CN102407332A - Preparation method of porous titanium - Google Patents
Preparation method of porous titanium Download PDFInfo
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- CN102407332A CN102407332A CN2011103971704A CN201110397170A CN102407332A CN 102407332 A CN102407332 A CN 102407332A CN 2011103971704 A CN2011103971704 A CN 2011103971704A CN 201110397170 A CN201110397170 A CN 201110397170A CN 102407332 A CN102407332 A CN 102407332A
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000010936 titanium Substances 0.000 title claims abstract description 97
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 238000005245 sintering Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 19
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- 230000008569 process Effects 0.000 claims abstract description 9
- 238000001723 curing Methods 0.000 claims abstract description 6
- 239000003292 glue Substances 0.000 claims abstract description 4
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- 230000000996 additive effect Effects 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000009736 wetting Methods 0.000 claims description 9
- 239000003085 diluting agent Substances 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
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- 238000000016 photochemical curing Methods 0.000 claims description 7
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- -1 glycidyl ester Chemical class 0.000 claims description 4
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- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 3
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 claims description 3
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 3
- SUXFTQHLBSWETF-UHFFFAOYSA-N methyl 2,3-dimethylbut-2-enoate Chemical compound COC(=O)C(C)=C(C)C SUXFTQHLBSWETF-UHFFFAOYSA-N 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical group OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
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- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 claims description 2
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a preparation method of porous titanium, which comprises the following steps: step 1: preparing titanium powder; step 2: preparing photosensitive adhesive; and step 3: three-dimensional printing and forming; and 4, step 4: curing; and 5: removing glue; step 6: and sintering. The technical scheme provided by the invention has the beneficial effects that: (1) by adopting a micro-droplet jetting technology, the forming of the workpiece is quick and simple, the working efficiency is high, the cost is low, the raw materials can be recycled, and the workpiece with a complex shape can be prepared by the control of a computer program; (2) by selecting a proper photosensitive adhesive and adopting a proper curing method, the forming precision of the workpiece is greatly improved; (3) the ball milling process is adopted to reduce the granularity of titanium powder, so that the granularity distribution is uniform, the pore size distribution of the prepared porous titanium product is uniform, the strength is improved, and porous titanium products with different porosity sizes can be prepared by controlling the type of photosensitive adhesive and the droplet spraying parameters and formulating different sintering processes.
Description
Technical field
The present invention relates to the POROUS TITANIUM technical field, the preparation method of particularly a kind of POROUS TITANIUM ultraviolet light polymerization and 3 D-printing moulding has realized the high preparation of product precision.
Background technology
Titanium and alloy thereof are that a kind of density is low, good biocompatibility, mechanical compatibility are good, the metal material of superior, have been widely used in medical embedded material.The institutional framework of POROUS TITANIUM has the pore structure that three dimensions connects, and not only can further reduce its elastic modelling quantity, and helps the growth and the body fluid transmission of biological tissue, is a kind of new medical metal material that far-reaching application prospect is arranged.At present; POROUS TITANIUM and alloy thereof have obtained many-sided application clinically, [Fujibayashi S, the Neo M such as titanium heart valve prosthesis that use when POROUS TITANIUM hip joint of using like the human synovial place and porous coating titanium alloy, the POROUS TITANIUM tooth implant of in gum is repaired, using, cardiac valves replacement operation; Kim H M; Et al, Biomaterials, 2004].
