CN101988166A - TiNiAg memory alloy with antibacterial function and preparation method thereof - Google Patents

Abstract

The invention provides a TiNiAg memory alloy with the antibacterial function and a preparation method thereof. The TiNiAg memory alloy contains 20%-80% of nickel, 0.1%-10% of silver and the balance of titanium by atomic percent. The alloy not only has good shape memory effect and superelasticity, but also has good matching of mechanical properties. Simultaneously, the alloy material has good corrosion resistance and biocompatibility in simulated body fluid, and cytotoxicity is in the same level of a TiNi alloy. In addition, the alloy material has a broad antimicrobial spectrum and can well inhibit Staphylococcus aureus, Escherichia coli, Staphylococcus epidermidis and other gram-negative and positive bacteria.

Description

Has TiNiAg memorial alloy of antibacterial and preparation method thereof

Technical field

What the present invention relates to is a kind of shape memory alloy, the invention still further relates to a kind of preparation method of shape memory alloy.Specifically a kind of shape memory alloy and preparation method thereof with medical antibacterial function.

Background technology

In in the past 30 years, the TiNi binary alloy becomes after stainless steel, vitallium, pure titanium, titanium aluminum vanadium alloy at the another metallic substance that is able to widespread use of medical field because of its good shape memory effect, super-elasticity, mechanical property, corrosion resistance, radiopacity, nucleus magnetic resonance do not have characteristics such as the property of influence.

When the fundamental characteristics of TiNi binary alloy such as shape memory effect or super-elasticity not being changed, in order to pursue certain characteristic, for example high transformation temperature, wide HYSTERESIS OF PHASE TRANSFORMATION TEMPERATURE, narrow HYSTERESIS OF PHASE TRANSFORMATION TEMPERATURE, low transformation temperature etc., people are base with the TiNi binary alloy just, realize by adding a spot of the 3rd constituent element.For example, the adding of copper (Cu) can make the TiNi alloy inhibition M _sTemperature suppresses Ti to the susceptibility of composition ₃Separating out of Ni4 phase, the hysteresis of phase transformation obviously narrows down, and produces the second order phase transformation.

Silver (Ag) is used widely in the bio-medical field.Silver can be divided into dental casting alloy and dental amalgam alloy as dental material.Also have acupuncture acupuncture needle, the silver-colored suturing with thread management injury of the bone and reticular tissue, silver-colored drainage tube.Prior function is that elements A g has bacteria resistance function.No matter silver still exists with particle, ionic species with the alloying element interpolation, and certain bacteriostatic action is all arranged, and wherein the silver-colored fungistatic effect of particle, ionic species existence is best.But, at present also seldom to the report of the TiNi alloy that contains Ag.Ag is joined in the TiNi alloy, the TiNi alloy is carried out functionalization, this TiNiAg alloy that possesses antibacterial may obtain certain application at medical instruments field.But, because the solid solubility of Ag in the TiNi alloy is very low under the room temperature, 0.26% weight percent (Oh KT, Joo UH, Park GH, Hwang CJ, Kim KN.J Biomed Mater Res B ApplBiomater 2006 only; 76:306-314), the TiNi alloy of high Ag content can't prepare, and yet there are no the patent report of TiNiAg alloy.

Summary of the invention

The object of the present invention is to provide a kind of have good shape memory effect and super-elasticity, the mechanical property coupling is good, the TiNiAg memorial alloy with antibacterial of broad-spectrum antimicrobial.The present invention also aims to provide a kind of preparation method with TiNiAg memorial alloy of antibacterial.

The object of the present invention is achieved like this:

TiNiAg memorial alloy with antibacterial of the present invention comprises atomic percent and is 20%～80% nickel, 0.1%～10% silver, and the titanium of surplus.

The total amount atomic percent of impurity that the present invention has the TiNiAg memorial alloy of antibacterial is less than 10%.

TiNiAg memorial alloy with antibacterial of the present invention is to adopt such method to prepare:

Step 1: by atomic percent is the titanium that the proportioning of the titanium of 20%～80% nickel, 0.1%～10% silver and surplus takes by weighing purity 99.9%, and purity is 99.9% nickel, and purity is 99.9% silver;

Step 2: titanium, nickel, silver material that step 1 takes by weighing are put into copper crucible refrigerative non-consumable vacuum melting furnace or vacuum induction melting furnace, suction 2 * 10 ^-4～2 * 10 ^-3Pa charges into high-purity argon gas to 5～10 * 10 ⁴Pa, under 1500～2500 ℃ of smelting temperatures, melt back 3～6 times makes TiNiAg alloy ingot;

Step 3: the TiNiAg alloy ingot that step 2 makes is put into heat treatment furnace, and 400～900 ℃ of down insulations 1～5 hour, water-cooled makes the TiNiAg alloy ingot of homogeneous grain size;

Step 4: the TiNiAg alloy ingot that step 3 is made by forge, the mode of rolling, drawing, obtain the TiNiAg alloy of desired shape;

Step 5: with the TiNiAg alloy that step 4 makes anneal, thermal treatment such as solid solution, timeliness, promptly obtain possessing the TiNiAg memorial alloy of antibacterial.

