CN104046951A - Method for preparing praseodymium-doped titanium nitride coating on surface of medical titanium alloy - Google Patents
Method for preparing praseodymium-doped titanium nitride coating on surface of medical titanium alloy Download PDFInfo
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- CN104046951A CN104046951A CN201410264533.0A CN201410264533A CN104046951A CN 104046951 A CN104046951 A CN 104046951A CN 201410264533 A CN201410264533 A CN 201410264533A CN 104046951 A CN104046951 A CN 104046951A
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Abstract
The invention discloses a method for preparing a praseodymium-doped titanium nitride coating on the surface of a medical titanium alloy. The method comprises the following steps: preparing a titanium nitride coating on the surface of the medical titanium alloy by utilizing a magnetron sputtering method; transferring the medical titanium alloy with the titanium nitride coating into a vacuum chamber A of a plasma-immersion-type ion implanter under the condition that a praseodymium target and a sample disk A are respectively arranged at two ends of the inside of the vacuum chamber A; fixing the medical titanium alloy with the titanium nitride coating on the sample disk A; regulating the vacuum degree of the vacuum chamber A under the condition that the praseodymium target is taken as an ion source of a cathode; regulating the rotating speed of the sample disk A and cooling the sample disk A in a water-cooling manner; and then, carrying out praseodymium ion implantation at a room temperature, thereby obtaining the praseodymium-doped titanium nitride coating prepared on the surface of the medical titanium alloy. According to the method disclosed by the invention, the corrosion resistance of the prepared praseodymium-doped titanium nitride coating is obviously superior to that of a common titanium nitride coating; the breeding and the spreading of a large quantity of vascular endothelial cells in the praseodymium-doped titanium nitride coating can be carried out, so that the biological performance of the medical titanium alloy is obviously improved.
Description
[technical field]
The invention belongs to coated material preparation field, be specifically related to a kind of method of preparing praseodymium doped titanium nitride coating on medical titanium alloy surface.
[background technology]
Cardiovascular systems class disease is a class serious threat human lives disease, at present owing to being applicable to the restriction of organ transplantation quantity and the horizontal regeneration techniques of human organ, medical circle mainly relies on intravascular stent, heart valve prosthesis, the graft of the titanium alloy class material manufactures such as kidney strainer is helped patient disease, and these titanium alloy materials are also referred to as medical titanium alloy biomaterial.Biomaterial must have good cell compatibility, erosion resistance, and suitable physical strength.The above-mentioned performance that the surface characteristic of biomaterial can affect.Surface chemistry and physical features, surface topography is all the important factor that affects biocompatibility.Can significantly improve the biocompatibility of biomaterial by comparatively ripe process for modifying surface.Now widely used medical human implant is all to manufacture with titanium alloy class material, but in human body various organs and tissue to graft materials require different, especially in blood tissues environment, the corrosive nature of blood constitutes a threat to the physical strength of metal species graft, make graft accelerated deterioration, and can cause some and be listed as bad physiological response, increase on the contrary patient's misery.Therefore need material to there is stronger corrosion resistance and biocompatibility, make graft adaptation blood tissues environment.
In order to obtain better biocompatibility and resistance to blood corrosive nature, generally all adopt physical gas phase deposition technology to prepare binary or the ternary coating of transition metal-type at material surface.Titanium nitride coating is the top coat that a kind of technology of preparing is very ripe, often uses at titanium alloy surface and improves biocompatibility, and wear resistance and erosion resistance.But some inherent structure feature of titanium nitride coating can cause its erosion resistance to decline gradually, as the small cavity in titanium nitride coating and other defect can make to cause the corrosion behavior of body material.
[summary of the invention]
The object of the invention is to for the deficiencies in the prior art, a kind of method of preparing praseodymium doped titanium nitride coating on medical titanium alloy surface is provided, praseodymium doped titanium nitride coating prepared by the method, has fundamentally solved the difficult problem of the resistance to blood corrosion in medical titanium alloy surface and biology performance deficiency.
