive, and take appropriate curing method greatly improves the precision molded parts; (3) the milling process, making smaller particle size titanium powder particle size distribution, pore size of porous titanium products prepared distribution, strength increased, by controlling the type of photoresist and droplet ejection parameters and the development of sintering processes can be prepared porous titanium parts different porosities size.

[0018] [0018]

附图说明 Brief Description

[0019] 图1是本发明的工艺流程图。 [0019] FIG. 1 is a flow chart of the present invention. [0020] [0020]

具体实施方式 DETAILED DESCRIPTION

[0021] 为使本发明的目的、技术方案和优点更加清楚,下面将结合附图对本发明实施方式作进一步地详细描述。 [0021] For the purpose, technical solutions, and advantages of the present invention will become clear below with reference to embodiments of the present invention will be further described in detail.

[0022] 实施例1 [0022] Example 1

一种多孔钛的制备方法,包括以下步骤: 步骤1 :制备粒度小,粒径分布窄的钛粉 Method for preparing porous titanium, comprising the following steps: Step 1: Preparation of small particle size, a narrow particle size distribution of the titanium powder

取200g粗制钛粉与50g无水乙醇混合均勻,并加入2g硬脂酸,取IOOOg不锈钢球,在真空环境下球磨Mh,并在60°C真空干燥4¾后得到最大粒度为2-48 μ m钛粉; 步骤2 :制备光敏胶 Take 200g crude titanium powder mixed with 50g ethanol and 2g of stearic acid was added, taking IOOOg stainless steel balls, ball milling in a vacuum environment Mh, and dried in vacuo at 60 ° C after 4¾ maximum particle size of 2-48 μ m titanium powder; Step 2: Preparation of photoresist

将50-70份环氧丙烯酸酯,20-30份N-乙烯基吡咯烷酮,1-2份安息香二甲醚,4份叔胺,2份伯胺于室温或加热至50°C混合搅拌均勻,即可制得光敏胶。 The 50 to 70 parts of epoxy acrylate, 20-30 parts of N- vinylpyrrolidone, 1-2 parts of benzoin dimethyl ether, 4 parts of a tertiary amine, 2 parts of a primary amine at room temperature or heated to 50 ° C, mixing evenly, the photoresist can be obtained.

[0023] 步骤3:三维打印成形 [0023] Step 3: Three Dimensional Printing

用计算机绘制所需多孔钛制件图形,编辑程序,将步骤1得到的钛粉平铺于工作台上,得到厚度为0. 5-lmm的钛粉层,将步骤2得到的光敏胶加入喷射腔中,加热喷射枪至150-300°C,加热时间为10-30min,待胶黏剂全部变为液体后以6m/s速率按所需图形喷射光敏胶液滴,液滴充分润湿钛粉后以紫外光照射固化IOOs成形,完全固化后在第一层钛粉上铺加新一层钛粉,并重复以上步骤逐层堆积至厚度为15-25mm。 Computer porous titanium parts needed for drawing graphics editing program, the titanium powder obtained in step 1 tile on the table, the titanium powder layer having a thickness of 0. 5-lmm will photoresist obtained in Step 2 into a jet chamber, heated spray gun to 150-300 ° C, the heating time is 10-30min, until all the adhesive becomes liquid 6m / s rate of the photoresist according to a desired pattern ejecting droplets, the droplets sufficiently wet titanium After the powder with UV radiation curing IOOs forming, completely cured after the first layer of titanium powder capped add a new layer of titanium powder, and repeat the above steps stacked layer by layer to a thickness of 15-25mm.

[0024] 步骤4 :真空排胶 [0024] Step 4: vacuum debinding

将步骤3中含胶黏剂的固态制件放置于干燥箱中于100°C干燥12-24h,将干燥后的制件放置于真空炉中以600°C排胶2-4h。 Step 3 solid articles containing adhesive is placed in oven at 100 ° C and dried 12-24h, the parts dried and placed in a vacuum furnace at 600 ° C latex 2-4h.

[0025] 步骤5 :烧结 [0025] Step 5: Sintering

将步骤4中经排胶处理的固态制件进行真空烧结,烧结的温度为1200°C,时间为lh。 Will step through the solid parts of the latex-treated 4 vacuum sintering, the sintering temperature of 1200 ° C, time is lh.