The TiNiAg alloy of described desired shape is sheet material, bar or wire rod.

TiNiAg memorial alloy with antibacterial of the present invention has following having a few: 1, have good shape memory effect or super-elasticity; 2, the mechanical property coupling is good, yield strength 200～600MPa, and tensile strength 400～1000MPa, unit elongation is more than 15%.3, has excellent erosion resistance; 4, the ion stripping quantity is little, and is little to tissue toxicity.5, lower to human toxicity; 6, anti-microbial property is good, and broad-spectrum antimicrobial all has good inhibition effect to various bacteria.

Though the solubleness of Ag in the TiNi matrix is very low under the room temperature, at high temperature Ag may have higher solubleness.The present invention adopts copper crucible refrigerative smelting furnace, quickened the process of cooling of alloy after melting, make Ag in melting, process of cooling, be difficult for separating out, improved the Ag content in the alloy greatly, thereby provide good assurance for the broad-spectrum antimicrobial characteristic of alloy.Though the TiNiAg alloy Ag content of the preparation of the present invention simultaneously is much higher than the solid solubility of Ag in the TiNi matrix, the content of same Ti, two kinds of elements of Ni is compared still very low, therefore the mechanical property of alloy, biocompatibility etc. is not produced big disadvantageous effect.

Alloy material of the present invention need contain the Ag simple substance of 0.1% atomic percent at least to guarantee its antibacterial effect.Alloy of the present invention not only has good shape memory effect and super-elasticity, and the mechanical property coupling is good.Simultaneously, this alloy material has good erosion resistance and biocompatibility in simulated body fluid, and cytotoxicity and TiNi alloy are all one-level.In addition, this alloy material broad-spectrum antimicrobial all has good inhibition effect to various gram-negatives, positive bacterias such as streptococcus aureus, intestinal bacteria, staphylococcus epidermidiss.

Description of drawings

Fig. 1 is the room-temperature mechanical property of a concrete scheme of the present invention;

Fig. 2 is the stretching memory effect of a concrete scheme of the present invention;

Fig. 3 is the corrosion resistance curve of a concrete scheme of the present invention;

Fig. 4 is the cytotoxicity result of a concrete scheme of the present invention;

Fig. 5 is the antibacterial effect to streptococcus aureus of a concrete scheme of the present invention.

Embodiment

For example the present invention is done more detailed description below:

1, preparation Ti _48.5Ni _48.5Ag ₃Alloy:

Step 1: take by weighing the titanium of purity 99.9% by proportioning, purity is 99.9% nickel, and purity is 99.9% silver;

Step 2: titanium, nickel, silver material that step 1 takes by weighing are put into the non-consumable vacuum melting furnace, suction 5 * 10 ^-4Pa charges into high-purity argon gas to 5 * 10 ⁴Pa, melt back 3～6 times makes Ti _48.5Ni _48.5Ag ₃The alloy ingot;

Step 3: the TiNiAg alloy ingot that step 2 makes is put into heat treatment furnace, and 800 ℃ of down insulations 2 hours, water-cooled makes the TiNiAg alloy ingot of homogeneous grain size;

Step 4: the Ti that step 3 is made _48.5Ni _48.5Ag ₃The alloy ingot obtains the TiNiAg sheet alloy of desired shape by rolling mode;

Step 5: the Ti that step 4 is made _48.5Ni _48.5Ag ₃Alloy carries out solution treatment, promptly obtains possessing the Ti of antibacterial _48.5Ni _48.5Ag ₃Memorial alloy.

Adopt wire cutting method, at Ti _48.5Ni _48.5Ag ₃Cut the standard tensile sample on the sheet alloy, adopt Instron3365 type universal testing machine to carry out Mechanics Performance Testing, tensile strain rate is 4 * 10 ^-4/ s, the about 200MPa of the yield strength of alloy, tensile strength 720MPa, unit elongation 18%.(see figure 1)

Adopt the shape memory effect of stretching method beta alloy, be out of shape 7%, 230 ℃ of heating under the room temperature and reply, its recoverable strain is 6.4% (see figure 2).

