CN109112358B - High-antibacterial titanium alloy used as metal implant - Google Patents
High-antibacterial titanium alloy used as metal implant Download PDFInfo
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 21
- 239000002184 metal Substances 0.000 title claims abstract description 21
- 239000007943 implant Substances 0.000 title claims abstract description 13
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 46
- 239000010936 titanium Substances 0.000 claims abstract description 38
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims description 7
- 241000894006 Bacteria Species 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000137 annealing Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- 238000003723 Smelting Methods 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 208000022362 bacterial infectious disease Diseases 0.000 abstract description 10
- 208000035143 Bacterial infection Diseases 0.000 abstract description 9
- 239000000956 alloy Substances 0.000 abstract description 9
- 239000011159 matrix material Substances 0.000 abstract description 6
- 230000000399 orthopedic effect Effects 0.000 abstract description 6
- 229910052733 gallium Inorganic materials 0.000 abstract description 4
- 229910045601 alloy Inorganic materials 0.000 abstract description 3
- 239000010949 copper Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 230000001954 sterilising effect Effects 0.000 description 5
- 238000004659 sterilization and disinfection Methods 0.000 description 5
- 230000001580 bacterial effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 208000015181 infectious disease Diseases 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- 230000003013 cytotoxicity Effects 0.000 description 3
- 231100000135 cytotoxicity Toxicity 0.000 description 3
- 238000005242 forging Methods 0.000 description 3
- 241000588724 Escherichia coli Species 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010587 phase diagram Methods 0.000 description 2
- 230000008439 repair process Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010011409 Cross infection Diseases 0.000 description 1
- 229910000807 Ga alloy Inorganic materials 0.000 description 1
- 206010031256 Osteomyelitis chronic Diseases 0.000 description 1
- 206010058046 Post procedural complication Diseases 0.000 description 1
- 206010067268 Post procedural infection Diseases 0.000 description 1
- 208000035965 Postoperative Complications Diseases 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 241001062472 Stokellia anisodon Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012925 biological evaluation Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000003203 everyday effect Effects 0.000 description 1
- 210000002950 fibroblast Anatomy 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002458 infectious effect Effects 0.000 description 1
- 230000003340 mental effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/002—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention relates to the field of titanium alloy materials, in particular to a high-antibacterial titanium alloy used as a metal implant. The titanium alloy material comprises the following chemical components (in percentage by weight): ga: 0.5-5.0%, Cu: 1.0-3.0%, and the balance of Ti and inevitable impurities. The alloy forms a titanium-gallium phase in a medical titanium alloy matrix through special antibacterial heat treatment, thereby endowing the medical titanium alloy with a stronger antibacterial function. The novel antibacterial titanium alloy material can be widely applied to various titanium metal medical instruments used in the medical clinical fields of stomatology, orthopedics and the like so as to reduce the risk of bacterial infection induced by metal implants.
Description
Technical Field
The invention relates to the field of medical titanium alloy materials, in particular to a high antibacterial titanium alloy used as a metal implant.
Background
Pure titanium for medical use has been widely used in the field of clinical medicine due to its excellent biocompatibility. As early as 50 years in the 20 th century, pure titanium was processed into bone plates, bone nails, femoral heads and other implanted medical devices for orthopedic repair operations. Subsequently, pure titanium is continuously being used clinically, and is now mainly used in the field of oral repair, such as: crown and bridge (inlay, nucleus, crown, bridge), bracket (partial denture bracket, complete denture base), various attachments, and prosthesis products.
However, as a common postoperative complication, bacterial infection caused by medical instruments has become one of the important problems to be solved urgently in the medical field of the 21 st century. Annual incidence of orthopedic implant-related infections in the united states is reported to reach around 4.3%. According to the data in the handbook of infection control and prevention in hospitals issued by the World Health Organization (WHO), more than 1400 million people are suffering from nosocomial infections every day around the world, of which 60% of bacterial infections are related to the medical devices used. Postoperative infection of orthopedics and the like can directly cause the wound of a patient to be not healed for a long time, often can cause operation failure, even can cause complications such as chronic osteomyelitis and the like, not only brings great physical and mental pain and heavy economic burden to the patient, but also can cause negative effects of different degrees to hospitals, society and the like. Therefore, research and development of medical titanium alloy materials with the function of resisting bacterial infection have great social and economic significance for eliminating or reducing bacterial infectious diseases caused by related medical instruments.