POROUS TITANIUM traditional preparation process method has powder metallurgic method, slurry foaming [Garrett R, Abhay P, Dimitrios P A, Biomaterials, 2006].Oh IH employing powder metallurgic methods such as [Oh IH, Nomura N, Masahashi N, et al, Scripta Materialia, 2003] the preparation crack degree that portals is 30% POROUS TITANIUM, and its Young's modulus and bending strength are respectively 12-25GPa and 115MPa.Li Hu [Li Hu, Yu Qifeng, Zhang Bo etc., rare metal and engineering, 2006] uses hydrogen peroxide solution as the slurry blowing agent, obtains porosity and be 58%, Young's modulus is the POROUS TITANIUM of 4.15GPa, compressive strength 190.7MPa.Three-dimensional printing-forming (3DP) technology is also claimed dusty material selectivity bonding; It is a kind of novel RP technique that development in recent years is got up; The 3 D-printing technology is to print and the notion of proposition with respect to two dimensional surface; Patent [sachs E, Cima M, Williams P have been applied in 1991 by people such as the Sachs E.M. of Massachusetts Institute Technology and Cima M.J. the earliest about 3 D-printing; Et al. Three dimensional printing:rapid tooling and prototypes directly from a CAD model. Journal of Engineering for Industry; 1992,114 (4): 481-488.], the three-dimensional printing-forming based on this Patent exploitation is to adopt Hewlett-Packard's thermal shower nozzle to spray adhesives to make the powder bonding forming.The operation principle of 3DP is similar to inkjet printing, is a kind of RP technique based on the drop ejector principle, promptly under the excitation of data signal; Make the liquid in the nozzle operation chamber form drop in moment; And spray from nozzle with certain speed and frequency, jet graphics CAD software is drawn, and successively piles up after adhesive solidifies; Obtain formation of 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.].The 3DP RP technique is the technology that has vitality in the present quick shaping most; This technology need not laser system; Only need select suitable adhesive just can make various dissimilar POROUS TITANIUM products; It has, and equipment is simple to operate, forming speed is fast, forming process is pollution-free, the precision of drip molding high, can be in advantages such as office environment uses.Therefore, 3DP is one of focus of present RP technique research, be particularly suitable for China the market demand [Li Xiaoyan, Wu Yonghui open daybreak. the new development of three-dimensional printing-forming technology. machine-building, 2005,43 (496): 62-64.], it has a extensive future.
In realizing process of the present invention, the inventor finds that there is following problem at least in prior art: the POROUS TITANIUM product surface topography based on the preparation of three-dimensional printing-forming technology is relatively poor, and intensity is lower than other manufacturing process.
Summary of the invention
The invention provides a kind of preparation method of POROUS TITANIUM; This preparation method can use the micron order titanium valve to be raw material; Can obtain the higher shaping product of precision fast through the 3DP technology, through select suitable photosensitive adhesive for use, with combine with the sintering process POROUS TITANIUM product that can obtain different porosities and significantly increase the intensity and the hardness of the POROUS TITANIUM for preparing of photocuring means, reduce its thermal conductivity; And the POROUS TITANIUM article shape precision with the method preparation is high; Even aperture distribution, porosity is adjustable, and is higher through suitable surface treatment product purity.
In order to realize the foregoing invention purpose, technical scheme of the present invention is following:
A kind of preparation method of POROUS TITANIUM, said preparation method may further comprise the steps:
Step 1: prepared sizes are little, the titanium valve of narrow diameter distribution
Rough titanium valve is mixed with absolute ethyl alcohol, add ball-milling additive, in vacuum drying 48h, said rough titanium valve mixes by mass ratio 4:1 with absolute ethyl alcohol behind the vacuum ball milling 24h;
Step 2: preparation light-sensitive emulsion
Under dark surrounds; Photosensitive resin, photo-curing monomer, organic solvent, other active additive are mixed by the certain mass ratio, under 20-60 ℃ of condition, behind mechanical agitation 30-120min, add light trigger; Continue to stir 10-30min, make light-sensitive emulsion;
Said photosensitive resin addition is mass parts 20-100; Said photo-curing monomer addition is mass parts 10-30; The addition of said organic solvent is mass parts 5-30; The addition of said light trigger is mass parts 0.5-3; The addition of said other additive is that quality is divided 0.1-1;
Said organic solvent comprises diluent and solvent;
Diluent is identical from essence with solvent, and diluent is in order to reduce the system viscosity, the filler of improvement system and product property; It can be traditional organic solvent; Also can be other type organic, solvent be meant " organic solvent " commonly used on the traditional concept, and it is equivalent to " dilution " effect of diluent is done enhancing; If the system flowability is still relatively poor after adding diluent, at this moment add some solvents;
Step 3: droplet ejection (being the 3 D-printing moulding)
With the titanium valve that step 1 obtains, be tiled on the workbench, the light-sensitive emulsion that step 2 is obtained is packed in the spray chamber, and the heating spray chamber also sprays liquid light-sensitive emulsion through required jet graphics of computer control and nozzle parameter;
Step 4: solidify
The titanium valve that step 3 is obtained after liquid photosensitive glue is wetting at room temperature carries out UV-irradiation, the light-sensitive emulsion polymerization reaction take place is solidified, thereby titanium valve is played a supportive role;
Step 5: successively pile up
On one deck titanium valve that has solidified, spread one deck titanium valve repeating step 3, the said process of step 4 in addition;
Step 6: vacuum binder removal and sintering
Carrying out drying under the low temperature environment after a period of time, in the high-temperature vacuum binder removal, insulation a period of time continued rising temperature is carried out sintering to sintering temperature, finally makes required POROUS TITANIUM with the product in the step 5.
