CN108220683A - A kind of low alloying Zn-Mn-Ag or Zn-Mn-Ca alloys and preparation method - Google Patents

Abstract

The invention discloses a low-alloyed Zn-Mn-Ag or Zn-Mn-Ca alloy and a preparation method thereof, and belongs to the technical field of composition design and preparation of non-ferrous metal alloy materials. The zinc alloy provided by the present invention is composed of the following components by mass percentage: (1) 0.1-5% Mn, 0.05-5% Ag, and the balance is Zn; (2) 0.1-5% Mn, 0.02-2 % Ca, the balance is Zn. Through rolling or extruding plastic deformation of the as-cast alloy obtained by vacuum smelting, the alloy structure is optimized, so that the alloy has good comprehensive mechanical properties. The rolling includes 4 process routes, and the extrusion includes 1 process route. The obtained deformed Zn-Mn-Ag and Zn-Mn-Ca alloys can be used as instrument shells, decorations, models and electrical parts and the like. In addition, the above-mentioned alloys also meet the mechanical properties required for biomedical implant materials, can be degraded in vivo and have excellent cell compatibility, and can be used as biomedical materials for implantation into animals or humans.

Description

A low-alloyed Zn-Mn-Ag or Zn-Mn-Ca alloy and its preparation method

technical field

The invention relates to the composition design, preparation method and application field of low-alloyed Zn-Mn-Ag and Zn-Mn-Ca alloys, and belongs to the technical field of composition design, preparation and processing of non-ferrous metal alloy materials.

Background technique

Zinc is an important metal material with abundant reserves and low cost in my country. Zinc has excellent corrosion resistance and is widely used as a coating protection material for steel. It has good casting performance and can be used in sand mold, metal mold and die-casting production, and can produce thin-walled and complex castings. Zinc is also widely used as a power dry battery due to its unique electrochemical properties. In addition, zinc and its alloys have excellent rolling performance, and their plates and strips are used in construction, machinery, transportation, instrumentation and other fields. In recent years, the potential application of zinc and its alloys in biodegradable biomedical materials has attracted extensive attention. The reported biomedical metal materials can be divided into non-degradable and degradable types. Non-degradable medical metal materials, such as 316L stainless steel, require a second operation to remove them after being implanted in the human body, which will increase the pain of the patient. However, medical metal materials that degrade too quickly, such as magnesium alloys, are difficult to meet the supporting force required by medical implants in the later stage, and may easily cause blood vessels to block again. The degradation rate of zinc in the human body is lower than that of magnesium but higher than that of iron, so it has recently gained attention as an important category of degradable biomedical metal materials.

To expand the use of zinc alloys, we must pay attention to the development of deformed zinc alloys. The existing deformed zinc alloys are mainly Zn-Al and Zn-Cu series zinc alloys, which are used in construction, machinery, transportation and other fields. The biomedical zinc alloys reported in the literature include Zn-Mg, Zn-Cu, Zn-Li, Zn-Sr, and Zn-Ag zinc alloys. Al is considered to cause Alzheimer's disease, and it is generally not used as an additive element in biomedical zinc alloys for implants.

The mechanical properties of pure zinc are poor, and the addition of manganese can improve the mechanical properties and wear resistance of the alloy. The addition of silver and calcium can refine the grains, and the solid solubility of silver in zinc is large, which can Improve the strength of zinc alloys by solid solution strengthening or age strengthening. In addition, zinc, manganese, silver and calcium are essential trace elements for the human body. Adults need 13-15 mg of zinc per day. Zinc is the coenzyme of hundreds of enzymes and plays an important role in maintaining cell structure, enhancing immunity and anti-aging. Manganese has a fat-removing effect, can effectively improve lipid metabolism in patients with atherosclerosis, participate in hematopoiesis, and can also enhance immunity. Silver can play a role in disinfection and sterilization. Nano-silver particles, as a new generation of natural antibacterial agent, can effectively sterilize bacteria and promote wound healing. Calcium is the main component of teeth and bones. It participates in activities such as heart beat, muscle contraction and blood coagulation. It can improve blood viscosity, maintain cell function, eliminate excess blood fat and cholesterol, and improve blood vessel elasticity.