The defects of the prior art are as follows: the medical pure titanium for the implant at present cannot cope with the bacterial infection environment with higher bacterial concentration or stronger bacterial activity due to the biological inertia, so as to eliminate or reduce the bacterial infection risk caused by the relevant implanted medical equipment.
Disclosure of Invention
The invention aims to provide a high antibacterial titanium alloy used as a metal implant, namely, a proper amount of gallium element and copper element are added into the existing medical pure titanium, and a titanium gallium phase is precipitated in a titanium matrix through special antibacterial heat treatment, so that the medical titanium alloy has stronger antibacterial effect. The novel antibacterial titanium alloy material can be widely applied to various titanium metal medical instruments used in the medical clinical fields of stomatology, orthopedics and the like so as to reduce the risk of bacterial infection induced by metal implants.
The technical scheme of the invention is as follows:
a highly antibacterial titanium alloy as a metal implant, characterized in that: the antibacterial stainless steel comprises the following chemical components in percentage by weight: ga: 0.5% to 5.0% (preferably 1.5% to 3.5%), Cu: 1.0-3.0% (preferably 1.5-2.5%), and the balance of Ti and inevitable impurities, wherein the content of impurity elements in the alloy meets the corresponding requirements in national standards of medical antibacterial titanium alloys.
In the composition design of the high antibacterial titanium alloy, gallium (Ga) is the most important alloying element in the alloy, and the Ga can form trivalent Ti with Ti in a certain temperature range according to a Ti-Ga binary phase diagram (figure 2)3A Ga phase. When the proper heat treatment condition is ensured, the Ga-rich phase can be uniformly dispersed and precipitated in the Ti matrix. When the content of Ga is low, even though special heat treatment is carried out, a Ga-rich phase is not easy to precipitate in a Ti matrix, and sufficient concentration of Ga ions cannot be precipitated when the Ti matrix is contacted with a solution medium, so that the normal proliferation activity of bacteria is inhibited, and the antibacterial effect of the Ga ions is fully exerted. When the Ga content is relatively excessively high, excessive Ga-rich phase may cause severe degradation of hot workability and cold formability of pure Ti, affecting practical use thereof. In addition, the high concentration of Ga ions released by excessive Ga-rich phase precipitation also affectsThe biological safety of pure Ti limits the practical application of pure Ti as a medical purpose.
As another alloying element Cu of the antibacterial titanium alloy, certain Ti can be precipitated under the aging system of the invention2And the Cu antibacterial phase provides a certain antibacterial function.
The invention also provides a special antibacterial heat treatment process of the antibacterial titanium alloy, which is also an important component of the invention and specifically comprises the following steps:
hot processing: homogenizing at 850-;
annealing heat treatment: treating at 650-700 deg.C for 0.5-3 hr, and cooling with air or water to room temperature.
Aging heat treatment: treating at 500 ℃ and 600 ℃ for 0.5-10 hours, and cooling in air or water to room temperature. The purpose is to ensure that enough Ga-rich phase can be separated out from a pure Ti matrix to play a role in resisting bacterial infection.
Therefore, the antibacterial titanium alloy for the implant innovatively realizes the perfect combination of Ga ions and Cu ions in titanium, endows the novel titanium alloy with stronger antibacterial infection resistance on the premise of ensuring good mechanical property and corrosion resistance, and can remarkably reduce the bacterial infection risk caused by the use of medical instruments such as titanium alloy for metal implants in the prior medical technology.
The invention has the beneficial effects that:
1. through experimental research, 0.5-5.0% (weight percentage) of Ga element is added into the existing medical pure titanium, and the medical antibacterial titanium metal new material with a stronger antibacterial function is obtained.
2. The antibacterial titanium alloy can be widely applied to various titanium metal medical instruments used in medical clinical fields of stomatology, orthopedics and the like.
