CN105671364A - Preparation method of porous titanium copper calcium material - Google Patents
Preparation method of porous titanium copper calcium material Download PDFInfo
- Publication number
- CN105671364A CN105671364A CN201610185484.0A CN201610185484A CN105671364A CN 105671364 A CN105671364 A CN 105671364A CN 201610185484 A CN201610185484 A CN 201610185484A CN 105671364 A CN105671364 A CN 105671364A
- Authority
- CN
- China
- Prior art keywords
- powder
- porous titanium
- preparation
- titanium copper
- alloying
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- KPWQKEUUJCLATM-UHFFFAOYSA-N [Ca].[Cu].[Ti] Chemical compound [Ca].[Cu].[Ti] KPWQKEUUJCLATM-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 239000000463 material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000843 powder Substances 0.000 claims abstract description 50
- 239000011575 calcium Substances 0.000 claims abstract description 31
- 239000010936 titanium Substances 0.000 claims abstract description 23
- 238000005275 alloying Methods 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 14
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 13
- 239000010949 copper Substances 0.000 claims abstract description 13
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 239000012567 medical material Substances 0.000 claims abstract description 10
- 238000005551 mechanical alloying Methods 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 238000000498 ball milling Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 239000012620 biological material Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000011812 mixed powder Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 239000010935 stainless steel Substances 0.000 claims description 5
- 229910001220 stainless steel Inorganic materials 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 2
- 210000000988 bone and bone Anatomy 0.000 abstract description 17
- 239000011148 porous material Substances 0.000 abstract description 12
- 230000004071 biological effect Effects 0.000 abstract description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 abstract description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 abstract description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 abstract description 2
- 239000001099 ammonium carbonate Substances 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 239000007943 implant Substances 0.000 description 18
- 229910000882 Ca alloy Inorganic materials 0.000 description 13
- 230000003115 biocidal effect Effects 0.000 description 8
- 210000001519 tissue Anatomy 0.000 description 5
- 239000000956 alloy Substances 0.000 description 4
- 230000001580 bacterial effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 208000015181 infectious disease Diseases 0.000 description 4
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920001817 Agar Polymers 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- 208000022362 bacterial infectious disease Diseases 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000010261 cell growth Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000012010 growth Effects 0.000 description 2
- 238000002513 implantation Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000002054 transplantation Methods 0.000 description 2
- 241000283973 Oryctolagus cuniculus Species 0.000 description 1
- 230000004520 agglutination Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 239000002763 biomedical alloy Substances 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 230000008468 bone growth Effects 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 230000003280 chronobiological effect Effects 0.000 description 1
- 238000003501 co-culture Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- IUYOGGFTLHZHEG-UHFFFAOYSA-N copper titanium Chemical compound [Ti].[Cu] IUYOGGFTLHZHEG-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 210000003716 mesoderm Anatomy 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 210000000963 osteoblast Anatomy 0.000 description 1
- 230000001582 osteoblastic effect Effects 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 230000001225 therapeutic effect Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/11—Making porous workpieces or articles
- B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
- B22F3/1125—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers involving a foaming process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses a preparation method of a porous titanium calcium copper medical material, and belongs to the technical field of preparation of biomedical materials. A biological material consists of titanium, copper and calcium biological active elements; Ti, Cu and Ca metal powder is weighed by the component ratios for ball milling mechanical alloying; the alloying powder and an ammonium bicarbonate pore forming agent are weighed by the porosity ratio and mixed; the powder is mechanically pressed as a block pressed blank after mixing; the block pressed blank is put in a discharge plasma sintering furnace; after the system vacuum is extracted to 2-6 Pa, the sintering is performed; the heating speed is 50-100 min/DEG C; the temperature is kept by 5-10 min at 800-1000 DEG C; and the porous titanium copper calcium medium material can be obtained after cooling to room temperature along with a furnace. The prepared biomedical porous titanium copper calcium has such advantages as pure components, high biological activity, low elastic modulus and controllable pore parameter (porosity and pore size), and can serve as an excellent artificial bone tissue replacement material.
Description
Technical field
The preparation method that the present invention relates to a kind of porous titanium copper calcium material, belongs to technical field of biological medical material preparation.