At present, there are no literature or patent reports on the composition, preparation method and performance of the low alloyed Zn-Mn-Ag and Zn-Mn-Ca alloy invented by this patent, and it is proposed to combine this Zn-Mn-Ag and Zn- Mn-Ca alloys are used in electrical parts, decorations and biomedical degradable materials.

Contents of the invention

The invention aims to provide composition design, preparation method and application field of low alloyed Zn-Mn-Ag and Zn-Mn-Ca alloys. The zinc alloy prepared by the invention has excellent mechanical properties and is suitable for the fields of instrument shells, decorations, models, electrical parts and the like. And because the Zn, Mn, Ag and Ca elements are essential trace elements for the human body, the above alloys can also be used for biomedical implant materials.

The Zn-Mn-Ag or Zn-Mn-Ca alloy provided by the present invention includes Zn element, Mn element, Ag element and Ca element. The composition range of alloying elements is: (1) 0.1-5% Mn, 0.05-5% Ag, and the balance is Zn; (2) 0.1-5% Mn, 0.02-2% Ca, and the balance is Zn, The above-mentioned ingredients are calculated by mass percentage.

As above-mentioned Zn-Mn-Ag or the preparation method of Zn-Mn-Ca alloy, concrete preparation steps are as follows:

1) Casting: Melting the zinc alloy with a vacuum induction melting furnace, using pure Zn, pure Mn, pure Ag and pure Ca as raw materials, heating to 750 ° C ~ 850 ° C under the protection of argon, and then refining and heat preservation for 3 ~ 15 minutes, Finally, it is poured into a high-purity graphite mold and air-cooled to room temperature.

2) Plastic processing: the processing method includes at least one of rolling or extrusion.

The above-mentioned rolling is divided into 4 kinds of rolling process routes, and the finished plate can be made according to any of these 4 kinds of process routes, which are respectively:

(1) Homogenization heat treatment → hot rolling → finished product;

(1) Homogenization heat treatment → hot rolling → warm rolling → finished product;

(3) Homogenization heat treatment → hot rolling → solid solution → cold rolling → finished product;

(4) Homogenization heat treatment → hot rolling → warm rolling → solid solution → cold rolling → finished product.

The above-mentioned extrusion process route is: homogenization heat treatment→extrusion→finished product.

The above-mentioned homogenization heat treatment process is 280-390°C for 5-20 hours; the hot rolling temperature is 200-350°C, and the deformation is 40-95%; the warm rolling temperature is 80-200°C, and the deformation is 30-95%; The solid solution process is 340-390 ° C for 10 minutes to 2 hours and then water quenching; the cold rolling deformation is 50-98%; further, the extrusion temperature is 150-350 ° C, and the extrusion ratio is 10-90 .

The Zn-Mn-Ag or Zn-Mn-Ca alloy of the invention has good mechanical properties and is easy to process and shape. In addition, the present invention selects Mn, Ag and Ca, which are beneficial to the human body, as additional elements to optimize the structure and properties of zinc, so that the alloy has good mechanical properties and biocompatibility.

The Zn-Mn-Ag and Zn-Mn-Ca alloys provided by the invention can be used for instrument shells, decorations, models, electrical parts and the like. In addition, the zinc alloy of the present invention can also be used in biomedical implant materials, such as bone nails, fixation screws, tracheal stents, urethral stents, and the like.

