CN111014664A - Preparation method of antibacterial porous titanium alloy - Google Patents
Preparation method of antibacterial porous titanium alloy Download PDFInfo
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- CN111014664A CN111014664A CN201911134266.4A CN201911134266A CN111014664A CN 111014664 A CN111014664 A CN 111014664A CN 201911134266 A CN201911134266 A CN 201911134266A CN 111014664 A CN111014664 A CN 111014664A
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 33
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 55
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 40
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052709 silver Inorganic materials 0.000 claims abstract description 24
- 239000004332 silver Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 22
- 229910001961 silver nitrate Inorganic materials 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 18
- 238000000498 ball milling Methods 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 239000002270 dispersing agent Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 9
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 9
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 9
- 238000003825 pressing Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 238000009740 moulding (composite fabrication) Methods 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 78
- 238000000034 method Methods 0.000 claims description 20
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 16
- 239000002244 precipitate Substances 0.000 claims description 13
- 229960005070 ascorbic acid Drugs 0.000 claims description 8
- 235000010323 ascorbic acid Nutrition 0.000 claims description 8
- 239000011668 ascorbic acid Substances 0.000 claims description 8
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 229910000048 titanium hydride Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 238000000748 compression moulding Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 239000011148 porous material Substances 0.000 abstract description 7
- 239000011812 mixed powder Substances 0.000 abstract description 3
- 238000001556 precipitation Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 10
- 208000015181 infectious disease Diseases 0.000 description 8
- 241000894006 Bacteria Species 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- 229910052719 titanium Inorganic materials 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 239000012620 biological material Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 238000009395 breeding Methods 0.000 description 3
- 230000001488 breeding effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007943 implant Substances 0.000 description 3
- 238000004663 powder metallurgy Methods 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 230000000845 anti-microbial effect Effects 0.000 description 2
- 229940088710 antibiotic agent Drugs 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000462 isostatic pressing Methods 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 208000034309 Bacterial disease carrier Diseases 0.000 description 1
- 208000035965 Postoperative Complications Diseases 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 230000002924 anti-infective effect Effects 0.000 description 1
- 229940121375 antifungal agent Drugs 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 230000010065 bacterial adhesion Effects 0.000 description 1
- 230000008952 bacterial invasion Effects 0.000 description 1
- 230000003385 bacteriostatic effect Effects 0.000 description 1
- 230000032770 biofilm formation Effects 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000036512 infertility Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 244000000010 microbial pathogen Species 0.000 description 1
- 230000000399 orthopedic effect Effects 0.000 description 1
- 238000010883 osseointegration Methods 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000069 prophylactic effect Effects 0.000 description 1
- -1 silver ions Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000003826 tablet Substances 0.000 description 1
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- 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
- B22F3/02—Compacting only
- B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
-
- 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
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
-
- 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
- B22F3/1103—Making porous workpieces or articles with particular physical characteristics
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- 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
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a preparation method of an antibacterial porous titanium alloy, which comprises the following steps of ball-milling raw material powder for later use; preparing silver nitrate solution, adding dispersant, and recording as solution A1(ii) a Preparing reducing agent solution A2(ii) a Mixing the solution A1And solution A2Heating in water bath to reaction temperature, dissolving in solution A1Adding the raw material powder, and adding into the solution A2Adjusting pH value and keeping constant, taking out reaction solution after reaction, dispersing and cleaning, and using deionized water and anhydrousWashing with ethanol for three times, centrifuging the reaction solution for precipitation, and drying to obtain mixed powder; adding ammonium bicarbonate into the mixed powder, uniformly mixing, pressing and forming the mixture, and then sintering in vacuum to finally obtain the silver-containing porous titanium alloy; the invention solves the problems that the process for preparing the antibacterial porous titanium alloy is complex and the pores of the porous titanium alloy do not have antibacterial capability in the prior art, and has the characteristics of simple equipment, convenient operation, strong controllability and the like.
Description
Technical Field
The invention belongs to the technical field of preparing titanium alloy by powder metallurgy, and particularly relates to a preparation method of an antibacterial porous titanium alloy.
Background
With the progress of medical technology and the continuous improvement of living standard of people, titanium alloy has been widely applied to clinical implant materials due to its excellent mechanical properties, specific strength, corrosion resistance and biocompatibility. In china, fractures alone are applied in more than 500 million cases per year, and an endophytic-related infection, which is one of the serious postoperative complications and is difficult to effectively prevent and treat, further increases the pain of patients, is called a "biomaterial-related infection". On average, the incidence of biomaterial-related infections is 0.5% -6%. Although various surgical preparations are made to prevent bacterial contamination, bacterial invasion often occurs post-operatively. In recent decades, anti-infective inter-plant materials have gradually become a major means of controlling biomaterial-related infections, based on improvements in sterility, sterile environment control and prophylactic use of antibiotics.