Background technology
Ti and alloy thereof are considered as the preferred material of the hard tissue substitutings such as artificial joint, backbone correcting internal fixation system, tooth implant and reparation, and wherein, the application of Ti is relatively broad. But the elastic modelling quantity of Ti (about 110GPa) is apparently higher than human bone elastic modelling quantity (1-30GPa), it is easily caused between transplant and host bone and causes " stress shielding " phenomenon because load transmission is inharmonious, occurring around implant that bone stress absorbs thus causing, ultimately resulting in loosening and fracture of implant; The biological activity of Ti is poor, it is impossible to form effective chemical bonding with bone tissue, thus the clinical practice of Ti can be limited. Additionally, in actual operation process, the bacterial infection of operation technique or implant itself is unavoidable, this will cause that implant longer a period of time in implantation organism is required for being infected by anti-inflammatory medicaments assist control, because individual variation is different, this infection is likely to result in adapting to increased periods or affecting the service life of implant between implant and bone tissue.
Patent CN201110232840.7, CN201110232842.6 and CN201110232843.0 add appropriate Cu element in medical titanium alloy, the matrix of medical titanium alloy precipitates out a kind of titanium copper phase, thus giving medical titanium alloy bacterial-infection resisting function, can be widely applied to all kinds of titanium medical apparatus and instruments used in the clinical medicine such as orthopaedics, department of stomatology field, to solve existing clinic is implanted the problems such as the antibacterial infection that causes by medical pure titanium medical apparatus and instruments. Above-mentioned patent has only related to antibiotic property, and material does not still have biological activity.
Calcium is a kind of biological active elements, and simple substance calcium Ca fusing point low (850 DEG C) and oxidizable, easily react with oxygen, and the introducing of oxygen will significantly reduce mechanical property (YuQ, LiangQ, the TsuruT of Ti, etal.Metallurgy.Originofdramaticoxygensolutestrengthenin geffectintitanium.Science, 2015,347 (6222): 635-639.) service life and the therapeutic effect of Ti transplant, are affected;The current research form adopting the compound such as calcium phosphate or apatite improves the biological activity of Ti more, but still cannot be avoided the introducing of oxygen.
Based on this, the present invention in conjunction with discharge plasma sintering technique, prepares the biomaterial of a kind of low elastic modulus, high intensity, superior bio activity and good antibiotic property by the mechanical alloying ball grinding method of the free of contamination pore creating material of employing and powder.
Summary of the invention
The present invention is directed to current Ti biomaterial Problems existing, it is provided that the preparation method of a kind of porous titanium copper calcium medical material; Purpose is in that to improve the mechanics activity of artificial implantation and antibiotic property further, solves implant simultaneously and does not mate with elastic modelling quantity and the mechanical property of osseous tissue and cause that bone produces stress shielding, hinders bone growth, healing problems.
Specifically include processing step as follows:
(1) by Ti85～97%, Cu1～5%, Ca2～10% mass percent, weigh Ti, Cu, Ca powder respectively, powder is put into ball grinder carries out mechanical alloying, it is evacuated to 20 ~ 30Pa after sealing with ethanol, then ball milling 50 ~ 100h, gained Ti-Cu-Ca alloying powder is still placed in ethanol, standby;
(2) by the Ti-Cu-Ca alloying powder obtained in step (1) and NH4HCO3Powder mixes 120 ~ 240min in batch mixer and obtains mixed-powder; In mixed-powder, the mass percent of Ti-Cu-Ca alloying powder is 95% ~ 75%, NH4HCO3The mass percent of powder is 5% ~ 25%.
(3) mixed-powder step (2) obtained loads stainless steel mould, cold moudling under the individual event pressure of 200 ~ 500MPa, obtains block pressed compact after moving back mould.
(4) block pressed compact step (3) obtained loads in graphite jig, insert in discharge plasma sintering stove again, system vacuum is sintered after being evacuated to 2 ~ 6Pa, heating rate is 50 ~ 100min/ DEG C, at 800～1000 DEG C be incubated 5～10min, cool to the furnace room temperature porous titanium copper calcium medical material.
Titanium metal powder purity >=99.95%, Cu metal dust purity >=99.99%, Ca metal dust purity >=99.9% in step of the present invention (1), above-mentioned powder mean particle sizes is within the scope of 25 μm ~ 1mm.