[0026] 实施例2 [0026] Example 2

一种多孔钛的制备方法,包括以下步骤: 步骤1 :制备粒度小,粒径分布窄的钛粉 Method for preparing porous titanium, comprising the following steps: Step 1: Preparation of small particle size, a narrow particle size distribution of the titanium powder

取200g粗制钛粉与50g无水乙醇混合均勻,并加入2g硬脂酸,取IOOOg不锈钢球,在真空环境下球磨Mh,并在60°C真空干燥4¾后得到最大粒度为2-48 μ m钛粉; 步骤2 :制备光敏胶 Take 200g crude titanium powder mixed with 50g ethanol and 2g of stearic acid was added, taking IOOOg stainless steel balls, ball milling in a vacuum environment Mh, and dried in vacuo at 60 ° C after 4¾ maximum particle size of 2-48 μ m titanium powder; Step 2: Preparation of photoresist

将30-50份甲基丙烯酸环氧树酯加热至40-50°C后依次加入10-15份苯基丙烯酸乙酯、 5-10份甲基丙烯酸羟乙酯,10-20份N,N- 二甲基苄胺,1-2份安息香二甲醚,1-3份过氧化苯甲酰混合搅拌均勻,即可制得光敏胶。 Were added to 30-50 parts of an epoxy resin of methacrylic acid was heated to 40-50 ° C after 10-15 parts phenyl ethyl acrylate, 5-10 parts of hydroxyethyl methacrylate, 10-20 parts of N, N - dimethylbenzylamine, 1-2 parts of benzoin dimethyl ether, 1-3 parts of benzoyl peroxide mixing evenly, can be obtained photoresist.

[0027] 步骤3:三维打印成形 [0027] Step 3: Three Dimensional Printing

用计算机绘制所需多孔钛制件图形,编辑程序,将步骤1得到的钛粉平铺于工作台上,得到厚度为0. 5-lmm的钛粉层,将步骤2得到的光敏胶加入喷射腔中,加热喷射枪至150-300°C,加热时间为10-30min,待胶黏剂全部变为液体后以6m/s速率按所需图形喷射光敏胶液滴,液滴充分润湿钛粉后以紫外光照射固化60s成形,完全固化后在第一层钛粉上铺加新一层钛粉,并重复以上步骤逐层堆积至厚度为15-25mm。 Computer porous titanium parts needed for drawing graphics editing program, the titanium powder obtained in step 1 tile on the table, the titanium powder layer having a thickness of 0. 5-lmm will photoresist obtained in Step 2 into a jet chamber, heated spray gun to 150-300 ° C, the heating time is 10-30min, until all the adhesive becomes liquid 6m / s rate of the photoresist according to a desired pattern ejecting droplets, the droplets sufficiently wet titanium After UV irradiation to cure the powder molding 60s, after complete curing of the first layer a layer of titanium powder capped add new titanium powder, and repeat the above steps a bulk layer by layer to a thickness of 15-25mm. [0028] 步骤4 :真空排胶 [0028] Step 4: vacuum debinding

将步骤3中含胶黏剂的固态制件放置于干燥箱中于100°C干燥12-24h,将干燥后的制件放置于真空炉中以600°C排胶2-4h。 Step 3 solid articles containing adhesive is placed in oven at 100 ° C and dried 12-24h, the parts dried and placed in a vacuum furnace at 600 ° C latex 2-4h.

[0029] 步骤5 :烧结 [0029] Step 5: Sintering

将步骤4中经排胶处理的固态制件进行真空烧结,烧结的温度为1200°C,时间为lh。 Will step through the solid parts of the latex-treated 4 vacuum sintering, the sintering temperature of 1200 ° C, time is lh.