The endophytes almost all have surfaces with certain roughness which are beneficial to osseointegration, but the rough surfaces make bacteria easier to adhere and increase the susceptibility of organisms to pathogenic microorganisms, i.e. the existence of the endophytes obviously reduces the pathogenic quantity of bacteria required for infection, so that the preparation of the implant material capable of resisting bacteria is necessary. Silver, as the most common inorganic antimicrobial agent, has the advantages of high efficiency, safety, broad antimicrobial spectrum and the like, and is widely applied to antimicrobial and antifungal products. The nano silver has high-efficiency antibacterial performance and lasting efficacy due to quantum effect, small-size effect and extremely large specific surface.
At present, an effective method for preventing bacterial colonization and bacterial biofilm formation in orthopedics is lacked, and the conventional method mainly uses antibiotics for preventing infection after operation, can reduce incision infection, but cannot prevent the breeding of prosthesis and surrounding bacteria.
Disclosure of Invention
The invention provides a sintered TiH2The powder, the element powder and the nano silver powder are introduced by a wet method, and the probability of bacterial adhesion in rough surfaces and pores is reduced by a method for preparing the antibacterial titanium alloy by a powder metallurgy method, so that the problem of biological material related infection caused by traditional implants is solved, and the antibacterial titanium alloy has the characteristics of simple equipment, convenience in operation, strong controllability and the like.
A preparation method of an antibacterial porous titanium alloy comprises the following specific steps:
(1) ball-milling the raw material powder until the particle size is less than 45um for later use;
(2) weighing silver nitrate, adding deionized water to prepare a silver nitrate solution with the concentration of 0.1-2 mol/L, adding a dispersing agent, and fully dissolving by adopting magnetic stirring to obtain a solution A1；
(3) Weighing reducing agent and adding deionized water to prepare reducing agent solution A2；
(4) Mixing the solution A1And solution A2Placing into a water bath, heating to reaction temperature, and dissolving in solution A1Adding the raw material powder which is well ball-milled into the solution A under the magnetic stirring2Carrying out reaction, adjusting the pH value of the mixed solution to 7-9 and keeping the pH value constant, taking out the reaction solution after the reaction is finished, placing the reaction solution into an ultrasonic cleaner for dispersion, respectively cleaning precipitates with deionized water and absolute ethyl alcohol for three times, placing the reaction solution into a centrifugal machine for centrifugal separation and precipitation, and finally drying the precipitates in a drying box at the temperature of 60-80 ℃ for 8-12 hours to obtain powder;
(5) and (4) adding ammonium bicarbonate into the powder in the step (4), uniformly mixing, carrying out isostatic pressing on the mixture, carrying out vacuum sintering on a pressed blank, and thus obtaining the silver-containing porous titanium alloy.
The raw material powder in the step (1) is TiH2Powder or TiH2The powder is mixed with one or more of Nb powder, Zr powder and Mo powder in any proportion, and the purity of the powder is high99.0% or more.
The dispersant in the step (2) is PVP, and the addition amount of the dispersant is solution A15% -15% of the mass of silver nitrate.
The reducing agent in the step (3) is ascorbic acid, and a reducing agent solution A2The concentration of the ascorbic acid is 0.1-1 mol/L.
Mixing the raw material powder obtained in the step (4) with the solution A1Adding the solution A into the silver-rich silver solution at a mass ratio of 100:3-101In (1).
Step (4) solution A1Silver nitrate in (1) and solution A2The molar ratio of the reducing agent(s) is 1-2: 1.
Step (4) solution A1And solution A2The temperature of the mixing reaction is 25-45 ℃, and the reaction time is 10-15 min.
And (4) adjusting the pH value by adopting dilute ammonia water or dilute nitric acid.
The mass ratio of the powder in the step (5) to the ammonium bicarbonate is 100: 30-40.
And (5) isostatic pressing and forming under the pressure of 6-8 MPa for 10-15 min.
