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Preparation method for porous titanium

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Publication number
CN102407332A
CN102407332A CN 201110397170 CN201110397170A CN102407332A CN 102407332 A CN102407332 A CN 102407332A CN 201110397170 CN201110397170 CN 201110397170 CN 201110397170 A CN201110397170 A CN 201110397170A CN 102407332 A CN102407332 A CN 102407332A
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titanium
porous
photosensitive
method
glue
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CN 201110397170
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Chinese (zh)
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刘会群
易丹青
王杰恩
胡海波
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烟台工程职业技术学院
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Abstract

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.

Description

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

技术领域 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 porous titanium technology, and particularly relates to a porous titanium UV curing and molding method for preparing a three-dimensional printing, to achieve a high precision of the product prepared.

[0002] [0002]

背景技术 Background technique

[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] Titanium and its alloys is a low density, good biocompatibility, good mechanical compatibility, excellent mechanical properties of metallic materials, have been widely used in medical implant materials. 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。 Structure of porous titanium having a porous 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, there is a profound 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 obtained in clinical applications in many aspects, such as porous titanium hip joint body and a porous coating layer applied titanium, porous titanium dental implant applied in gums repair, heart valve replacement surgery titanium application of 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] Traditional production of porous titanium powder metallurgy method, a slurry foaming method 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] were prepared by powder metallurgy like a porosity of 30% 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。 Hu Li [Li Hu, Yu Qifeng, Bo et al., Metals and Engineering, 2006] using hydrogen peroxide slurry as a blowing agent, to give a porosity of 58%, a Young's modulus of 4. 15GPa, the 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 the powder material, in recent years developed a new rapid prototyping technique, three-dimensional printing technology is a two-dimensional plane with respect to the concept proposed printing, first proposed by Massachusetts Tech Mchs EM and Cima MJ et al filed a patent application on the three-dimensional 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 the development of this patent is the use of the three dimensional printing HP thermal bubble ejecting the adhesive material 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 similar to ink-jet printing, rapid prototyping technology is based on the principle of liquid droplet ejection, i.e. the excitation signal is digital, the liquid droplets in the working chamber of the nozzle is formed in an instant, and at a rate and frequency from the nozzle, the spray pattern drawing CAD software, after curing the adhesive layer by layer stacking, to obtain molded parts Shu J [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 can only select a suitable adhesive made of different types of porous titanium parts, having a simple apparatus, molding speed, forming no pollution, high-precision shaped member, the advantages can be used in an office environment and the like. 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 currently one of the hot technology of rapid prototyping, especially suited to China's market demand [Li Xiaoyan, Wu Yonghui, Zhang Shu new technological advances Three Dimensional Printing Machinery, 2005, 43 (496): 62-64. ], its 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] During the implementation of the present invention, the inventors found that the prior art at least has the following problems: poor surface morphology on porous titanium article prepared by Three Dimensional Printing techniques, and the strength is low compared with other molding methods. 发明内容 SUMMARY

[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 method can be prepared using micron-sized titanium powder as a raw material, can quickly obtain a high precision formed article by 3DP technique, by appropriate choice of the photosensitive adhesive, the the photocurable means and a sintering process of combining the porous titanium parts is possible to obtain different porosities and significantly increase the strength and hardness of the porous titanium is prepared, reducing its thermal conductivity and a high porous titanium article shape accuracy prepared by this method, pore size distribution, porosity is adjustable by a suitable surface treatment product high purity.