The NH adopted in the present invention4HCO3The particle diameter of powder is 100 ~ 700 μm.
Principles of the invention: owing to pure titanium has higher elasticity modulus, only is difficult to reduce its elastic modelling quantity by interpolation Cu and Ca, thus causing that implant produces " stress shielding " phenomenon with surrounding tissue. Therefore, the pore structure introducing uniqueness in Ti-Cu-Ca alloy can not only be conducive to osteoblast in its surface adhesion, propagation, new bone tissue is promoted to grow into hole thus realizing implant and forming chronobiological in host and fix, also effectively reduce the elastic modelling quantity of implant, weaken " stress shielding ", thus greatly reducing the risk that implant loosens and ruptures.
Compared with prior art, it is an advantage of the current invention that:
(1) antibiotic property is good, and biological activity is high. Containing sterilization element Cu and biological active elements Ca in its material structure, the infection in transplant operation transplantation process can be prevented, biological active elements Ca induced cell growth can be passed through again, increase the biological activity of transplant, can be used for human body hard tissue and substitute and repair.
(2) hole parameter is controlled, good biocompatibility. Prepared porous titanium copper calcium alloy porosity is 20% ~ 50%, pore-size is 100 ~ 700 μm, and its unique controlled hole parameter is conducive to cell to grow in its surface adhesion, makes to form permanently effective biological fixation between implant and host.
(3) elastic modelling quantity is good with the matching of people's bone. Prepared porous titanium copper calcium alloy intensity is 25 ~ 195MPa, elastic modelling quantity is 6 ~ 18GPa, with people's bone (elastic modelling quantity≤20GPa, comprcssive strength 100 ~ 230MPa) match, thus alleviate and eliminate " stress shielding " effect, it is to avoid loosening and fracture of implant.
(4) porous titanium copper calcium alloy prepared by employing the inventive method can as desirable people's osseous tissue alternate material, and the inventive method technique is simple, easy to operate, with low cost simultaneously, it is easy to accomplish industrialized production.
Accompanying drawing explanation
Fig. 1 is the low multiple pore appearance figure of embodiment of the present invention porous titanium copper calcium medical material;
Fig. 2 is the high multiple hole wall shape appearance figure of embodiment of the present invention porous titanium copper calcium medical material.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail, but protection scope of the present invention is not limited to described content.
Embodiment 1
(1) by the mass percent of Ti97%, Cu1%, Ca2% weigh respectively in glove box purity be 99.95%, 99.99%99.9%, particle mean size respectively 25 μm, 53 μm, 1mm Ti, Cu, Ca powder, powder is put into ball grinder carries out mechanical alloying, it is evacuated to 20Pa after sealing with anhydrous alcohol, then ball milling 50h, gained Ti-Cu-Ca alloying powder is still placed in anhydrous alcohol, standby;
(2) by the Ti-Cu-Ca alloying powder obtained in step (1) and NH4HCO3Powder mixes 240min in batch mixer and obtains mixed-powder; In mixed-powder, the mass percent of Ti-Cu-Ca alloying powder is 80%, the NH of 200 μm of particle diameters4HCO3Powder quality percentage ratio is 20%.
(3) mixed-powder step (2) obtained loads stainless steel mould, cold moudling under the individual event pressure of 200MPa, obtains block pressed compact after moving back mould.
(4) block pressed compact step (3) obtained loads in graphite jig, inserting in discharge plasma sintering stove again, system vacuum is sintered after being evacuated to 6Pa, and heating rate is 100min/ DEG C, at 900 DEG C be incubated 5min, cool to the furnace room temperature porous titanium copper calcium medical material.