Among the above-mentioned preparation method; Step 3 is figure, the jet velocity of shower nozzle, the emitted doses of drawing through the computer control shower nozzle; Spray one deck powder is pressed required form then by the nozzle parameter injection adhesive of setting on platform earlier, prepares cylinder and cuboid sample respectively, and droplet ejection is exactly through the heating spray chamber; Liquid photosensitive glue is ejected on the titanium valve layer with the form of droplet; Spread between powder through wetting action, through adjust its jet velocity, emitted dose is adjusted this wetting effect, through changing the formation size that heating-up temperature changes drop.Step 3,4,5 integrates and is the 3 D-printing forming technique; When sample of preparation; Wherein step 3 is that injection light-sensitive emulsion, step 4 are that curing light-sensitive emulsion, step 5 are step to required thickness of sample of repetition 3,4, and 3,4 step conditions are not made any change in the repetitive process.
Further, in the said step 1, said ball-milling additive is a stearic acid, and its addition is a titanium valve quality 1%; Said milling parameters is ratio of grinding media to material 1:5, rotating speed 300r/min, and said titanium valve baking temperature is 60 ℃.The steel ball of using when ratio of grinding media to material refers to ball milling and the mass ratio of titanium valve.
Further, in the said step 2, said photosensitive resin is: epoxy acrylate, propylene oxide acid glycidyl ester, methacrylic acid epoxy resin, bisphenol A epoxide resin; Said photo-curing monomer is N-vinyl pyrrolidone, N, N-dimethyl benzylamine, N, N-dimethylacetylamide; Catalyst is triethanolamine, tertiary amine; Said diluent is ethyl phenylacrylate, hydroxyethyl methacrylate, isobornyl methacrylate, the fervent ester of methacrylic acid tetrahydrochysene, pentaerythrite tetramethyl acrylic acid ester, methacrylic acid hexadecanol ester; Said solvent is toluene, ethylene glycol; Said light trigger is styrax ethers, benzophenone; Said other additive is wetting agent glycerine, thixotropic agent hydroxyethylcellulose, fire retardant hydroquinones, crosslinking agent benzoyl peroxide.
In the said step 3, adopt droplet ejection three-dimensional printing-forming technology, jet graphics is square, circular, and the spray nozzle diameter is 50 μ m, and jet velocity is 6m/s, and standard drop emitted dose is 80pl; Said heating-up temperature is 150-300 ℃.
The light-sensitive emulsion that step 2 is obtained is behind 150-300 ℃ of heating 10-30min; Change liquid into, liquid sprays on the titanium valve layer with the droplet form through shower nozzle, after fully wetting; At room temperature ultraviolet light polymerization 20-100s makes and is bonded to the product with required form between the particle;
Three-dimensional printing-forming: draw required POROUS TITANIUM product figure with computer drawing software, edit routine, the titanium valve that step 1 is obtained is tiled on the workbench; The light-sensitive emulsion that step 2 is obtained adds in the spray chamber; The heating ejecting gun, and with given pace by required pattern light-sensitive emulsion drop, behind the abundant wetting titanium valve of drop with the UV-irradiation solidified forming; Solidify the back fully and add new one deck titanium valve, and repeat above step on ground floor titanium valve upper berth.
In the said step 4, said curing is a ultraviolet light polymerization, and be 20-100s hardening time.
In the said step 5, titanium valve successively ulking thickness is 15-25mm.
In the said step 6, baking temperature is that be 12-24h 100 ℃ of drying times, and the vacuum dump temperature is 600 ℃, and be 2-4h heat time heating time, and sintering temperature is 1200 ℃, and temperature retention time is 1h.
During the vacuum binder removal, solid-state product is positioned in the drying box in 100 ℃ of dry 12-24h, dried product is positioned in the vacuum drying oven with 600 ℃ of binder removal 2-4h.
The beneficial effect that technical scheme provided by the invention is brought is: droplet ejection technology is adopted in (1), and it is simple fast to make that product is shaped, high efficiency, and cost is low, and the product that can make complicated shape is controlled in the recyclable utilization of raw material through computer program; (2) through selecting suitable photosensitive adhesive for use, and take the curing that suits, improved the forming accuracy of product greatly; (3) adopt ball-milling technology; Make that the titanium valve granularity is less, even particle size distribution, the POROUS TITANIUM goods even aperture distribution of preparation; Intensity improves, through control light-sensitive emulsion kind with the droplet ejection parameter and formulate different agglomerant artistic skills and make the big or small POROUS TITANIUM product of different porosities.
