CN115852305A - Method for alloying and preparing coating on surface of pure magnesium - Google Patents
Method for alloying and preparing coating on surface of pure magnesium Download PDFInfo
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- CN115852305A CN115852305A CN202211489820.2A CN202211489820A CN115852305A CN 115852305 A CN115852305 A CN 115852305A CN 202211489820 A CN202211489820 A CN 202211489820A CN 115852305 A CN115852305 A CN 115852305A
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Abstract
The invention discloses a method for alloying and preparing a coating on the surface of pure magnesium, which comprises the following steps: alloying on the surface of pure magnesium: the double glow plasma alloying technology is adopted, the used heat-insulating cover is a pure zinc plate and is connected with the cathode objective table, the heat-insulating cover is connected with the target zinc sheet, pure magnesium is used as a matrix and is connected with the other cathode electrode, and the cavity is used as an anode and is grounded; (2) preparing a composite coating: the plating treatment is carried out on the pure magnesium alloyed with zinc by adopting a magnetron sputtering technology, and one or two of high-purity metal oxide or noble metal is/are used as a target material. The invention adopts the surface alloying of the double-glow plasma to prepare the pure magnesium surface alloy layer which is taken as the transition layer, and then adopts the magnetron sputtering to realize the preparation of the functional coating on the transition layer.
Description
Technical Field
The invention relates to a surface modification method, in particular to a method for alloying and preparing a coating on the surface of pure magnesium.
Background
The magnesium and the magnesium alloy have the advantages of light specific gravity, high specific strength, good electromagnetic shielding performance, good shock resistance, easy processing, recyclability, good biocompatibility and degradability, and have wide application prospects in the fields of automobiles, aerospace and biomedicine. Currently, traditional biomedical metal implant materials, such as titanium, titanium alloys, stainless steel, are biologically inert, requiring a secondary operation to remove these implants, which greatly increases medical costs and delays the recovery process. Magnesium and its alloys are promising biodegradable implant materials because their elastic modulus and compressive yield strength approach those of human bone, thus avoiding stress shielding effects. However, the degradation rate of magnesium and its alloys is difficult to control and the surface strength is insufficient, thereby limiting its wide application in the biomedical field.
In order to overcome the disadvantages of magnesium and its alloys, surface modification has become an effective method for improving its corrosion resistance, mechanical properties and biocompatibility. Surface modification includes ion implantation, plasma spraying, laser plasma techniques, physical Vapor Deposition (PVD), and the like. Ion implantation is a process of introducing high-energy ions into the surface layer of a substrate by bombardment. This method allows selective surface modification without adversely affecting the substrate, but the high cost and relatively shallow depth of modification has hindered further development. Plasma spraying is a process in which a material is melted into droplets and ejected in an energetic manner to a surface, causing individual particles to adhere and coalesce. This technique enables any molten material to form a coating, minimal heating of the substrate during deposition, and the ability to strip and reapply worn or damaged coatings without changing the properties or dimensions of the part. However, this technique is narrow in the line of sight, does not allow the coating of small deep cavities, and the coating needs to be sealed. The surface of magnesium and magnesium alloys can be modified by using high density energy laser beam technology to obtain finer microstructures, but at higher cost and with complicated operations. The double-layer glow plasma discharge phenomenon has been successfully applied to the preparation of different metal surface alloying layers, but is rarely used for the surface alloying of low-melting-point metals.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the technical problems in the prior art, the invention aims to provide a method for alloying and preparing a coating on the surface of pure magnesium, which has low cost, controllable modification depth and good modification effect.
The technical scheme is as follows: the method for alloying and preparing the coating on the surface of the pure magnesium comprises the following steps:
(1) Alloying on the surface of pure magnesium: the double glow plasma alloying technology is adopted, the used heat-insulating cover is made of a pure zinc plate and is connected with a cathode objective table, the heat-insulating cover is connected with a target zinc sheet, pure magnesium is used as a matrix to be connected with another cathode electrode, and a cavity is used as an anode to be grounded; under the protection of high vacuum, the target material zinc sheet and pure magnesium are subjected to pre-bombardment, then the target material zinc sheet is subjected to low glow bombardment and deposition, and the zinc alloyed pure magnesium is obtained after rapid cooling and heat preservation;
(2) Preparing a composite coating: the pure magnesium with the zinc alloying is plated by adopting a magnetron sputtering technology, one or two of high-purity metal oxide or noble metal is used as a target material, the pure magnesium with the zinc alloying is pre-sputtered under the protection of high vacuum, and then the target material is sputtered, so that the pure magnesium with the coating and the zinc alloying is obtained.