By process conditions identical in this example, the powder of mixing is sintered at 800 DEG C, 850 DEG C, 950 DEG C, 1000 DEG C after cold moudling, together with the porous titanium copper calcium alloy that this example obtains at 900 DEG C of sintering, measure by relative density method, and by calculating the porosity obtaining POROUS TITANIUM copper calcium alloy, reference ASTME8-89a standard is as shown in table 1 by elastic modelling quantity and the comprcssive strength of mechanics compression experiment acquisition porous Ti-1Cu-2Ca alloy:
Table 1:
From measurement result, under 800 DEG C, 850 DEG C, 900 DEG C, 950 DEG C, 1000 DEG C five kinds of sintering temperatures, rising with sintering temperature, porosity is gradually reduced from 49.3% to 44.1%, and comprcssive strength is gradually increased from 6.3GPa to 11.6GPa with elastic modelling quantity from 45MPa to 158MPa, match with people's compact bone osseous tissue mechanical property (elastic modelling quantity 2 ~ 20GPa, comprcssive strength 130 ~ 230MPa), it is possible to effectively solve " stress shielding " phenomenon of implant.
The pattern tissue (as shown in Figure 1) of sintered specimen by observation by light microscope, the hole of sample is uniform distribution, and part connection, and aperture is at 100 ~ 700 μ m, there is uniform little pore size distribution around macropore, the requirement clinically to material pore scale can be met; The hole wall pattern of material being further looked at (as shown in Figure 2), it can be seen that in sintering process, material powder granule has just melted in short 5 minutes and has been bound up, and sintering state is good.Using escherichia coli and staphylococcus aureus (reference culture and antibiotic sensitive bacterial strain) as object of study, porous titanium copper calcium alloy prepared by discharge plasma sintering carries out antibiotic property experiment, result shows: on agar media surface, and the bacterial growth of surrounding materials is compared with blank group and is subject to obvious suppression.
Embodiment 2
(1) weighing purity in glove box respectively by the mass percent of Ti95%, Cu2%, Ca3% is 99.95%, 99.99%, 99.9%, particle mean size respectively 44 μm, 74 μm, 1.5mm Ti, Cu, Ca powder, powder is put into ball grinder carries out mechanical alloying, it is evacuated to 30Pa after sealing with ethanol, then ball milling 100h, institute's Ti-Cu-Ca alloying powder is still placed in ethanol, standby;
(2) by the Ti-Cu-Ca alloying powder obtained in step (1) and NH4HCO3Powder mixes 120min in batch mixer and obtains mixed-powder; In mixed-powder, the mass percent of Ti-Cu-Ca alloying powder is 95%, the NH of 300 μm of particle diameters4HCO3The mass percent of powder is 5%.
(3) mixed-powder step (2) obtained loads stainless steel mould, cold moudling under the individual event pressure of 500MPa, obtains block pressed compact after moving back mould.
(4) block pressed compact step (3) obtained loads in graphite jig, inserting in discharge plasma sintering stove again, system vacuum is sintered after being evacuated to 2Pa, and heating rate is 50min/ DEG C, at 1000 DEG C be incubated 10min, cool to the furnace room temperature porous titanium copper calcium medical material.
Ti, Cu, Ca powder is weighed respectively by the mass percent of Ti93%, Cu2%, Ca5% and the mass percent of Ti85%, Cu5%, Ca10%, powder is put into ball grinder carries out mechanical alloying, again by process conditions identical in this example, porous titanium copper calcium alloy together with the heterogeneity that this example sintering obtains, measure by relative density method, and by calculating the porosity obtaining POROUS TITANIUM copper calcium alloy, reference ASTME8-89a standard is as shown in table 2 by elastic modelling quantity and the comprcssive strength of mechanics compression experiment acquisition porous titanium copper calcium alloy:
Table 2:
From measurement result, the porous titanium copper calcium sample of three kinds of heterogeneities, porosity increases with alloying element and is gradually increased from 30.3% to 39.1%, and comprcssive strength is gradually reduced from 17.8GPa to 13.2GPa with elastic modelling quantity from 195MPa to 185MPa, with people compact bone osseous tissue mechanical property (elastic modelling quantity 2 ~ 20GPa, comprcssive strength 130 ~ 230MPa) match, it is possible to effectively solve " stress shielding " phenomenon of implant.
Using escherichia coli and staphylococcus aureus (reference culture and antibiotic sensitive bacterial strain) as object of study, porous titanium copper calcium alloy prepared by discharge plasma sintering carries out antibiotic property experiment, result shows: on agar media surface, and the bacterial growth of surrounding materials is compared with blank group and is subject to obvious suppression. After material and adult rabbits medulla mesenchyma co-culture of cells 2 weeks, it has been found that three kinds of materials all have the biological activity of excellence compared with pure titanium.