Description of drawings
Fig. 1 is a process chart of the present invention.
The specific embodiment
For making the object of the invention, technical scheme and advantage clearer, will combine accompanying drawing that embodiment of the present invention is done to describe in detail further below.
Embodiment 1
A kind of preparation method of POROUS TITANIUM may further comprise the steps:
Step 1: prepared sizes are little, the titanium valve of narrow diameter distribution
Get rough titanium valve of 200g and 50g absolute ethyl alcohol and mix, and add the 2g stearic acid, get the 1000g stainless steel ball, ball milling 24h under vacuum environment, and behind 60 ℃ of vacuum drying 48h, to obtain maximum particle size be 2-48 μ m titanium valve;
Step 2: preparation light-sensitive emulsion
With 50-70 part epoxy acrylate, 20-30 part N-vinyl pyrrolidone, 1-2 part styrax dimethyl ether, 4 parts of tertiary amines, 2 parts of primary amine are in room temperature or be heated to 50 ℃ of mixing and stirring, can make light-sensitive emulsion.
Step 3: three-dimensional printing-forming
With the required POROUS TITANIUM product of computer drawing figure, edit routine, the titanium valve that step 1 is obtained is tiled on the workbench; Obtaining thickness is the titanium valve layer of 0.5-1mm; The light-sensitive emulsion that step 2 is obtained adds in the spray chamber, and the heating ejecting gun is to 150-300 ℃, and be 10-30min heat time heating time; Treat that adhesive all becomes behind the liquid with 6m/s speed by required pattern light-sensitive emulsion drop; Solidify 100s with UV-irradiation behind the abundant wetting titanium valve of drop and be shaped, solidify the back fully and adds new one deck titanium valve, and repeating above step, successively to be accumulated to thickness be 15-25mm on ground floor titanium valve upper berth.
Step 4: vacuum binder removal
The solid-state product that contains adhesive in the step 3 is positioned in the drying box in 100 ℃ of dry 12-24h, dried product is positioned in the vacuum drying oven with 600 ℃ of binder removal 2-4h.
Step 5: sintering
The solid-state product of handling through binder removal in the step 4 is carried out vacuum-sintering, and the temperature of sintering is 1200 ℃, and the time is 1h.
Embodiment 2
A kind of preparation method of POROUS TITANIUM may further comprise the steps:
Step 1: prepared sizes are little, the titanium valve of narrow diameter distribution
Get rough titanium valve of 200g and 50g absolute ethyl alcohol and mix, and add the 2g stearic acid, get the 1000g stainless steel ball, ball milling 24h under vacuum environment, and behind 60 ℃ of vacuum drying 48h, to obtain maximum particle size be 2-48 μ m titanium valve;
Step 2: preparation light-sensitive emulsion
Add 10-15 part ethyl phenylacrylate, 5-10 part hydroxyethyl methacrylate successively after 30-50 part methacrylic acid epoxy resin is heated to 40-50 ℃; 10-20 part N; The N-dimethyl benzylamine; 1-2 part styrax dimethyl ether, 1-3 part benzoyl peroxide mixing and stirring can make light-sensitive emulsion.
Step 3: three-dimensional printing-forming
With the required POROUS TITANIUM product of computer drawing figure, edit routine, the titanium valve that step 1 is obtained is tiled on the workbench; Obtaining thickness is the titanium valve layer of 0.5-1mm; The light-sensitive emulsion that step 2 is obtained adds in the spray chamber, and the heating ejecting gun is to 150-300 ℃, and be 10-30min heat time heating time; Treat that adhesive all becomes behind the liquid with 6m/s speed by required pattern light-sensitive emulsion drop; Solidify 60s with UV-irradiation behind the abundant wetting titanium valve of drop and be shaped, solidify the back fully and adds new one deck titanium valve, and repeating above step, successively to be accumulated to thickness be 15-25mm on ground floor titanium valve upper berth.
Step 4: vacuum binder removal
The solid-state product that contains adhesive in the step 3 is positioned in the drying box in 100 ℃ of dry 12-24h, dried product is positioned in the vacuum drying oven with 600 ℃ of binder removal 2-4h.
Step 5: sintering
The solid-state product of handling through binder removal in the step 4 is carried out vacuum-sintering, and the temperature of sintering is 1200 ℃, and the time is 1h.