[0030] 实施例3 [0030] Example 3

一种多孔钛的制备方法,包括以下步骤: 步骤1 :制备粒度小,粒径分布窄的钛粉 Method for preparing porous titanium, comprising the following steps: Step 1: Preparation of small particle size, a narrow particle size distribution of the titanium powder

取200g粗制钛粉与50g无水乙醇混合均勻,并加入2g硬脂酸,取IOOOg不锈钢球,在真空环境下球磨Mh,并在60°C真空干燥4¾后得到最大粒度为2-48 μ m钛粉; 步骤2 :制备光敏胶 Take 200g crude titanium powder mixed with 50g ethanol and 2g of stearic acid was added, taking IOOOg stainless steel balls, ball milling in a vacuum environment Mh, and dried in vacuo at 60 ° C after 4¾ maximum particle size of 2-48 μ m titanium powder; Step 2: Preparation of photoresist

将70-100份聚氨酯基丙烯酸环氧树脂、10-30双酚A环氧树脂、10-15份苯基丙烯酸乙酯、5-20份甲基丙烯酸异冰片酯、5-20份甲基丙烯酸四氢慷酯、5-10份季戊四醇四甲基丙烯酸酯、1-2份安息香二甲醚、1-2份二苯甲酮、0. 5-1份丙三醇、0. 5-2份羟乙基纤维素、 0. 1-0. 3份对苯二酚、0. 5-2份过氧化苯甲酰于混料机中混合均勻,即可制得光敏胶。 70-100 parts of the polyurethane-based epoxy acrylate, bisphenol A epoxy resin 10-30, 10-15 parts of phenyl ethyl acrylate, 5-20 parts of isobornyl acrylate, 5-20 parts of methacrylic acid tetrahydro generous acrylate, 5-10 parts of pentaerythritol tetra methacrylate, 1-2 parts of benzoin dimethyl ether, 1-2 parts of benzophenone, 0. 5-1 parts of glycerol, 0. 5-2 parts hydroxyethyl cellulose, 0. 1-0. 3 parts of hydroquinone, 0. 5-2 parts of benzoyl peroxide mixed in the blender, the photoresist can be obtained.

[0031] 步骤3:三维打印成形 [0031] Step 3: Three Dimensional Printing

用计算机绘制所需多孔钛制件图形,编辑程序,将步骤1得到的钛粉平铺于工作台上,得到厚度为0. 5-lmm的钛粉层,将步骤2得到的光敏胶加入喷射腔中,加热喷射枪至150-300°C,加热时间为10-30min,待胶黏剂全部变为液体后以6m/s速率按所需图形喷射光敏胶液滴,液滴充分润湿钛粉后以紫外光照射固化20s成形,完全固化后在第一层钛粉上铺加新一层钛粉,并重复以上步骤逐层堆积至厚度为15-25mm。 Computer porous titanium parts needed for drawing graphics editing program, the titanium powder obtained in step 1 tile on the table, the titanium powder layer having a thickness of 0. 5-lmm will photoresist obtained in Step 2 into a jet chamber, heated spray gun to 150-300 ° C, the heating time is 10-30min, until all the adhesive becomes liquid 6m / s rate of the photoresist according to a desired pattern ejecting droplets, the droplets sufficiently wet titanium After UV irradiation to cure the powder molding 20s, after complete curing of the first layer a layer of titanium powder capped add new titanium powder, and repeat the above steps a bulk layer by layer to a thickness of 15-25mm.

[0032] 步骤4 :真空排胶 [0032] Step 4: vacuum debinding

将步骤3中含胶黏剂的固态制件放置于干燥箱中于100°C干燥12-24h,将干燥后的制件放置于真空炉中以600°C排胶2-4h。 Step 3 solid articles containing adhesive is placed in oven at 100 ° C and dried 12-24h, the parts dried and placed in a vacuum furnace at 600 ° C latex 2-4h.

[0033] 步骤5 :烧结 [0033] Step 5: Sintering

将步骤4中经排胶处理的固态制件进行真空烧结,烧结的温度为1200°C,时间为lh。 Will step through the solid parts of the latex-treated 4 vacuum sintering, the sintering temperature of 1200 ° C, time is lh.

[0034] 。 [0034].

[0035] 实施例1一3的制备方法制备得到的光敏胶性能数据如表1所示。 Photoresist performance data 1 Preparation of a 3 [0035] obtained in Example 1 as shown in Table.