[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] In order to achieve the above object, the technical solution of the present invention is as follows: A method for preparing porous titanium, the preparation method comprises the following steps: Step 1: Preparation of small particle size, 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 mixed with ethanol, added to aid milling, ball milling vacuo 24h 48h after drying in vacuo, the crude titanium powder and ethanol in a mass ratio 4: 1 mixture; Step 2: Preparation of photosensitive adhesive

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 photosensitive resin, photocurable monomer, organic solvent, at a certain mass of other reactive additives were mixed to homogeneity, at 20-60 ° C under conditions of light after 30-120min initiator is added by mechanical stirring, and stirring was continued 10-30min, to obtain photosensitive adhesive;

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 photosensitive resin additive amount of 20-100 parts by mass; the mass of the photocurable monomer added in an amount 10-30; parts by mass of the organic solvent is added in an amount of 5-30; addition amount of the photoinitiator 0. 5-3 parts by mass; the additional mass of the additive added in an amount of 0. 1-1 minutes;

所述有机溶剂包括稀释剂和溶剂; The organic solvent comprises a diluent and a solvent;

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 that essentially the same, a diluent to reduce system viscosity, improve system performance and product filler may be a conventional organic solvent may be an organic compounds other solvent commonly refers to the traditional concept of " organic solvent ", which corresponds to the diluent" diluting "effect do enhanced, if the system is still inferior in fluidity after 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 (i.e., 3D Printer)

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 was charged in the injection chamber, the injection chamber and heated by a computer controlling the injection parameters and the desired spray pattern spraying liquid photosensitive adhesive; 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 was obtained after the liquid photosensitive adhesive wetting Titanium powder is irradiated with ultraviolet light at room temperature to cure the photoresist polymerization reaction, thereby play a supportive role titanium powder; Step 5: stacking in layers

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 Another plated on solidified layer of titanium powder, a titanium powder Repeat step 3, the 4-step process; Step 6: debinding and sintering in vacuo

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 the drying step for a period of 5 parts in a low-temperature environment, a high temperature vacuum debinding, temperature continues to rise after the incubation period to the sintering temperature for 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 above preparation method, the step 3 is controlled by a computer graphic rendering of the nozzle, the nozzle ejection speed, injection quantity, to spray a layer of powder on the platform and press the desired shape by injection parameter setting adhesive injection , posts and rectangular samples were prepared by heating the droplet injection chamber is injected, the liquid photosensitive adhesive sprayed in the form of droplets onto the layer of titanium powder, the diffusion between the powder by wetting action, by adjusting the injection rate, injection this adjusts the amount of wetting, to change the size of the droplets formed by changing the heating temperature. 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。 3,4,5 step together as 3D printing, when preparing a sample, wherein step 3 is ejecting the photoresist, the photoresist curing step 4, step 5 is a step of repeating 3,4 to a desired sample thickness repeat steps 3 and 4 during the condition 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, in the step 1, the milling aid is stearic acid, which is added in an amount of 1% by mass titanium powder; milling parameters as the Charge Ratio 1: 5, the rotational speed of 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。 It refers to a ratio of ball to powder mass ratio when used in 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 resin, bisphenol A epoxy resin; the photocurable monomer is N- vinyl pyrrolidone, N, N- dimethylbenzylamine, N, N- dimethylacetamide; catalyst is triethanolamine, tertiary amines; the diluent is phenyl acrylate, hydroxyethyl methacrylate, methacrylate, isobornyl methacrylate, tetrahydro Kang, pentaerythritol tetra methacrylate, methacrylate, cetyl esters; the solvent is toluene, ethylene glycol; the photoinitiator is benzoin ethers, benzophenone; other additives the wetting agent is glycerin, hydroxyethylcellulose thixotropic agents, 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 step 3, a droplet ejection Three Dimensional Printing technique, the spray pattern is square, circular, a nozzle diameter of the nozzle 50 μ m, the ejection 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 [0012] The photosensitive adhesive obtained in Step 2 was heated 10-30min at 150-300 ° C, into a liquid, through a liquid ejection head in the form of droplets on the layer of titanium powder, after sufficiently wetted, UV at room temperature the photocurable 20-100S, the bonded article into between the particles having a desired shape;

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: porous titanium parts using computer graphics software needed for drawing graphics, the editing program, step 1 was plated titanium powder on the table, the photosensitive adhesive obtained in Step 2 into the jet chamber, heated spray gun, and at a rate desired by the photoresist pattern ejecting droplets, the droplets titanium powder sufficiently wetted to ultraviolet light curable molding, a first layer of fully cured plated titanium powder add a new layer of titanium powder, and repeating the above 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。 In [0013] step 4, the curing method is UV-curing, curing time 20-100S.