Embodiment 3
A kind of preparation method of POROUS TITANIUM may further comprise the steps:
Step 1: prepared sizes are little, the titanium valve of narrow diameter distribution
Get rough titanium valve of 200g and 50g absolute ethyl alcohol and mix, and add the 2g stearic acid, get the 1000g stainless steel ball, ball milling 24h under vacuum environment, and behind 60 ℃ of vacuum drying 48h, to obtain maximum particle size be 2-48 μ m titanium valve;
Step 2: preparation light-sensitive emulsion
70-100 part polyurethane-base acrylic acid epoxy resin, 10-30 bisphenol A epoxide resin, 10-15 part ethyl phenylacrylate, 5-20 part isobornyl methacrylate, the fervent ester of 5-20 part methacrylic acid tetrahydrochysene, 5-10 part pentaerythrite tetramethyl acrylic acid ester, 1-2 part styrax dimethyl ether, 1-2 part benzophenone, 0.5-1 part glycerine, 0.5-2 part hydroxyethylcellulose, 0.1-0.3 part hydroquinones, 0.5-2 part benzoyl peroxide are mixed in batch mixer, can make light-sensitive emulsion.
Step 3: three-dimensional printing-forming
With the required POROUS TITANIUM product of computer drawing figure, edit routine, the titanium valve that step 1 is obtained is tiled on the workbench; Obtaining thickness is the titanium valve layer of 0.5-1mm; The light-sensitive emulsion that step 2 is obtained adds in the spray chamber, and the heating ejecting gun is to 150-300 ℃, and be 10-30min heat time heating time; Treat that adhesive all becomes behind the liquid with 6m/s speed by required pattern light-sensitive emulsion drop; Solidify 20s with UV-irradiation behind the abundant wetting titanium valve of drop and be shaped, solidify the back fully and adds new one deck titanium valve, and repeating above step, successively to be accumulated to thickness be 15-25mm on ground floor titanium valve upper berth.
Step 4: vacuum binder removal
The solid-state product that contains adhesive in the step 3 is positioned in the drying box in 100 ℃ of dry 12-24h, dried product is positioned in the vacuum drying oven with 600 ℃ of binder removal 2-4h.
Step 5: sintering
The solid-state product of handling through binder removal in the step 4 is carried out vacuum-sintering, and the temperature of sintering is 1200 ℃, and the time is 1h.
。
The light-sensitive emulsion performance data that the preparation method of embodiment 1-3 prepares is as shown in table 1.
The light-sensitive emulsion performance data that table 1 embodiment 1-3 prepares
| Specific embodiment | Viscosity (cPs) | Surface tension (mN/m) | Hardening time (s) |
| Embodiment 1 | 48-69 | 36-51 | 60-80 |
| Embodiment 2 | 16-24 | 27-40 | 50-90 |
| Embodiment 3 | 3-9 | 19-32 | 10-35 |
The POROUS TITANIUM performance data that the preparation method of embodiment 1-3 prepares is as shown in table 2.
The POROUS TITANIUM performance data that table 2 embodiment 1-3 prepares
| Specific embodiment | Relative density g/cm 3 | Open porosity | Compressive strength (MPa) |
| Embodiment 1 | 2.54 | 24% | 140-170 |
| Embodiment 2 | 2.36 | 31% | 160-190 |
| Embodiment 3 | 2.08 | 33% | 170-200 |
Adopt black formula viscosimeter and N D J-7 9 type rotary viscosimeter to measure the viscosity under the light-sensitive emulsion specified temp; Adopt JK99B type surface tension instrument to measure the surface tension under the light-sensitive emulsion specified temp; Adopt liquid immersion method to measure material and open porosity: the aerial mass M 1 of first weighing drying test; Again that the sample infiltration is extremely saturated in distilled water, saturated sample is suspended on the hook of hydrostatic balance bottom, measure the suspended weights M2 of saturated sample in distilled water; From distilled water, take out saturated sample then, measure the aerial weight M3 of sample behind the removal surface water.Can open porosity P perforate=(M3-M1)/M3-M2 total porosity and be P total=1-M1 ρ 1/ (M3-M2) ρ 0 wherein ρ 1 be the density of pure titanium for the density p 0 of water; Material mechanical performance is tested by the DDL100 electronic universal tester; The performance of comparing the POROUS TITANIUM product with conventional method depends primarily on selected photosensitive adhesive; Therefore can be through preparing the POROUS TITANIUM product that different photosensitive adhesives obtain different performance; Adopt the three-dimensional printing-forming technology to make that the POROUS TITANIUM product shape of preparation is more complicated; Precision is higher, and forming speed is exceedingly fast.Through taking ball-milling technology, ultraviolet light polymerization, vacuum binder removal and sintering to make that the POROUS TITANIUM gap structure is complete, intensity obviously improves.