The present invention has the following advantages:

(1) The Zn-Mn-Ca alloy designed by the present invention has low total content of added elements, low alloy cost, and is suitable for wide-scale popularization and use;

(2) The Zn-Mn-Ag alloy designed by the present invention, when used as a biomedical material, the addition of the Ag element strengthens the antibacterial properties of the alloy, making the alloy suitable for biological materials with special requirements;

(3) In the Zn-Mn-Ag and Zn-Mn-Ca alloys designed by the present invention, both the Ag element and the Ca element can refine the grains, especially the Ca element, which significantly refines the as-cast structure of the alloy. In addition, the solid solubility of Ag element in zinc is relatively large, so that the deformed zinc alloy can further improve the strength of the alloy through solid solution strengthening or aging strengthening. When the zinc alloy designed in the invention is used in biomedical materials, it can simultaneously meet the strength and plasticity required by medical implants, and the alloy can be degraded in vivo and has good biocompatibility.

Description of drawings

Fig. 1 is the metallographic photograph of the as-cast zinc alloy prepared in embodiment 1.

Among them, Fig. 1a is a metallographic photo of as-cast Zn-0.8Mn-0.4Ag alloy.

Figure 1b is a metallographic photo of the as-cast Zn-0.8Mn-0.4Ca alloy.

Fig. 2 is the tensile stress-strain curve of the warm-rolled zinc alloy sheet prepared in Example 1.

Figure 2a is the tensile stress-strain curve of the warm-rolled Zn-0.8Mn-0.4Ag alloy plate.

Figure 2b is the tensile stress-strain curve of the warm-rolled Zn-0.8Mn-0.4Ca alloy sheet.

Fig. 3 is the tensile stress-strain curve of the hot-rolled Zn-0.8Mn-0.8Ag alloy plate prepared in Example 2.

Fig. 4 is the tensile stress-strain curve of the extruded zinc alloy rod prepared in Example 5.

Figure 4a is the tensile stress-strain curve of the extruded Zn-0.8Mn-0.4Ag alloy rod.

Figure 4b is the tensile stress-strain curve of the extruded Zn-0.8Mn-0.4Ca alloy rod.

Fig. 5 is the tensile stress-strain curve of the extruded Zn-0.8Mn-0.8Ag alloy rod prepared in Example 6.

Detailed ways

The experimental methods used in the following examples are conventional methods unless otherwise specified.

Materials used in the following examples can be obtained from commercial sources unless otherwise specified.

The percentages used in the following examples are mass percentages.

The following examples are intended to illustrate the present invention without further limiting the invention.

Example 1:

The warm-rolled Zn-0.8Mn-0.4Ag and Zn-0.8Mn-0.4Ca alloy sheets were prepared and the mechanical properties of the materials were measured.

Process route: casting→homogenizing heat treatment→hot rolling→warm rolling→finished product.

The raw material that smelting uses is pure Zn (99.99%), pure Mn (99.9%), pure Ag (99.5%) and pure Ca (99.99%), carry out batching according to following mass percentage: (1) Mn is 0.8%, Ag 0.4%, the rest is Zn; (2) Mn is 0.8%, Ca is 0.4%, and the rest is Zn. Put the batched raw materials into the _Al2O3 crucible of _the vacuum induction melting furnace. After that, the vacuum is drawn, and argon gas is introduced when the pressure in the furnace drops to about 30Pa, and heating is started when the pressure reaches 0.035MPa. When the temperature rises to 780°C, heating is stopped and refining is carried out. The refining time is 5 minutes. During the whole melting process Perform electromagnetic stirring. Then the alloy melt was poured into a cylindrical high-purity graphite mold with a diameter of 80mm, and air-cooled to room temperature to prepare Zn-0.8Mn-0.4Ag and Zn-0.8Mn-0.4Ca alloy ingots. Fig. 1 is the metallographic photograph of the as-cast zinc alloy prepared by smelting, compared with the as-cast structure of pure zinc, the as-cast structure of the alloy has been significantly refined, and the fineness of the Zn-0.8Mn-0.4Ca alloy effect is particularly pronounced.

A plate with a thickness of 30mm was cut from the obtained alloy ingot, and homogenized heat treatment was carried out. The specific process of heat treatment was 380°C for 20 hours, and water quenching after the heat preservation was completed.