Further, in the step (1), the parameters of the pre-bombardment are as follows: the working pressure is 20-35Pa, the two cathode voltages are 100-250V, and the bombardment time is 1-10min; the parameters of the low glow bombardment were: the voltage of the heat-preserving cover is 200-450V, the working temperature is 200-350 ℃, and the bombardment time is 5-60min; the parameters of the high vacuum were: vacuum degree of 3X 10 -4 -6×10 -4 Pa; the parameters of rapid cooling and heat preservation are as follows: the working air pressure is 10-25Pa, the heat preservation is carried out for 10-60min, and the pure magnesium substrate is suspended in the center of the heat preservation cover and is not contacted with the target material.
Further, in the step (2), the metal oxide is titanium dioxide, and the noble metal is tantalum, niobium or zirconium; the distance between the target and the zinc alloyed pure magnesium is 5-8cm, the pre-sputtering time is 5-10min, and the pre-sputtering function is as follows: on one hand, the surface of the sample to be sputtered can be cleaned, and on the other hand, the surface of the sample to be sputtered can be activated so as to facilitate the adsorption of active atoms; the time of sputtering the target is 10-120min, the radio frequency power of sputtering the metal oxide is 100-350W, the direct current power of sputtering the noble metal is 100-200W, the pure magnesium with the coating and zinc alloying takes the zinc layer as the middle layer, and takes the metal oxide layer or the noble metal layer or the composite layer of the metal oxide and the noble metal as the coating.
The invention principle is as follows: the invention utilizes the double glow discharge phenomenon, takes high-purity low-melting-point metal zinc as a target material, firstly prepares a magnesium-zinc alloying layer on the surface of pure magnesium which is simply and mechanically polished, the alloying layer not only plays a role of enhancing the surface mechanics, but also can improve the surface structure of the pure magnesium, takes the alloying layer as a transition layer, then adopts titanium dioxide and noble metal tantalum as target material elements, and utilizes the magnetron sputtering technology to sputter and deposit a coating on the surface of a metal matrix, thereby further improving the mechanical property and the degradation property of the pure magnesium.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages:
(1) The zinc-alloyed pure magnesium material with the coating, which is prepared by the invention, has excellent biocompatibility, mechanical property and corrosion resistance, and degradation controllability, and experimental data show that the zinc-alloyed pure magnesium material with the coating has a better effect than a pure magnesium material without the coatingThe hardness of the treated pure magnesium is only 38HV 10 The hardness of the modified pure magnesium is improved to 185HV 10 The improvement is 4.9 times;
(2) The invention carries out surface treatment on pure magnesium by combining the double-glow plasma alloying technology and the magnetron sputtering technology, has simple process, safety, environmental protection, controllable modification degree, high raw material utilization rate and low cost, and is suitable for surface treatment of large-batch pure magnesium substrates.
Drawings
FIG. 1 is a microscopic morphology and element distribution diagram of a material prepared in example 1 of the present invention;
FIG. 2 is a microscopic morphology and element distribution diagram of a material prepared in example 3 of the present invention;
FIG. 3 is a cross-sectional profile and elemental profile of a material made according to example 3 of the present invention;
FIG. 4 is a microscopic morphology and element distribution diagram of the material prepared in example 4 of the present invention;
FIG. 5 is a cross-sectional view of a material obtained in example 4 of the present invention;
FIG. 6 is a microscopic morphology and elemental distribution plot of a material prepared in comparative example 2 of the present invention;
FIG. 7 is a cross-sectional profile and elemental profile of a material made according to comparative example 2 of the present invention;
FIG. 8 is a graph comparing hardness of materials prepared in comparative example 1, comparative example 2 and example 2 according to the present invention;
FIG. 9 is a plot of polarization of the materials prepared in comparative example 1, comparative example 2 and example 2 of the present invention;
fig. 10 is a schematic top view of a dual-glow plasma apparatus used in the present invention.
Detailed Description
The present invention will be further described with reference to the following specific examples and the accompanying drawings.