The above is merely preferred embodiment of the present invention, and is in order to restriction the present invention, not all within spirit of the present invention and principle, any modification of being done, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. the preparation method of a POROUS TITANIUM is characterized in that, said preparation method may further comprise the steps:
Step 1: the titanium valve that prepared sizes are suitable
Rough titanium valve is mixed with absolute ethyl alcohol, add ball-milling additive, in vacuum drying 48h, said rough titanium valve mixes by mass ratio 4:1 with absolute ethyl alcohol behind the vacuum ball milling 24h;
Step 2: preparation light-sensitive emulsion
Photosensitive resin, photo-curing monomer, organic solvent, light trigger and other active additive are mixed according to a certain ratio, make light-sensitive emulsion after stirring and preservation under the room temperature dark surrounds;
Said photosensitive resin addition is mass parts 20-100; Said photo-curing monomer addition is mass parts 10-30; The addition of said organic solvent is mass parts 5-30; The addition of said light trigger is mass parts 0.5-3; The addition of said other additive is that quality is divided 0.1-1;
Step 3: droplet ejection
With the titanium valve that step 1 obtains, be tiled on the workbench, the light-sensitive emulsion that step 2 is obtained is packed in the spray chamber, and the heating spray chamber also sprays liquid light-sensitive emulsion through required jet graphics of computer control and nozzle parameter;
Step 4: solidify
The titanium valve that step 3 is obtained after liquid photosensitive glue is wetting at room temperature carries out UV-irradiation, the light-sensitive emulsion polymerization reaction take place is solidified, thereby titanium valve is played a supportive role;
Step 5: successively pile up
On one deck titanium valve that has solidified, spread one deck titanium valve repeating step 3, the said process of step 4 in addition;
Step 6: vacuum binder removal and sintering
Carrying out drying under the low temperature environment after a period of time, in the high-temperature vacuum binder removal, insulation a period of time continued rising temperature is carried out sintering to sintering temperature, finally makes required POROUS TITANIUM with the product in the step 5.
2. preparation method according to claim 1 is characterized in that, in the said step 1, said ball-milling additive is a stearic acid, and its addition is a titanium valve quality 1%; Said milling parameters is ratio of grinding media to material 1:5, rotating speed 300r/min, and said titanium valve baking temperature is 60 ℃.
3. preparation method according to claim 1 is characterized in that, in the said step 2, said photosensitive resin is: epoxy acrylate, propylene oxide acid glycidyl ester, methacrylic acid epoxy resin, bisphenol A epoxide resin; Said photo-curing monomer is N-vinyl pyrrolidone, N, N-dimethyl benzylamine, N, N-dimethylacetylamide; Catalyst is triethanolamine, tertiary amine; Said organic solvent comprises diluent and solvent, and said diluent is ethyl phenylacrylate, hydroxyethyl methacrylate, isobornyl methacrylate, the fervent ester of methacrylic acid tetrahydrochysene, pentaerythrite tetramethyl acrylic acid ester, methacrylic acid hexadecanol ester; Said solvent is toluene, ethylene glycol; Said light trigger is styrax ethers, benzophenone; Said other additive is wetting agent glycerine, thixotropic agent hydroxyethylcellulose, fire retardant hydroquinones, crosslinking agent benzoyl peroxide.
4. preparation method according to claim 1 is characterized in that, in the said step 3; Adopt droplet ejection three-dimensional printing-forming technology, jet graphics is square, circular, and the spray nozzle diameter is 50 μ m; Jet velocity is 6m/s, and standard drop emitted dose is 80pl; Said heating-up temperature is 150-300 ℃.
?
5. preparation method according to claim 1 is characterized in that, in the said step 4, said curing is a ultraviolet light polymerization, and be 20-100s hardening time.
6. preparation method according to claim 1 is characterized in that, in the said step 5, titanium valve successively ulking thickness is 15-25mm.
7. preparation method according to claim 1 is characterized in that, in the said step 6, baking temperature is that be 12-24h 100 ℃ of drying times, and the vacuum dump temperature is 600 ℃, and be 2-4h heat time heating time, and sintering temperature is 1200 ℃, and temperature retention time is 1h.
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