In simulate saliva to Ti _48.5Ni _48.5Ag ₃Alloy carries out electro-chemical test, and the passivation current density of alloy is lower, and about 10 ^-5A/cm ²Magnitude possesses good erosion resistance.(see figure 3)

Preparation Ti _48.5Ni _48.5Ag ₃The alloy vat liquor carries out cell toxicity test, and the toxicity of alloy is one-level, and is same with the binary TiNi alloy phase.(see figure 4)

To Ti _48.5Ni _48.5Ag ₃Alloy carries out the anti-microbial property test, and alloy is good to the rejection of streptococcus aureus.(see figure 5)

2, preparation Ti _48.5Ni _44.5Ag ₇Alloy:

Step 1: take by weighing the titanium of purity 99.9% by proportioning, purity is 99.9% nickel, and purity is 99.9% silver;

Step 2: titanium, nickel, silver material that step 1 takes by weighing are put into the non-consumable vacuum melting furnace, suction 5 * 10 ^-4Pa charges into high-purity argon gas to 5 * 10 ⁴Pa, melt back 3～6 times makes Ti _48.5Ni _48.5Ag ₃The alloy ingot;

Step 3: the TiNiAg alloy ingot that step 2 makes is put into heat treatment furnace, and 800 ℃ of down insulations 2 hours, water-cooled makes the TiNiAg alloy ingot of homogeneous grain size;

Step 4: the Ti that step 3 is made _48.5Ni _44.5Ag ₇The alloy ingot obtains the TiNiAg sheet alloy of desired shape by rolling mode;

Step 5: the Ti that step 4 is made _48.5Ni _44.5Ag ₇Alloy carries out solution treatment, promptly obtains possessing the Ti of antibacterial _48.5Ni _44.5Ag ₇Memorial alloy.

3, preparation Ti ₆₄Ni ₃₀Ag ₆Alloy:

Step 1: take by weighing the titanium of purity 99.9% by proportioning, purity is 99.9% nickel, and purity is 99.9% silver;

Step 2: titanium, nickel, silver material that step 1 takes by weighing are put into the non-consumable vacuum melting furnace, suction 5 * 10 ^-4Pa charges into high-purity argon gas to 5 * 10 ⁴Pa, melt back 3～6 times makes Ti _48.5Ni _48.5Ag ₃The alloy ingot;

Step 3: the TiNiAg alloy ingot that step 2 makes is put into heat treatment furnace, and 800 ℃ of down insulations 2 hours, water-cooled makes the TiNiAg alloy ingot of homogeneous grain size;

Step 4: the Ti that step 3 is made ₆₄Ni ₃₀Ag ₆The alloy ingot obtains the TiNiAg sheet alloy of desired shape by rolling mode;

Step 5: the Ti that step 4 is made ₆₄Ni ₃₀Ag ₆Alloy carries out solution treatment, promptly obtains possessing the Ti of antibacterial ₆₄Ni ₃₀Ag ₆Memorial alloy.

Claims (4)

1. TiNiAg memorial alloy with antibacterial is characterized in that comprising atomic percent and is 20%～80% nickel, 0.1%～10% silver, and the titanium of surplus.

2. the TiNiAg memorial alloy with antibacterial according to claim 1 is characterized in that the total amount atomic percent of impurity is less than 10%.

3. preparation method with TiNiAg memorial alloy of antibacterial is characterized in that:

Step 1: by atomic percent is the titanium that the proportioning of the titanium of 20%～80% nickel, 0.1%～10% silver and surplus takes by weighing purity 99.9%, and purity is 99.9% nickel, and purity is 99.9% silver;

Step 2: titanium, nickel, silver material that step 1 takes by weighing are put into copper crucible refrigerative non-consumable vacuum melting furnace or vacuum induction melting furnace, suction 2 * 10 ^-4～2 * 10 ^-3Pa charges into high-purity argon gas to 5～10 * 10 ⁴Pa, under 1500～2500 ℃ of smelting temperatures, melt back 3～6 times makes TiNiAg alloy ingot;

Step 3: the TiNiAg alloy ingot that step 2 makes is put into heat treatment furnace, and 400～900 ℃ of down insulations 1～5 hour, water-cooled makes the TiNiAg alloy ingot of homogeneous grain size;

Step 4: the TiNiAg alloy ingot that step 3 is made by forge, the mode of rolling, drawing, obtain the TiNiAg alloy of desired shape;

Step 5: with the TiNiAg alloy that step 4 makes anneal, thermal treatment such as solid solution, timeliness, promptly obtain possessing the TiNiAg memorial alloy of antibacterial.

4. the preparation method with TiNiAg memorial alloy of antibacterial according to claim 3 is characterized in that: the TiNiAg alloy of described desired shape is sheet material, bar or wire rod.

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