The vacuum sintering process in the step (5) comprises the following steps: the heating rate is 5 ℃/min to 10 ℃/min, the temperature is respectively kept at 400 ℃ and 600 ℃ for 30min, then the temperature is heated to 800 ℃ to 1100 ℃ and kept for 60min to 150min, the vacuum pumping is continuously carried out in the sintering process, and the vacuum degree is kept to be less than or equal to 10-2Pa。
The method comprises the steps of reducing nano silver by a hydrothermal method by using a powder metallurgy method, uniformly mixing the nano silver and mixed powder in a magnetically stirred solution, and enabling the nano silver to account for 3% -10% of raw material powder when the nano silver reducing solution is prepared so as to achieve an antibacterial effect.
The invention has the beneficial effects that:
(1) by mixing in the solution, the generated nano silver is possible to wrap the alloy powder or the reduced silver can be uniformly mixed with the alloy powder;
(2) the porosity and pore size of the porous titanium can be controlled by adding ammonium bicarbonate with different contents and controlling the pressure of a pressed compact, so that the strength of the porous titanium is matched with the strength of a human bone;
(3) the nano silver is added by a wet method, so that the pores of the matrix contain silver, the possibility of bacteria breeding on rough surfaces and in the pores is reduced, the pores also have a sterilization effect, and the silver and the titanium of the matrix are firmly combined by mixing and sintering, so that excessive silver ions are not easily released;
(4) the method provided by the invention is convenient to operate, does not need subsequent heat treatment, and has the characteristics of simple equipment, convenience in operation, strong controllability and the like.
Drawings
FIG. 1 is an XRD pattern of porous titanium prepared in example 1;
FIG. 2 is a macroscopic view of the porous titanium prepared in example 1.
Detailed Description
The invention will be further described with reference to the drawings and the embodiments without limiting the scope of the invention thereto. The experimental equipment used in the examples of the present invention: planetary high-energy ball mill, powder tablet press, ultrasonic oscillator, centrifuge, vacuum sintering furnace.
Example 1
A preparation method of an antibacterial porous titanium alloy comprises the following specific steps:
(1) weighing TiH2Putting the powder into a ball milling tank according to a ball-material ratio of 4:1, wherein the charging volume is 40%, setting the ball milling rotation speed to be 150r/min and the ball milling time to be 150min by adopting a planetary ball mill, and performing ball milling until the particle size is less than 45um for later use, wherein the purity of the powder is more than or equal to 99.0%;
(2) weighing silver nitrate, adding deionized water to prepare a silver nitrate solution with the concentration of 0.1mol/L, adding a dispersant PVP, fully dissolving, and marking as a solution A1The dispersant is added into the solution A15% of the mass of silver nitrate;
(3) weighing reducing agent ascorbic acid and adding to removeThe sub-water is prepared into a reducing agent solution A with the concentration of 0.2mol/L2；
(4) Mixing the solution A1And solution A2Placing into a water bath, heating to reaction temperature of 35 deg.C, and adding solution A1Mixing the raw material powder obtained in the step (1) with the solution A under magnetic stirring1Adding the solution A into the silver-containing solution according to the mass ratio of 100:31In (b), the whole solution is added to A2In solution, solution A1Silver nitrate in (1) and solution A2The molar ratio of the reducing agent is 1:1, the pH value of the reaction is controlled to be 7-9 by ammonia water and nitric acid, and the reaction is continued for 10min at 35 ℃;
(5) placing the reacted mixed solution into an ultrasonic cleaner for ultrasonic dispersion, respectively cleaning precipitates with deionized water and absolute ethyl alcohol for three times, then centrifuging the precipitates by adopting a centrifugal machine, and finally placing the precipitates into a drying box at 60 ℃ for drying for 12 hours;
(6) uniformly mixing the dry powder and ammonium bicarbonate according to a mass ratio of 100:30, then placing the mixture into a cylindrical mould pressing die, and tabletting by using a powder tabletting machine, wherein the pressing pressure is 6MPa, and the pressure maintaining time is 15 min;
(7) placing the pressed compact into a high vacuum sintering furnace for sintering, continuously vacuumizing in the sintering process, and keeping the vacuum degree less than or equal to 10-2Pa, setting the basic heating rate to be 5 ℃/min, setting heat preservation platforms at 400 ℃ and 600 ℃ respectively, preserving the heat of each platform for 30 minutes, then heating to 900 ℃, preserving the heat for 120 minutes, and then cooling along with the furnace to obtain the silver-containing porous titanium alloy.