Example 1: the method for alloying and preparing the coating on the surface of the pure magnesium comprises the following steps:
(1) Alloying on the surface of pure magnesium:
(1) putting the pure magnesium of the matrix wiped by absolute ethyl alcohol into a heat-insulating cover made of a pure zinc plate, wherein the heat-insulating cover is connected with a cathode objective table in a double-layer glow plasma furnace, target zinc sheets are placed around the heat-insulating cover, the pure magnesium of the matrix is connected with another cathode electrode, and the cavity is grounded as an anode;
(2) high vacuum protection: opening the double-layer glow plasma alloying water pump equipment, pumping the air pressure of the coating furnace body to 3Pa by using a mechanical pump, and further pumping the air pressure of the furnace body to 4 multiplied by 10 by using a molecular pump -4 Pa, keeping the furnace in a high vacuum state;
(3) low glow bombardment and deposition: argon is filled to 25Pa, two cathode power supplies are respectively opened, 250V voltage is applied, the target zinc sheet and the substrate pure magnesium are pre-bombarded for 10 minutes, after the pre-bombardment, the voltage of the heat-insulating cover is gradually adjusted to a test value of 300V, so that the target zinc sheet reaches the working temperature of 200 ℃, each process parameter is stabilized, and the heat insulation is started for 5-10 minutes;
(4) and (3) rapid cooling and heat preservation: rapidly closing the power supply of the target and the workpiece substrate, adjusting the argon to the working pressure of 15Pa, and continuously maintaining for 10-60min;
(5) the cathode power supply and the argon gas source are closed in sequence, and the vacuum furnace is pumped to 3 multiplied by 10 -4 Pa vacuum degree, cooling to room temperature, discharging to obtain pure magnesium alloyed with zinc, namely MgZn;
(2) Preparing a composite coating:
(1) placing Mg-Zn on a magnetron sputtering objective table, installing a high-purity titanium dioxide target material, and keeping the distance between the target material and a sample at 6cm;
(2) high vacuum protection: opening plasma sputtering equipment and a cooling system matched with the plasma sputtering equipment, pumping the air pressure of a coating furnace body to be below 3Pa by using a mechanical pump, and further pumping the air pressure of the furnace body to be 5 multiplied by 10 by using a molecular pump -4 Pa, keeping the furnace in a high vacuum state;
(3) argon is filled into the furnace to 2Pa, and the sample is pre-sputtered for about 10 minutes;
(4) after pre-sputtering, turning on a radio frequency power supply, adjusting the radio frequency power to 200W, and sputtering titanium dioxide for 60min;
(5) after sputtering is finished, the target baffle, the direct current power supply and the argon gas source are closed in sequence, the furnace is cooled to room temperature and then is subjected to gas discharge sampling, and the target sputtering target is obtainedPure magnesium with titanium dioxide coating and alloyed with zinc, labelled MgZn-TiO 2 。
Example 2: the method for alloying and preparing the coating on the surface of the pure magnesium comprises the following steps:
(1) Alloying on the surface of pure magnesium:
(1) putting pure magnesium wiped by absolute ethyl alcohol into a heat-insulating cover made of a pure zinc plate, wherein the heat-insulating cover is connected with a cathode objective table in a double-layer glow plasma furnace, four zinc targets are placed around the heat-insulating cover, the pure magnesium of a matrix is connected with another cathode electrode, and a cavity is grounded as an anode;
(2) high vacuum protection: opening double-layer glow plasma alloying water pump equipment, pumping the air pressure of a coating furnace body to 2Pa by using a mechanical pump, and further pumping the air pressure of the furnace body to 3 x 10 < -4 > Pa by using a molecular pump so as to keep the high vacuum state in the furnace;
(3) low glow bombardment and deposition: argon is filled to 20Pa, two cathode power supplies are respectively opened, 100V voltage is applied, bombardment is carried out on the target zinc sheet and the substrate pure magnesium for 1-10min, after the bombardment is carried out, the voltage of the heat preservation cover is gradually adjusted to a test value of 250V, the target zinc sheet reaches the working temperature of 300 ℃, each process parameter is stabilized, and heat preservation is started for 5min;
(4) and (3) rapid cooling and heat preservation: rapidly closing the power supplies of the target and the workpiece substrate, adjusting the argon to the working pressure of 20Pa, and continuously maintaining for 60min;
(5) the cathode power supply and the argon gas source are closed in sequence, and the vacuum furnace is pumped to 4 multiplied by 10 -4 Pa vacuum degree, cooling to room temperature, discharging to obtain pure magnesium alloyed with zinc, namely MgZn;