[0014] 所述步骤5中,钛粉逐层堆积厚度为15_25mm。 In [0014] step 5, the titanium powder layer by layer deposition thickness of 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。 In [0015] step 6, the drying temperature is 100 ° C drying time 12_24h, vacuum dump 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] debinding vacuum, the solid article is placed in oven at 100 ° C drying 1214h, the dried article is placed in a vacuum oven at 600 ° C debinding 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 present invention provides a technical solution is beneficial effects: (1) a droplet ejection technologies, such molded parts quick and simple, high efficiency, low cost, recyclable material, may be prepared by a process control computer have a complex shape parts; (2) by appropriate choice of the photosensitive adhesive, and take appropriate curing method greatly improves the precision of molding parts; and (3) ball milling process, such that the titanium powder particle size smaller , particle size distribution, pore size of porous titanium articles made uniform distribution, strength is improved by controlling the kind and the photoresist parameters and the development of droplet ejection sintering processes can be made of porous titanium parts of different sizes porosity.

[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 process flow diagram 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] To make the objectives, technical solutions, and advantages of the present invention will become apparent in conjunction with the accompanying drawings of the following embodiments of the present invention will be described in further 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 Preparation method of porous titanium, comprising the following steps: Step 1: Preparation of small particle size, 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 of crude 50g titanium powder and mixed ethanol and 2g of stearic acid were added, taking IOOOg stainless steel ball, ball Mh under vacuum, and dried in vacuo at 60 ° C after 4¾ maximum particle size of 2-48 μ m titanium powder; step 2: preparation of photosensitive adhesive

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。 50-70 parts of the epoxy acrylate, 20-30 parts of N- vinyl pyrrolidone, 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, you can be prepared photosensitive adhesive.

[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。 Draw the desired pattern of porous titanium parts with a computer, the editing program, step 1 was plated titanium powder on the table, a thickness of 0. 5-lmm titanium powder layer, the photosensitive adhesive obtained in Step 2 into a jet chamber, the spray gun is heated to 150-300 ° C, the heating time is 10-30min, at / s rate 6m ejecting the photoresist pattern desired droplet until all the adhesive becomes liquid droplets sufficiently wet titanium after UV irradiation to cure IOOs powder molding, a first layer of fully cured plated titanium powder add a new layer of titanium powder, and repeat the above steps in layers deposited 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 The solid-containing adhesive article is placed in oven at 100 ° C drying 12-24h, the dried article is placed in a vacuum oven at 600 ° C debinding 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。 The solid article in the step of debinding treatment was carried out 4 vacuum sintering, the sintering temperature of 1200 ° C, time 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 Preparation method of porous titanium, comprising the following steps: Step 1: Preparation of small particle size, 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 of crude 50g titanium powder and mixed ethanol and 2g of stearic acid were added, taking IOOOg stainless steel ball, ball Mh under vacuum, and dried in vacuo at 60 ° C after 4¾ maximum particle size of 2-48 μ m titanium powder; step 2: preparation of photosensitive adhesive

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。 After successively added epoxy resin 30 to 50 parts of methacrylic acid was heated to 40-50 ° C 10-15 parts phenyl ethyl acrylate, hydroxyethyl methacrylate 5-10 parts, 10-20 parts of N, N - dimethylbenzylamine, 1-2 parts of benzoin dimethyl ether, 1-3 parts of benzoyl peroxide mixing evenly, can be prepared photosensitive adhesive.