[0036] 表1实施例1一3制备得到的光敏胶性能数据 [0036] Table 1 1 a photoresist performance data obtained in Preparation Example 3

Figure CN102407332AD00081

实施例1一3的制备方法制备得到的多孔钛性能数据如表2所示。 Preparation of porous titanium performance data 1 a obtained in Example 3 shown in Table 2. [0037] 表2实施例1一3制备得到的多孔钛性能数据 [0037] [Table 2] 1 a porous titanium performance data obtained in Preparation Example 3

Figure CN102407332AD00082

采用乌式黏度计和NDJ - 7 9型旋转式粘度计测定光敏胶特定温度下的黏度,采用JK99B型表面张力仪测定光敏胶特定温度下的表面张力,采用液体浸渍法测定材料开孔隙度:先称量干燥试验在空气中的质量M1,再将试样浸润在蒸馏水中至饱和,将饱和试样悬挂在液体静力天平下部的挂钩上,测量饱和试样在蒸馏水中的悬挂重量M2;然后从蒸馏水中取出饱和试样,去除表面水后测量试样在空气中的重量M3。 Ubbelohde viscometer and NDJ - 7 9 type rotary viscometer viscosity photoresist at a specific temperature, using JK99B type surface tension meter measuring the surface tension of the photoresist at a specific temperature, the material was measured by liquid immersion method open porosity: First weigh drying test M1 in air quality, and then soaked in distilled water sample to saturation, saturated specimen hung on hooks hydrostatic balance the lower part of the measurement sample in distilled water saturated suspension weight M2; then removed from the distilled water saturated specimen, after removal of the surface water samples in air measured weight M3. 可得开孔隙度P开孔=(M3-M1) /M3-M2总孔隙度为P总=I-Ml P 1/(M3-M2) P 0其中Pl为水的密度P 0为纯钛的密度;材料力学性能由DDL100电子万能试验机测试;与传统方法相比多孔钛制件的性能主要取决于所选择的光敏胶黏剂,因此可通过制备不同光敏胶黏剂来获得不同性能的多孔钛制件,采用三维打印成形技术使得制备的多孔钛制件形状更为复杂,精度更高,且成形速度极快。 Available open porosity P hole = (M3-M1) / M3-M2 total porosity P total = I-Ml P 1 / (M3-M2) P 0 where Pl is the density of water as pure titanium P 0 density; mechanical properties of materials by the DDL100 electronic universal testing machine; porous titanium parts performance compared with the traditional method chosen depends on the light-sensitive adhesive, and therefore different properties can be obtained by preparing different photosensitive porous adhesive titanium parts, using three dimensional printing technology allows the preparation of porous titanium parts shape is more complex, higher accuracy, and forming fast. 通过采取球磨工艺、紫外光固化、真空排胶和烧结使得多孔钛空隙结构完整、强度明显提高。 By taking milling technology, UV curing, vacuum debinding and sintering so porous titanium void structural integrity, strength improved significantly.

[0038] 以上所述仅为本发明的较佳实施例,并不用以限制本发明,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。 [0038] The foregoing is only preferred embodiments of the present invention is not intended to limit the invention within the spirit and principles of the invention, any changes made, equivalent replacement, or improvement should be included in this within the scope of the invention.

Citas de patentes
Patente citada Fecha de presentación Fecha de publicación Solicitante Título
CN101010161A *16 May 20051 Ago 2007通用汽车公司Aluminum/magnesium 3D-printing rapid prototyping
CN101279106A *21 May 20088 Oct 2008北京科技大学Preparation of gel injection molding of porous titanium-cobalt alloy medical implant article
CN101690828A *29 Sep 20097 Abr 2010西北工业大学Preparation method of gradient porous bioceramic scaffold
CN101927346A *9 Sep 201029 Dic 2010上海交通大学医学院附属第九人民医院Three-dimensional printing technology based method for forming medical porous pure titanium implant
CN102093646A *29 Oct 201015 Jun 2011华南理工大学Material for rapid three dimensional printing forming and preparation method thereof
US5204055 *8 Dic 198920 Abr 1993Massachusetts Institute Of TechnologyThree-dimensional printing techniques
US5387380 *5 Jun 19927 Feb 1995Massachusetts Institute Of TechnologyThree-dimensional printing techniques
Otras citas
Referencia
1 *孙竞博,李勃,等: "基于光敏浆料的直写精细无模三维成型", 《无机材料学报》, vol. 24, no. 6, 30 September 2009 (2009-09-30), pages 1147 - 1150
2 *张南哲,柳乐仙,杜春梅: "LCD用UV固化光敏胶的研制", 《延边大学学报(自然科学版)》, vol. 28, no. 1, 30 March 2002 (2002-03-30), pages 37 - 40
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