After the heat treatment is completed, the plate is first hot-rolled. The specific process is: heat the plate at 320°C for 1 hour, and then take it out of the heating furnace for rolling. After 4 passes, the plate is rolled from 30mm thick to 10mm thick. The content is 66.7%. During the rolling process, the furnace is annealed after every 2 passes. The annealing temperature is still 320°C, and the holding time is 10 minutes. After the hot rolling, the plate is water quenched. Then carry out warm rolling to the above plate, the specific process is: heat the hot rolled plate at 150°C for 30 minutes and then take it out of the furnace for 2 passes of rolling to further reduce its thickness to 5mm, then water quenching, the deformation amount is 50%. After the above plate is hot rolled and warm rolled, the thickness is reduced from 30mm to 5mm, and the total deformation is 83.3%.

According to "GB/T 228.1-2010 Metal Materials Tensile Test Part 1: Room Temperature Test Method", prepare the plate tensile sample, use the universal material tensile mechanics testing machine to carry out the tensile test at room temperature, and the tensile strain rate is 10 ^-3 /s. The tensile engineering stress-strain curves of the warm-rolled Zn-0.8Mn-0.4Ca and Zn-0.8Mn-0.4Ag alloys are shown in Figure 2. It can be seen that the tensile yield strength of the Zn-0.8Mn-0.4Ag alloy is 118.7MPa, The tensile yield strength is 221.4MPa, the elongation is 58.4%; the yield strength of the Zn-0.8Mn-0.4Ca alloy is 153.7MPa, the tensile strength is 246.3MPa, and the elongation is 6.2%.

Example 2:

The hot-rolled Zn-0.8Mn-0.8Ag alloy sheet was prepared and the mechanical properties of the material were measured.

Process route: casting→homogenizing heat treatment→hot rolling→finished product.

The composition of the alloy is as follows: Mn is 0.8%, Ag is 0.8%, and the rest is Zn. A Zn-0.8Mn-0.8Ag alloy ingot was prepared according to the smelting method provided in Example 1, and a plate with a thickness of 20 mm was cut from the ingot. Homogenized heat treatment is first performed on the plate at a temperature of 360°C for 6 hours, and then water quenched. Afterwards, the plate is hot-rolled, and the plate is kept at 320° C. for 1 hour, and then the thickness is reduced to 2 mm through 5 rolling passes, and the total deformation is 90%.

According to the method provided in Example 1, the mechanical properties of the hot-rolled Zn-0.8Mn-0.8Ag alloy sheet were tested. The tensile engineering stress-strain curve of the hot-rolled Zn-0.8Mn-0.8Ag alloy is shown in Figure 3. It can be seen that the yield strength is 144.1MPa, the tensile strength is 212.4MPa, and the elongation is 56.3%.

Example 3:

Cold-rolled Zn-0.8Mn-0.4Ag and Zn-0.8Mn-0.4Ca alloy sheets were prepared and the mechanical properties of the materials were measured.

Process route: casting→homogenizing heat treatment→hot rolling→warm rolling→solution→cold rolling→finished product.

The composition of the alloy is as follows: (1) Mn is 0.8%, Ag is 0.4%, and the rest is Zn; (2) Mn is 0.8%, Ca is 0.4%, and the rest is Zn. Perform alloy casting→homogenizing heat treatment→hot rolling→warm rolling according to the method provided in Example 1 to obtain warm-rolled Zn-0.8Mn-0.4Ag and Zn-0.8Mn-0.4Ca alloy sheets with a thickness of 5mm. Firstly, the warm-rolled Zn-0.8Mn-0.4Ag and Zn-0.8Mn-0.4Ca alloy sheets are subjected to solution treatment, and the specific process is to keep the temperature at 380° C. for 1 hour, and then water quench. Then the warm-rolled Zn-0.8Mn-0.4Ag and Zn-0.8Mn-0.4Ca alloy plates are fed into the cold rolling mill, and the thickness is reduced to 1mm after 4 passes, and the cold rolling deformation reaches 90%.