Embodiment 3
(1) by the mass percent of Ti89%, Cu4%, Ca7% weigh respectively in glove box purity be 99.95%, 99.99%99.9%, particle mean size respectively 25 μm, 61 μm, 0.8mm Ti, Cu, Ca powder, powder is put into ball grinder carries out mechanical alloying, it is evacuated to 25Pa after sealing with ethanol, then ball milling 80h, gained Ti-Cu-Ca alloying powder is still placed in ethanol, standby;
(2) by the Ti-Cu-Ca alloying powder obtained in step (1) and NH4HCO3Powder mixes 200min in batch mixer and obtains mixed-powder; In mixed-powder, the mass percent of Ti-Cu-Ca alloying powder is 75%, the NH of 100 μm of particle diameters4HCO3The mass percent of powder is 25%.
(3) mixed-powder step (2) obtained loads stainless steel mould, cold moudling under the individual event pressure of 300MPa, obtains block pressed compact after moving back mould.
(4) block pressed compact step (3) obtained loads in graphite jig, inserting in discharge plasma sintering stove again, system vacuum is sintered after being evacuated to 4Pa, and heating rate is 80min/ DEG C, at 1000 DEG C be incubated 8min, cool to the furnace room temperature porous Ti-4Cu-7Ca medical material.
By process conditions identical in this example, the ammonium hydrogen carbonate of alloying titanium copper calcium powder and the different-grain diameter of 100 μm, 200 μm, 600 μm, 700 μm is mixed, together with the porous titanium copper calcium alloy that this example obtains at sintering, measure by relative density method, and by calculating the mean porosities of porous titanium copper calcium alloy obtaining control pore yardstick and average pore scale respectively 40% and about 500 μm, such pore structure is conducive to the osteoblastic transmission grown into body fluid, accelerates the agglutination at osseous tissue defect place.
The above results shows: utilize porous titanium copper calcium medical alloy material prepared by the inventive method to have the advantage that (1) can prevent the infection in transplant operation transplantation process, biological active elements induced cell growth can be passed through again, increase the biological activity of transplant, can be used for human body hard tissue and substitute and repair. (2) mean porosities be 20% ~ 50%, average pore size be 100 ~ 700 μm, its unique controlled hole parameter is conducive to cell to grow in its surface adhesion, makes to form permanently effective biological fixation between implant and host. (3) alloy strength is 25 ~ 195MPa, elastic modelling quantity is 6 ~ 18GPa, matches with people's bone (elastic modelling quantity≤20GPa, comprcssive strength 100 ~ 230MPa), thus alleviating and eliminating " stress shielding " effect, it is to avoid the loosening and fracture of implant. Therefore, porous titanium copper calcium biomedical alloy material prepared by the inventive method is adopted can to substitute embedded material as good people's bone. The inventive method technique is simple, easy to operate, with low cost simultaneously, it is easy to accomplish industrialized production.
Claims (4)
1. the preparation method of a porous titanium copper calcium material, it is characterised in that processing step is as follows:
(1) by Ti85～97%, Cu1～5%, Ca2～10% mass percent, weigh Ti, Cu, Ca powder respectively, powder is put into ball grinder carries out mechanical alloying, evacuation then ball milling 50 ~ 100h after sealing with anhydrous alcohol, gained Ti-Cu-Ca alloying powder is still placed in anhydrous alcohol, standby;
(2) by the Ti-Cu-Ca alloying powder obtained in step (1) and NH4HCO3Powder mixes 120 ~ 240min in batch mixer and obtains mixed-powder; In mixed-powder, the mass percent of Ti-Cu-Ca alloying powder is 95% ~ 75%, NH4HCO3The mass percent of powder is 5% ~ 25%;
(3) mixed-powder step (2) obtained loads stainless steel mould, cold moudling under the individual event pressure of 200 ~ 500MPa, obtains block pressed compact after moving back mould;
(4) block pressed compact step (3) obtained loads in graphite jig, insert in discharge plasma sintering stove again, system vacuum is sintered after being evacuated to 2 ~ 6Pa, heating rate is 50 ~ 100min/ DEG C, at 800～1000 DEG C be incubated 5～10min, cool to the furnace room temperature porous titanium copper calcium medical material.