(2) Preparing a composite coating:
(1) placing Mg-Zn on a magnetron sputtering objective table, installing a high-purity titanium dioxide target material and a noble metal tantalum target, and keeping the distance between the two target materials and a sample to be 6cm;
(2) high vacuum protection: opening the plasma sputtering equipment and a cooling system matched with the plasma sputtering equipment, pumping the air pressure of the coating furnace body to be below 5Pa by using a mechanical pump, and further pumping the air pressure of the furnace body to be 6 multiplied by 10 by using a molecular pump -4 Pa, making the furnace insideMaintaining a high vacuum state;
(3) filling argon into the furnace to 3Pa, and carrying out pre-sputtering on the sample for 10 minutes; (ii) a
(4) After pre-sputtering, turning on a direct-current power supply and a baffle of a titanium dioxide target, firstly adjusting the radio frequency power to 200W, and sputtering titanium dioxide for 60min; closing the baffle of the titanium dioxide target, opening the baffle of the flat target, adjusting the direct current power to 200W, and sputtering the tantalum target for 30min;
(5) after sputtering is finished, the tantalum metal baffle, the direct current power supply and the argon gas source are closed in sequence, the furnace is cooled to room temperature and then is subjected to gas discharge and sampling, and pure magnesium which has a titanium dioxide and tantalum metal composite coating and is alloyed with zinc is obtained and is marked as Mg-Zn-TiO 2 /Ta。
Example 3: the difference from the embodiment 1 is that in the step (2), the target material is tantalum metal, the direct current power is adjusted to 200W, the tantalum target is sputtered for 30min, and the obtained material is MgZn-Ta.
Example 4: the difference from example 2 is that in step (2), (4) was repeated twice and the material obtained was MgZn-TiO 2 /Ta-TiO 2 /Ta。
Comparative example 1: pure magnesium, labeled as Mg.
Comparative example 2: the difference from example 1 is that step (2) is not included, and pure magnesium alloyed with zinc is obtained, and is marked as MgZn.
The materials obtained in examples 1 to 4 and comparative examples 1 to 2 were subjected to the performance test, as shown in FIGS. 1 to 9.
FIG. 1 shows MgZn-TiO prepared in example 1 2 The SEM image and the element distribution diagram of the film are shown in the left image of FIG. 1, and the magnetron sputtering technology is utilized to sputter oxides, so that the number of surface defect sites is increased, and the later nucleation growth is facilitated; mgZn-TiO can be obtained from the right picture of figure 1 2 The ratio of the elements in (1), and thus, mgZn-TiO 2 Is effectively MgZn 86.59 -Ti 5.52 O 7.89 。
FIG. 2 is an SEM image and an element distribution diagram of MgZn-Ta prepared in example 3, and it can be seen from the left image in FIG. 2 that the surface of the noble metal tantalum target sputtered by the magnetron sputtering technique is cellular and has obvious gaps; in MgZn-Ta as can be obtained from the right diagram of FIG. 2The ratio of the elements, therefore, mgZn-Ta is actually MgZn 0.06 -Ta 99.94 。
FIG. 3 is a cross-sectional morphology and an element distribution diagram of MgZn-Ta prepared in example 3. As can be seen from the left image in FIG. 3, ta atoms deposited in the MgZn alloy layer clearly show that the surface is dense and the bonding is tight, and the coating thickness reaches 3.98um.
FIG. 4 shows MgZn-TiO prepared in example 4 2 /Ta-TiO 2 The microscopic morphology and the element distribution diagram of the/Ta show that the surface is in a continuous cellular structure and the structure is compact as shown in the left diagram of FIG. 4; mgZn-TiO can be obtained from the right picture of figure 4 2 /Ta-TiO 2 The ratio of the elements/Ta, thus MgZn-TiO 2 /Ta-TiO 2 Ta is actually Mg 0.36 Zn 0.58 -TiO 2.11 /Ta-TiO 2.11 /Ta 96.96 。
FIG. 5 shows MgZn-TiO prepared in example 4 2 /Ta-TiO 2 The cross section appearance of/Ta, the coating is 5.63um, the surface is smooth, and the structure is compact.
FIG. 6 is a graph showing the microscopic morphology and elemental distribution of MgZn prepared in comparative example 2, wherein the left graph in FIG. 6 shows that a magnesium-zinc alloyed layer is prepared on the surface of pure magnesium by using a dual-glow plasma technique, and the surface is curled; as is clear from the right diagram of FIG. 6, the ratio of each element in MgZn, so MgZn is Mg/Mg in reality 1.82 Zn 98.18 。
FIG. 7 is a cross-sectional morphology and an element distribution diagram of the material prepared in comparative example 2, and it can be seen from the left image of FIG. 7 that the MgZn alloying layer has a loose cross-section and increased defect sites.