According to the method provided in Example 1, the mechanical properties of the cold-rolled Zn-0.8Mn-0.4Ag and Zn-0.8Mn-0.4Ca alloy sheets were tested. The yield strength of the cold-rolled Zn-0.8Mn-0.4Ag alloy sheet is 162.8MPa, the tensile strength is 214.9MPa, and the elongation is 28.2%; the yield strength of the cold-rolled Zn-0.8Mn-0.4Ca alloy sheet is 261.5 MPa, the tensile strength is 308.2MPa, and the elongation is 3.2%.

Example 4:

The cold-rolled Zn-0.8Mn-0.8Ag alloy sheet was prepared and the mechanical properties of the material were measured.

Process route: casting→homogenization heat treatment→hot rolling→solution→cold rolling→finished product.

The composition of the alloy is as follows: Mn is 0.8%, Ag is 0.8%, and the rest is Zn. Perform alloy casting→homogenizing heat treatment→hot rolling according to the method provided in Example 2 to obtain a hot-rolled Zn-0.8Mn-0.8Ag alloy plate with a thickness of 2mm. Firstly, the hot-rolled Zn-0.8Mn-0.8Ag alloy plate is subjected to solution treatment, and the specific process is to keep the temperature at 380° C. for 1 hour, and then water quench. Then the plate is sent into the cold rolling mill, and its thickness is reduced to 0.3 mm through 4 passes, and the cold rolling deformation is 85%.

According to the method provided in Example 1, the mechanical properties of the cold-rolled Zn-0.8Mn-0.8Ag alloy plate were tested. The yield strength of the obtained cold-rolled Zn-0.8Mn-0.8Ag alloy plate is 129.0MPa, the tensile strength is 179.0MPa, and the elongation is 68.5%;

Example 5:

The extruded Zn-0.8Mn-0.4Ag and Zn-0.8Mn-0.4Ca alloy rods were prepared and the mechanical properties of the materials were measured.

Process route: casting→homogenizing heat treatment→extrusion→finished product.

The composition of the above alloy is as follows: (1) Mn is 0.8%, Ag is 0.4%, and the rest is Zn; (2) Mn is 0.8%, Ca is 0.4%, and the rest is Zn. Zn-0.8Mn-0.4Ag and Zn-0.8Mn-0.4Ca alloy ingots were prepared according to the method provided in Example 1, and rods with a diameter of 40 mm were cut from the ingots. Homogenized heat treatment is carried out on the bar before extrusion. The heat treatment process is to keep warm at 380°C for 20 hours, and then water quench after the heat preservation is completed. Put the bar into an extrusion die at 230°C for 5 minutes, and then carry out vertical forward extrusion. A bar with a diameter of 10mm is extruded in one pass, and the extrusion ratio is 16. Extruded bars have good surface quality and no cracks.

According to "GB/T 228.1-2010 Metal Material Tensile Test Part 1: Room Temperature Test Method", the bar tensile sample was prepared, and the tensile test was carried out at room temperature using a universal material tensile mechanics testing machine, and the tensile strain rate was 2×10 ^-3 /s. The tensile engineering stress-strain curves of extruded Zn-0.8Mn-0.4Ca and Zn-0.8Mn-0.4Ag alloys are shown in Figure 4. It can be seen that the yield strength of Zn-0.8Mn-0.4Ag alloy is 160.0MPa, and the The tensile strength is 255.0MPa, the elongation is 65.6%; the yield strength of the Zn-0.8Mn-0.4Ca alloy is 254.1MPa, the tensile strength is 344.0MPa, and the elongation is 9.1%.

Embodiment 6:

The extruded Zn-0.8Mn-0.8Ag alloy rods were prepared and the mechanical properties of the materials were measured.

Process route: casting→homogenizing heat treatment→extrusion→finished product.