2. the preparation method of porous titanium copper calcium material according to claim 1, it is characterised in that: in ma process, vacuum is 20 ~ 30Pa.
3. the preparation method of titanium calcium copper biomaterial according to claim 1, it is characterized in that: titanium metal powder purity >=99.95%, Cu metal dust purity >=99.99%, Ca metal dust purity >=99.9% in step (1), above-mentioned powder mean particle sizes is within the scope of 25 μm ~ 1mm.
4. the preparation method of porous titanium copper calcium material according to claim 1, it is characterised in that: NH in step (2)4HCO3The particle diameter of powder is 100 ~ 700 μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610185484.0A CN105671364A (en) | 2016-03-29 | 2016-03-29 | Preparation method of porous titanium copper calcium material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610185484.0A CN105671364A (en) | 2016-03-29 | 2016-03-29 | Preparation method of porous titanium copper calcium material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105671364A true CN105671364A (en) | 2016-06-15 |
Family
ID=56225409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610185484.0A Pending CN105671364A (en) | 2016-03-29 | 2016-03-29 | Preparation method of porous titanium copper calcium material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105671364A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107243634A (en) * | 2017-05-26 | 2017-10-13 | 广西师范大学 | A kind of preparation method of porous metal material |
| CN107824790A (en) * | 2017-10-25 | 2018-03-23 | 成都先进金属材料产业技术研究院有限公司 | A kind of preparation method of porous vanadium chromium titanium material |
| CN109602957A (en) * | 2018-12-19 | 2019-04-12 | 云南大学 | A kind of bio-medical porous titanium niobium copper orthopedic implanting material and its preparation method and application |
| CN114470317A (en) * | 2022-01-21 | 2022-05-13 | 江苏科技大学 | Titanium alloy material for repairing skull and preparation method thereof |
| CN114505480A (en) * | 2020-11-16 | 2022-05-17 | 鞍钢股份有限公司 | Method for preparing foam steel |
| CN115747596A (en) * | 2022-11-18 | 2023-03-07 | 东莞宜安科技股份有限公司 | Antibacterial osteogenesis-promoting medical nano porous tantalum-copper alloy and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5984683A (en) * | 1997-01-20 | 1999-11-16 | Injex Corporation | Prosthetic restoration and manufacturing method thereof |
| CN102936671A (en) * | 2011-08-15 | 2013-02-20 | 中国科学院金属研究所 | Anti-infective medical titanium metal material |
| CN104131195A (en) * | 2014-08-14 | 2014-11-05 | 昆明理工大学 | Preparation method of biomedical porous titanium |
| CN105349831A (en) * | 2015-08-18 | 2016-02-24 | 张志军 | Preparation method for medical artificial joint material |
| CN105349832A (en) * | 2015-08-18 | 2016-02-24 | 赵丽 | Material for preparing medical bone fixing device |
| CN105369062A (en) * | 2015-08-18 | 2016-03-02 | 张志军 | Material for making medical artificial joint |
| CN105369063A (en) * | 2015-08-18 | 2016-03-02 | 赵丽 | Manufacturing method for medical bone fixing device |
| CN105385862A (en) * | 2015-11-19 | 2016-03-09 | 淄博永辰环境影响评价有限公司 | Manufacturing method for medical artificial limb |
-
2016
- 2016-03-29 CN CN201610185484.0A patent/CN105671364A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5984683A (en) * | 1997-01-20 | 1999-11-16 | Injex Corporation | Prosthetic restoration and manufacturing method thereof |
| CN102936671A (en) * | 2011-08-15 | 2013-02-20 | 中国科学院金属研究所 | Anti-infective medical titanium metal material |
| CN104131195A (en) * | 2014-08-14 | 2014-11-05 | 昆明理工大学 | Preparation method of biomedical porous titanium |
| CN105349831A (en) * | 2015-08-18 | 2016-02-24 | 张志军 | Preparation method for medical artificial joint material |
| CN105349832A (en) * | 2015-08-18 | 2016-02-24 | 赵丽 | Material for preparing medical bone fixing device |
| CN105369062A (en) * | 2015-08-18 | 2016-03-02 | 张志军 | Material for making medical artificial joint |
| CN105369063A (en) * | 2015-08-18 | 2016-03-02 | 赵丽 | Manufacturing method for medical bone fixing device |