Drawings
FIG. 1 shows the killing of Escherichia coli by antibacterial titanium alloy (bacteria concentration is 10)7Photographs of bactericidal effect of CFU/m L), (a) a Ga-containing titanium alloy (example 2), and (b) pure medical titanium.
FIG. 2 is a Ti-Ga binary phase diagram.
Detailed Description
According to the chemical composition range set by the antibacterial titanium alloy, 50 kg of vacuum consumable furnace is adopted to smelt the Ti-Ga alloy of the invention shown in the examples 1-7 and the pure Ti metal of the comparative example of the furnace 1, and the chemical compositions are shown in the table 1.
The hot processing technology comprises the following steps: homogenizing at 900 ℃ for 2 hours, cogging and forging, forging into a blank in multiple passes, and performing final forging at 770 ℃;
annealing heat treatment: treating at 680 deg.C for 1 hr, and air cooling to room temperature.
Aging heat treatment: treating at 520 deg.C for 5 hr, and air cooling to room temperature.
TABLE 1 chemical composition
1. Detection of antibacterial Properties
The sterilization rate of ordinary pure Ti and novel Ti-Ga antibacterial titanium alloy in the shown examples and comparative examples after the action of common infectious bacteria (escherichia coli and staphylococcus aureus) is quantitatively tested according to relevant standards of ' JIS Z2801-2000 ' antibacterial processed product-antibacterial property test method and antibacterial effect ' and GB/T2591-2003 ' antibacterial property test method and antibacterial effect ' respectively, wherein the sterilization rate is calculated by the formula of (%) sterilization rate ═ × 100 (blank control sample viable count-pure Ti or antibacterial titanium alloy viable count)/blank control viable count), the comparison sample viable count is viable count after bacterial culture under a single blank medium condition, and the Ti or antibacterial titanium alloy viable count is viable count after bacterial culture on pure Ti metal and novel antibacterial titanium alloy, wherein the antibacterial material is a material with the sterilization rate of more than 90%.
2. Evaluation of biosafety
The antibacterial titanium alloy and the pure Ti metal of the examples are subjected to related biological evaluation according to the national standard GBT16886.5-2003, and the cytotoxicity of L929 (mouse fibroblasts) of the titanium metal of the examples and the titanium metal of the comparative examples is evaluated in 1-7 days, wherein the grades 0 and 1 meet the requirements of biomedical materials.
The results of the bactericidal rate and cytotoxicity are shown in table 2. Test results show that the antibacterial titanium alloy provided by the invention has better antibacterial performance and biosafety. Among them, the antibacterial titanium alloy having a preferable Ga content has the best antibacterial efficiency and biosafety combined performance.
TABLE 2 Sterilization Rate and cytotoxicity results of examples and comparative examples
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (6)
1. A highly antibacterial titanium alloy as a metal implant, characterized in that: the antibacterial titanium alloy comprises the following chemical components in percentage by weight: ga: 0.5% -2.0% or 2.3% -5.0%, Cu: 1.0-3.0%, and the balance of Ti and inevitable impurities;
annealing heat treatment: treating at 650-700 deg.c for 0.5-3 hr, and air cooling or water cooling to room temperature;
aging heat treatment: treating at 500 ℃ and 600 ℃ for 0.5-10 hours, and cooling in air or water to room temperature;
the titanium alloy has a concentration of 107The bacteria of CFU/m L have effective antibacterial effect.
2. The titanium alloy of claim 1, wherein: the chemical components by weight percentage are as follows: ga: 1.5% -2.0% or 2.3% -3.5%, Cu: 1.5-2.5 percent, and the balance of Ti.
3. A method of producing the titanium alloy according to claim 1, characterized by: the antibacterial titanium alloy is obtained by adopting a vacuum consumable smelting mode.
4. A method for producing a titanium alloy as claimed in claim 3, wherein: the titanium alloy obtained by smelting adopts the following hot processing technology:
hot processing: homogenizing at 850-.
5. Use of the titanium alloy of claim 1 for the preparation of various types of titanium metal medical devices used in the medical clinical field.
6. Use according to claim 5, characterized in that: the titanium alloy is used for preparing titanium metal medical instruments for stomatology and orthopaedics.
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