[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。 Draw the desired pattern of porous titanium parts with a computer, the editing program, step 1 was plated titanium powder on the table, a thickness of 0. 5-lmm titanium powder layer, the photosensitive adhesive obtained in Step 2 into a jet chamber, the spray gun is heated to 150-300 ° C, the heating time is 10-30min, at / s rate 6m ejecting the photoresist pattern desired droplet until all the adhesive becomes liquid droplets sufficiently wet titanium after UV irradiation to cure 60s powder molding, a first layer of fully cured plated titanium powder add a new layer of titanium powder, and repeat the above steps in layers deposited 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 The solid-containing adhesive article is placed in oven at 100 ° C drying 12-24h, the dried article is placed in a vacuum oven at 600 ° C debinding 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。 The solid article in the step of debinding treatment was carried out 4 vacuum sintering, the sintering temperature of 1200 ° C, time 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 Preparation method of porous titanium, comprising the following steps: Step 1: Preparation of small particle size, 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 of crude 50g titanium powder and mixed ethanol and 2g of stearic acid were added, taking IOOOg stainless steel ball, ball Mh under vacuum, and dried in vacuo at 60 ° C after 4¾ maximum particle size of 2-48 μ m titanium powder; step 2: preparation of photosensitive adhesive

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 a urethane acrylate, an epoxy group, a 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, dimethyl ether, benzoin parts 1-2, 1-2 parts of benzophenone, 0. 5-1 parts of glycerin, 0. 5-2 parts hydroxyethyl cellulose, 0. 1-0. 3 parts of hydroquinone, 0. 5-2 parts by benzoyl peroxide were mixed uniformly in the blender, to prepare photosensitive adhesive.

[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。 Draw the desired pattern of porous titanium parts with a computer, the editing program, step 1 was plated titanium powder on the table, a thickness of 0. 5-lmm titanium powder layer, the photosensitive adhesive obtained in Step 2 into a jet chamber, the spray gun is heated to 150-300 ° C, the heating time is 10-30min, at / s rate 6m ejecting the photoresist pattern desired droplet until all the adhesive becomes liquid droplets sufficiently wet titanium after UV irradiation to cure 20s powder molding, a first layer of fully cured plated titanium powder add a new layer of titanium powder, and repeat the above steps in layers deposited 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 The solid-containing adhesive article is placed in oven at 100 ° C drying 12-24h, the dried article is placed in a vacuum oven at 600 ° C debinding 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。 The solid article in the step of debinding treatment was carried out 4 vacuum sintering, the sintering temperature of 1200 ° C, time 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。 Preparation Method [0035] 3 of Example 1 to give a photosensitive adhesive performance data are shown in Table 1.

[0036] 表1实施例1一3制备得到的光敏胶性能数据 [0036] Table 1 photosensitive adhesive performance data obtained in Example 1 a prepared embodiment 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。 1 a Preparation Example 3 Preparation of porous titanium obtained performance data 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 Example 1 Porous titanium performance data obtained in a prepared 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 in the photoresist certain temperature, measuring the surface tension of the photoresist particular temperature employed JK99B type surface tension meter, determined by measuring the liquid immersion method opening Porosity: first weighing the test mass M1 dried in air, and then the sample in distilled water to saturation infiltration, the saturated sample is suspended on the hook the lower portion of the hydrostatic balance, saturation measurement M2 by weight of the sample is suspended in distilled water; saturated sample is then removed from the distilled water, measured sample weight M3 in the air after removal of the surface water. 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 opening open porosity P = (M3-M1) / M3-M2 is the total porosity P total = I-Ml P 1 / (M3-M2) P 0 where P Pl 0 is the density of water is pure titanium density; DDL100 mechanical properties of electronic universal testing machine; photosensitive adhesive selected depending on the properties of the porous titanium parts as compared with the conventional method, thus different properties can be obtained by preparing a porous different photosensitive adhesive titanium parts, three-dimensional printing technique such shaped articles of porous titanium made more complex shape, more accurate, fast and shaped. 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 ball milling process, UV curing, vacuum debinding and sintering such porous titanium void structural integrity, strength is significantly improved.

[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, not intended to limit the present invention within the spirit and principle of the present invention, any modification, equivalent replacement, or improvement, it should be included in the present within the scope of the invention.