| CN105385862A (en) * | 2015-11-19 | 2016-03-09 | 淄博永辰环境影响评价有限公司 | Manufacturing method for medical artificial limb |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107243634A (en) * | 2017-05-26 | 2017-10-13 | 广西师范大学 | A kind of preparation method of porous metal material |
| CN107824790A (en) * | 2017-10-25 | 2018-03-23 | 成都先进金属材料产业技术研究院有限公司 | A kind of preparation method of porous vanadium chromium titanium material |
| CN109602957A (en) * | 2018-12-19 | 2019-04-12 | 云南大学 | A kind of bio-medical porous titanium niobium copper orthopedic implanting material and its preparation method and application |
| CN114505480A (en) * | 2020-11-16 | 2022-05-17 | 鞍钢股份有限公司 | Method for preparing foam steel |
| CN114470317A (en) * | 2022-01-21 | 2022-05-13 | 江苏科技大学 | Titanium alloy material for repairing skull and preparation method thereof |
| CN115747596A (en) * | 2022-11-18 | 2023-03-07 | 东莞宜安科技股份有限公司 | Antibacterial osteogenesis-promoting medical nano porous tantalum-copper alloy and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105671364A (en) | Preparation method of porous titanium copper calcium material | |
| CN105397090B (en) | A kind of preparation method of porous nickel-titanium/hydroxyapatite composite material | |
| Xu et al. | Porous Ti-10Mo alloy fabricated by powder metallurgy for promoting bone regeneration | |
| CN106552940B (en) | A kind of preparation method of the ordered porous TiAg alloys of gradient | |
| CN103357063B (en) | The metallic composite of a kind of bootable osteogenesis and application thereof | |
| CN102512267A (en) | Bone restoration body with composite porous structure and preparation method thereof | |
| Kim et al. | Pressureless sintering and mechanical and biological properties of fluor‐hydroxyapatite composites with zirconia | |
| CN102312128B (en) | Method for preparing titanium niobium tantalum zirconium biomedical titanium alloys by discharge plasma sintering | |
| Yang et al. | Mechanical properties of porous Ti-Mo and Ti-Nb alloys for biomedical application by gelcasting | |
| Vasconcellos et al. | Novel production method of porous surface Ti samples for biomedical application | |
| CN104826174A (en) | Method for preparation of bone hydroxyapatite-imitating bone repair material | |
| CN105251057A (en) | Preparation method of porous titanium/hydroxyapatite composite material | |
| WO2012142952A1 (en) | Porous tantalum rod | |
| CN101912635A (en) | Bio-medicinal porous titanium material and preparation method thereof | |
| KR101633660B1 (en) | Method for preparing a low young's modulus porous titanium-zirconium-niobium composites for biomaterial and a low young's modulus porous titanium-zirconium-niobium composites for biomaterial | |
| CN104131195A (en) | Preparation method of biomedical porous titanium | |
| CN108273126A (en) | A kind of preparation method of gradient medical composite material | |
| CN104152738A (en) | Method for manufacturing biomedical porous nickel titanium alloy | |
| CN110054491B (en) | Preparation method of nano zinc oxide doped hydroxyapatite porous bioceramic | |
| CN104857566B (en) | A kind of preparation method of titanium niobium zirconium base titanium/hydroxyl apatite biological composite material | |
| Chu et al. | Fabrication and characterization of hydroxyapatite reinforced with 20 vol% Ti particles for use as hard tissue replacement | |
| CN107904424A (en) | A kind of preparation method of the medical porous Ti Cu alloys of biologically active antimicrobial form | |
| CN104894420B (en) | A kind of preparation method of titanium niobium zirconium base calcium pyrophosphate Biocomposite material | |
| CN115747596A (en) | Antibacterial osteogenesis-promoting medical nano porous tantalum-copper alloy and preparation method thereof | |
| Bhushan et al. | Fabrication and characterization of a new range of β-type Ti-Nb-Ta-Zr-xHaP (x= 0, 10) alloy by mechanical alloying and spark plasma sintering for biomedical applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20160615 |
|
| RJ01 | Rejection of invention patent application after publication |