FIG. 8 is a graph showing a comparison of hardness of the materials obtained in comparative example 1, comparative example 2 and example 2, and Mg, mgZn alloyed layer, mgZn-TiO layer measured by a microhardness tester 2 Hardness of-Ta is 38HV 10 、57HV 10 、138HV 10 It is demonstrated that the composite coating prepared on pure magnesium is beneficial to improving the mechanical properties of the coating.
FIG. 9 is a graph showing polarization curves of the materials obtained in comparative example 1, comparative example 2 and example 2, and it can be seen that MgZn-TiO 2 The corrosion current of-Ta is minimum, the corrosion voltage is maximum, and the composite coating can delay the corrosion of pure magnesium。
Fig. 10 is a schematic top view of a dual-glow plasma apparatus used in the present invention, wherein a pure magnesium substrate is disposed in a protective cover for surface treatment.
In conclusion, the zinc alloying layer is prepared on the surface of pure magnesium by using the double-glow plasma sputtering technology, the alloying elements enter the surface of the matrix to form a loose film through adsorption, deposition and diffusion, the titanium dioxide and the tantalum coating are prepared through magnetron sputtering, the titanium dioxide and the tantalum nucleate at the defect position in the initial nucleation stage, and the titanium dioxide and the tantalum begin to deposit and grow after the nucleation process of the defect position is finished; and finally, in a secondary nucleation stage, new defects appear, and titanium dioxide and tantalum nucleate again on the surface to finally form a coating on the surface of pure magnesium.
Claims (10)
1. A method for alloying and preparing a coating on the surface of pure magnesium is characterized by comprising the following steps:
(1) Alloying on the surface of pure magnesium: the double glow plasma alloying technology is adopted, the used heat-insulating cover is made of a pure zinc plate and is connected with a cathode objective table, the heat-insulating cover is connected with a target zinc sheet, pure magnesium is used as a matrix to be connected with another cathode electrode, and a cavity is used as an anode to be grounded; under the protection of high vacuum, the target material zinc sheet and pure magnesium are subjected to pre-bombardment, then the target material zinc sheet is subjected to low glow bombardment and deposition, and the zinc alloyed pure magnesium is obtained after rapid cooling and heat preservation;
(2) Preparing a composite coating: the pure magnesium with the zinc alloying is plated by adopting a magnetron sputtering technology, one or two of high-purity metal oxide or noble metal is used as a target material, the pure magnesium with the zinc alloying is pre-sputtered under the protection of high vacuum, and then the target material is sputtered, so that the pure magnesium with the coating and the zinc alloying is obtained.
2. The method according to claim 1, wherein in step (1), the parameters of the pre-bombardment are: the working pressure is 20-35Pa, the two cathode voltages are 100-250V, and the bombardment time is 1-10min.
3. The method according to claim 1, wherein in step (1), the parameters of the low glow bombardment are: the voltage of the heat-preserving cover is 200-450V, the working temperature is 200-350 ℃, and the bombardment time is 5-60min.
4. The method according to claim 1, wherein in step (1), the parameters of the high vacuum are: vacuum degree of 3X 10 -4 -6×10 -4 Pa。
5. The method according to claim 1, wherein in the step (1), the parameters of rapid cooling and heat preservation are as follows: working air pressure is 10-25Pa, and heat preservation is carried out for 10-60min.
6. The method according to claim 1, wherein in the step (1), the pure magnesium substrate is suspended in the center of the heat-preserving cover.
7. The method of claim 1, wherein in step (2), the metal oxide is titania and the noble metal is tantalum, niobium or zirconium.
8. The method of claim 1, wherein in step (2), the target is spaced from the zinc-alloyed pure magnesium by 5-8cm.
9. The method according to claim 1, wherein in the step (2), the time for sputtering the target is 10-120min, the RF power for sputtering the metal oxide is 100-350W, and the DC power for sputtering the noble metal is 100-200W.
10. The method according to claim 1, wherein the coated and zinc alloyed pure magnesium is coated with a zinc layer as an intermediate layer and a metal oxide layer or a noble metal layer or a composite layer of metal oxide and noble metal.
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