Claims (7)

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 A method for producing a porous titanium, wherein said preparation method comprises the following steps: Step 1: Preparation of titanium powder particle size Suitable crude titanium powder mixed with ethanol, added to aid milling, ball milling 24h vacuo after drying in vacuo 48h, the crude titanium powder and ethanol in a mass ratio 4: 1 mixture; step 2: preparation of the photoresist photosensitive resin, photocurable monomer, organic solvent, photoinitiators and other additives were active compound by mixing uniformly and thoroughly stirred to obtain photosensitive adhesive evenly and stored at room temperature, the dark; addition amount of the photosensitive resin is 20-100 parts by mass; the addition amount of the photocurable monomer 10-30 parts by mass; the parts by mass of the organic solvent is added in an amount of 5-30; the addition amount of photoinitiator parts by mass of 0. 5-3; the additional mass of the additive added in an amount of 0. 1-1 points; step 3: the droplet ejection titanium powder obtained in step 1, the tile on the table, the photosensitive adhesive obtained in step 2 was charged in the injection chamber, the injection chamber and heated by a computer controlling the injection parameters and the desired spray pattern spraying liquid photosensitive adhesive; step 4: curing step 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。 Step 3 was titanium powder obtained after the liquid photosensitive adhesive wetting UV irradiation at room temperature, so that the photoresist curing polymerization reaction, thereby play a supportive role titanium powder; Step 5: layer by layer deposited on the solidified layer of titanium further laying a layer of titanium powder on the powder repeat step 3, the 4-step process; step 6: after vacuum debinding step and sintering the dried article 5 a period of time at low temperatures, high temperature vacuum debinding, insulation temperature continues to rise to a sintering temperature for a period of time after firing, 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, in the step 1, the milling aid is stearic acid, which is added in an amount of 1% by mass titanium powder; the ball milling process parameters material ratio of 1: 5, the rotational speed of 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。 The production method according to claim 1, wherein, in the step 2, the photosensitive resin is: epoxy acrylate, epoxy acrylate, glycidyl methacrylate, epoxy resin, bisphenol A an epoxy resin; a photocurable monomer is N- vinyl pyrrolidone, N, N- dimethylbenzylamine, N, N- dimethylacetamide; triethanol amine catalyst is a tertiary amine; the organic solvent comprises diluents and solvents, the diluent is phenyl acrylate, hydroxyethyl methacrylate, isobornyl methacrylate, tetrahydro Kang, pentaerythritol tetra methacrylate, methyl acrylate, hexadecyl ester; the solvent is toluene, ethylene glycol; the photoinitiator is benzoin ethers, benzophenone; other additives the wetting agent is glycerin, hydroxyethylcellulose thixotropic agents, hindered hydroquinone flame retardant, a crosslinking agent benzoyl peroxide.
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, a droplet ejection Three Dimensional Printing technique, the spray pattern is square, circular, a nozzle diameter of the nozzle 50 μ m, the ejection velocity 6m / s, the standard droplet ejection amount of 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。 The production method according to claim 1, wherein, in the step 4, the curing method is UV-curing, 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, wherein said step 5, the titanium powder layer by layer deposition thickness of 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 The production method according to claim 1, wherein, in the step 6, the drying temperature is 100 ° C the drying time is 12-Mh, vacuum debinding temperature is 600 ° C, the heating time is 2-4h the sintering temperature is 1200 ° C, holding time Ih0
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CN103801697A (en) * 2014-02-11 2014-05-21 北京科技大学 Method for forming mould-free gel with metal sizing agents through 3D printing
CN104149337A (en) * 2014-07-02 2014-11-19 中国电子科技集团公司第五十五研究所 Photocuring material for three-dimensional printing and application method thereof
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CN104353835A (en) * 2014-11-15 2015-02-18 安徽省新方尊铸造科技有限公司 Part manufacturing method combining 3D (three-dimensional) printing with powder metallurgy
CN105397091A (en) * 2015-10-30 2016-03-16 苏州大学张家港工业技术研究院 Preparation method for porous graphene reinforced titanium matrix nanometer composite material based on laser sintering technology
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