The composition of the above alloy is as follows: Mn is 0.8%, Ag is 0.8%, and the rest is Zn. A Zn-0.8Mn-0.8Ag alloy ingot was prepared according to the method provided in Example 1, and a rod with a diameter of 40 mm was cut from the ingot. Homogenized heat treatment is carried out on the bar before extrusion, the specific process is 360 ° C for 6 hours, and then water quenching. Put the bar into an extrusion die at 230°C for 5 minutes, and then carry out vertical forward extrusion. A bar with a diameter of 10mm is extruded in one pass, and the extrusion ratio is 16. Extruded bars have good surface quality and no cracks.

According to the method provided in Example 5, the mechanical properties of the extruded Zn-0.8Mn-0.8Ag alloy rod were tested. The tensile engineering stress-strain curve of the extruded Zn-0.8Mn-0.8Ag alloy is shown in Figure 5. It can be seen that the yield strength of the Zn-0.8Mn-0.8Ag alloy is 140.4MPa, the tensile strength is 252.3MPa, and the elongation was 68.0%.

Embodiment 7:

In vitro cytotoxicity tests were performed on the zinc alloys prepared in Examples 1-3.

In this example, an in vitro cytotoxicity test was performed on zinc alloys according to the national standard GB/T 16886.5-2003, and the cells used were L-929 cells. The cells were placed in the extract solution obtained from the degradation of the zinc alloy, and cultured in the incubator for 24 hours, 48 hours and 96 hours respectively. After the culture, the cell absorbance was measured by the MTT method and the relative proliferation rate was calculated. The results show that the relative value-added rate of the cells is above 80%, and the cytotoxicity is grade 1, so the degradation products of the Zn-Mn-Ag and Zn-Mn-Ca alloys in this example are non-toxic to the cells, and the alloys exhibit excellent cytotoxicity. compatibility.

Claims (4)

1. a kind of low alloying Zn-Mn-Ag or Zn-Mn-Ca alloys, it is characterised in that the composition range of alloying element is：(1) 0.1~5% Mn, 0.05~5% Ag, surplus Zn；(2) 0.1~5% Mn, 0.02~2% Ca, surplus Zn, on Ingredient is stated to calculate by percentage to the quality.

2. the preparation method of low alloying Zn-Mn-Ag as described in claim 1 or Zn-Mn-Ca alloys, it is characterised in that tool Preparation step is as follows：

(1) it casts：Using pure Zn, pure Mn, pure Ag or pure Ca as raw material, dispensing is carried out according to alloy proportion, is placed in argon gas atmosphere In vacuum induction melting furnace under protection, refining heat preservation 3~15 minutes, are then poured into graphite after being heated to 750 DEG C~850 DEG C Mold is hollow to be cooled to room temperature；

(2) plastic processing：Processing method includes at least one of rolling or extruding.

3. the preparation method of low alloying Zn-Mn-Ag as claimed in claim 2 or Zn-Mn-Ca alloys, it is characterised in that system Preparation Method is divided into 4 kinds of rolling mill practice routes, and any by this 4 kinds of process routes can finished product plank；

(1) heat treatment → hot rolling → finished product is homogenized；

(1) heat treatment → hot rolling → warm-rolling → finished product is homogenized；

(3) heat treatment → hot rolling → solid solution → cold rolling → finished product is homogenized；

(4) heat treatment → hot rolling → warm-rolling → solid solution → cold rolling → finished product is homogenized；

Above-mentioned homogenizing heat treatment keeps the temperature 5~20 hours for 280~390 DEG C；Hot-rolled temperature is 200~350 DEG C, deflection It is 40~95%；Warm-rolling temperature is 80~200 DEG C, and deflection is 30~95%；Solid solution craft keeps the temperature 10 points for 340~390 DEG C Water quenching is carried out behind clock~2 hour；Cold rolling reduction is 50~98%.

4. such as the preparation method of low alloying Zn-Mn-Ag or the Zn-Mn-Ca alloy in claim 2, it is characterised in that plasticity Extrusion process route is as follows in processing：Heat treatment → extruding → finished product is homogenized, homogenizing heat treatment is 280~390 DEG C Heat preservation 5~20 hours；Extrusion temperature is 150~350 DEG C, and extrusion ratio is 10~90.