Fig. 1 shows XRD of the silver-containing porous titanium alloy prepared in this example, which shows that silver is compounded on the sample, and as shown in fig. 2, the silver is distributed on the surface of the silver-containing porous titanium alloy sample prepared in this example, so that the silver can well exert bacteriostatic action and antibacterial action, and the sample also contains silver inside, so that bacteria can be prevented from breeding in the pores thereof.
Example 2
A preparation method of an antibacterial porous titanium alloy comprises the following specific steps:
(1) according to the formula Ti-13Nb-13ZrWeighing TiH according to the proportion of components required by alloy standard2Putting the powder, Nb powder and Zr powder with the purity of more than or equal to 99.0% into a ball milling tank according to the ball-material ratio of 4:1, wherein the loading volume is 40%, setting the ball milling speed to be 150r/min and the ball milling time to be 150min by adopting a planetary ball mill, and ball milling until the particle size is less than 45um for later use;
(2) weighing silver nitrate, adding deionized water to prepare a silver nitrate solution with the concentration of 0.5mol/L, adding a dispersant PVP, fully dissolving, and marking as a solution A1The dispersant is added into the solution A 110% of the mass of silver nitrate;
(3) weighing a reducing agent ascorbic acid, adding deionized water to prepare a reducing agent solution A with the concentration of 1mol/L2；
(4) Mixing the solution A1And solution A2Placing into a water bath, heating to reaction temperature of 25 deg.C, and adding solution A1Mixing the raw material powder obtained in the step (1) with the solution A under magnetic stirring1Adding the solution A into the silver-containing solution according to the mass ratio of 100:51In (b), the whole solution is added to A2In solution, solution A1Silver nitrate in (1) and solution A2The molar ratio of the reducing agent is 1.5:1, the pH value of the reaction is controlled to be 7-9 by ammonia water and nitric acid, and the reaction is continued for 15min at 25 ℃;
(5) placing the reacted mixed solution into an ultrasonic cleaner for ultrasonic dispersion, respectively cleaning precipitates with deionized water and absolute ethyl alcohol for three times, then centrifuging the precipitates by adopting a centrifugal machine, and finally placing the precipitates into a drying box at 70 ℃ for drying for 10 hours;
(6) uniformly mixing the dry powder and ammonium bicarbonate according to a mass ratio of 100:35, then placing the mixture into a cylindrical mould pressing die, and tabletting by using a powder tabletting machine, wherein the pressing pressure is 7MPa, and the pressure maintaining time is 12 min;
(7) placing the pressed compact into a high vacuum sintering furnace for sintering, continuously vacuumizing in the sintering process, and keeping the vacuum degree less than or equal to 10-2Pa, setting the basic heating rate to 8 ℃/min, setting heat preservation platforms at 400 ℃ and 600 ℃ respectively, preserving heat for 30 minutes for each platform, heating to 800 ℃ and preserving heat for 150min, and then carrying out furnace-following treatmentAnd cooling to obtain the silver-containing porous titanium alloy.
Example 3
A preparation method of an antibacterial porous titanium alloy comprises the following specific steps:
(1) weighing TiH according to the component proportion required by the standard of a multipurpose near β type medical titanium alloy developed by Ti (3-6) Zr (2-4) Mo (24-27) Nb (TLE, northwest nonferrous metals research institute)2The method comprises the following steps of (1) putting powder, Zr powder, Mo powder and Nb powder with the powder purity of 99.0% or more into a ball milling tank according to a ball-to-material ratio of 4:1, wherein the loading volume is 40%, a planetary ball mill is adopted, the ball milling speed is set to be 150r/min, the ball milling time is set to be 150min, and the ball milling is carried out until the particle size is less than 45um for later use;
(2) weighing silver nitrate, adding deionized water to prepare a silver nitrate solution with the concentration of 2mol/L, adding a dispersant PVP, fully dissolving, and marking as a solution A1The dispersant is added into the solution A115% of the mass of silver nitrate;
(3) weighing a reducing agent ascorbic acid, adding the ascorbic acid into deionized water to prepare a reducing agent solution A with the concentration of 0.1mol/L2；
(4) Mixing the solution A1And solution A2Placing into a water bath, heating to 45 deg.C, and adding the solution A1Mixing the raw material powder obtained in the step (1) with the solution A under magnetic stirring1Adding the solution A into the silver-containing solution according to the mass ratio of 100:101In (b), the whole solution is added to A2In solution, solution A1Silver nitrate in (1) and solution A2The molar ratio of the reducing agent is 2:1, the pH value of the reaction is controlled to be 7-9 by ammonia water and nitric acid, and the reaction is continued for 11min at 45 ℃;
(5) placing the reacted mixed solution into an ultrasonic cleaner for ultrasonic dispersion, respectively cleaning precipitates with deionized water and absolute ethyl alcohol for three times, then centrifuging the precipitates by adopting a centrifugal machine, and finally placing the precipitates into a drying box at 80 ℃ for drying for 8 hours;
(6) uniformly mixing the dry powder and ammonium bicarbonate according to a mass ratio of 100:40, then placing the mixture into a cylindrical mould pressing die, and tabletting by using a powder tabletting machine, wherein the pressing pressure is 8MPa, and the pressure maintaining time is 10 min;
(7) placing the pressed compact into a high vacuum sintering furnace for sintering, continuously vacuumizing in the sintering process, and keeping the vacuum degree less than or equal to 10-2Pa, setting the basic heating rate to be 10 ℃/min, setting heat preservation platforms at 400 ℃ and 600 ℃ respectively, preserving the heat of each platform for 30 minutes, then heating to 1100 ℃, preserving the heat for 60 minutes, and then cooling along with the furnace to obtain the silver-containing porous titanium alloy.
Claims (10)
1. The preparation method of the antibacterial porous titanium alloy is characterized by comprising the following specific steps of:
(1) ball-milling the raw material powder until the particle size is less than 45um for later use;
(2) preparing silver nitrate solution with the concentration of 0.1-2 mol/L, adding a dispersing agent, stirring and fully dissolving, and marking as solution A1；
(3) Preparing reducing agent solution A2；
(4) Mixing the solution A1And solution A2Heating in water bath to reaction temperature, dissolving in solution A1Adding the raw material powder obtained in the step (1), uniformly mixing, and adding the mixture into the solution A under magnetic stirring2Carrying out reaction, adjusting the pH value of the mixed solution to 7-9 and keeping the pH value constant, carrying out ultrasonic dispersion after the reaction is finished, respectively cleaning the precipitate with deionized water and absolute ethyl alcohol for three times, then carrying out centrifugal separation on the precipitate, and drying at the temperature of 60-80 ℃ for 8-12 hours to obtain powder;
(5) and (4) adding ammonium bicarbonate into the powder obtained in the step (4), uniformly mixing, pressing and forming the mixture, and then sintering in vacuum to obtain the silver-containing porous titanium alloy.
2. The method for preparing the antibacterial porous titanium alloy according to claim 1, wherein the raw material powder in the step (1) is TiH2Powder or TiH2The powder is mixed with one or more of Nb powder, Zr powder and Mo powder in any proportion, and the purity of the powder is more than or equal to 99.0 percent.
3. The preparation method of antibacterial porous titanium alloy according to claim 1, wherein the dispersant in step (2) is PVP,the addition amount of the dispersant is solution A15% -15% of the mass of silver nitrate.
4. The method for preparing antibacterial porous titanium alloy according to claim 1, wherein the reducing agent in step (3) is ascorbic acid, and the reducing agent solution A2The concentration of the ascorbic acid is 0.1-1 mol/L.
5. The method for preparing antibacterial porous titanium alloy according to claim 1, wherein the raw material powder in the step (4) is prepared by mixing the raw material powder with the solution A1Adding the solution A into the silver-rich silver solution at a mass ratio of 100:3-101In (1).
6. The method for preparing antibacterial porous titanium alloy according to claim 1, wherein the solution A in the step (4)1Silver nitrate in (1) and solution A2The molar ratio of the reducing agent(s) is 1-2: 1.
7. The preparation method of the antibacterial porous titanium alloy according to claim 1, wherein the reaction temperature in the step (4) is 25-45 ℃ and the reaction time is 10-15 min.
8. The preparation method of the antibacterial porous titanium alloy according to claim 1, wherein the mass ratio of the powder in the step (5) to the ammonium bicarbonate is 100: 30-40.
9. The preparation method of the antibacterial porous titanium alloy according to claim 1, wherein the pressure for the compression molding in the step (5) is 6-8 MPa, and the time is 10-15 min.
10. The preparation method of the antibacterial porous titanium alloy according to claim 1, wherein the vacuum sintering process in the step (5) is as follows: the heating rate is 5 ℃/min to 10 ℃/min, the temperature is respectively kept at 400 ℃ and 600 ℃ for 30min, then the temperature is heated to 800 ℃ to 1100 ℃ and kept for 60min to 150min, the vacuum pumping is continuously carried out in the sintering process, and the vacuum degree is kept to be less than or equal to 10-2Pa。
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