To achieve these goals, the present invention takes following technical scheme:
A method of preparing praseodymium doped titanium nitride coating on medical titanium alloy surface, comprises the following steps:
1) on medical titanium alloy surface, adopt the method for magnetron sputtering to prepare titanium nitride coating, wherein, the thickness of the titanium nitride coating preparing is 500nm-2 μ m;
2) will transfer to the medical titanium alloy of titanium nitride coating in the vacuum chamber A of PIC method in plasma immersion ion implanter, two ends in this vacuum chamber A are respectively equipped with praseodymium target and platter A, be fixed on platter A with the medical titanium alloy of titanium nitride coating upper, regulating the vacuum tightness of vacuum chamber A is 10
-4-10
-3pa, negative electrode uses praseodymium target to be used as ion source, the rotating speed of adjusting sample dish A is 8～35 revs/min, and rely on water-cooled to lower the temperature to platter A, then carry out at normal temperatures praseodymium ion injection, prepare praseodymium doped titanium nitride coating on medical titanium alloy surface, wherein, the acceleration voltage of praseodymium ion is 30KV～80KV, and injection length is 0.5～1h.
The present invention further improves and is, step 1) in, on medical titanium alloy surface, adopt the method for magnetron sputtering to prepare titanium nitride coating, comprise the following steps:
A) by immersing ultrasonic cleaning in acetone after medical titanium alloy surface degreasing, polishing, finally adopt dehydration of alcohol;
B) the good medical titanium alloy of pre-treatment is transferred in the vacuum chamber B of magnetron sputtering ion plating equipment, the platter B, well heater and the Ti target that in this vacuum chamber B, are provided with, well heater and platter B are successively set on the upper surface in vacuum chamber B from top to bottom, Ti target as Ti source is arranged on the lower surface in vacuum chamber B, and the angle of the Ti emission of ions direction of Ti target and the lower surface of platter B is acute angle, on the wall of vacuum chamber B, be also provided with the outlet of entrance and the waste of argon gas and nitrogen;
C) regulating the vacuum tightness of vacuum chamber B is 1 × 10
-3～1 × 10
-4pa, meanwhile, the rotating speed of adjusting sample dish B is 10～30 revs/min;
D) open the intake valve of argon gas, regulate argon flow amount to 5～15sccm, vacuum chamber B air pressure is adjusted to 4.2～8.6mTorr, Ti target power output is 15～150W, first the good medical titanium alloy of pre-treatment is carried out the deposition of 1～10min titanium simple substance, obtain Ti simple substance layer at medical titanium alloy, open again the gas valve of nitrogen, regulate nitrogen flow to 4～10sccm, on the Ti of medical titanium alloy simple substance layer, generate titanium nitride coating, wherein, in the coating process of titanium nitride coating, vacuum chamber B temperature is 200～800 DEG C, and the plated film time is 90～300min.
The present invention further improves and is, step c) in, adopt molecular pump to make vacuum tightness to 1 × 10 of vacuum chamber B
-4pa.
The present invention further improves and is, steps d) in, the angle of the Ti emission of ions direction of Ti target and the lower surface of platter B is 45 degree.
The present invention further improves and is, step 2) in, adopting mechanical pump and molecular pump to make the vacuum tightness of vacuum chamber A is 1 × 10
-3-1 × 10
-4pa.
Compared with prior art, the present invention has advantages of as follows:
Praseodymium doped titanium nitride coating prepared by the present invention, praseodymium doped titanium nitride coating is crystalline structure after measured, and coating is evenly distributed and is comparatively smooth on matrix, and praseodymium ion distributes also very even in coating; By electrochemical corrosion experimental, to this coating, the corrosion behavior in blood plasma detects discovery, the praseodymium doped titanium nitride coating contrast titanium nitride coating that praseodymium ion injects in the blood plasma of 37 DEG C, corrosion resistance be improved significantly.Hemolytic experiment shows, compared with titanium nitride coating, the praseodymium doped titanium nitride coating hemolysis rate that praseodymium ion injects significantly reduces, and reaches 3% left and right, shows that it almost can ignore the destructiveness of hemocyte.Cell compatibility experimental result shows, the praseodymium doped titanium nitride coating that praseodymium ion injects obviously promotes the propagation of vascular endothelial cell, endotheliocyte can intensive sprawling in this coating, show that praseodymium doped titanium nitride coating is less to the side effect of vascular surgery, the biology performance that it has improved medical titanium alloy significantly, has the effect that extends artificial graft's instrumentation life-span of being manufactured by medical titanium alloy.
[brief description of the drawings]
Fig. 1 is magnetron sputtering ion plating device structure schematic diagram of the present invention;
Fig. 2 is PIC method in plasma immersion ion injection device structural representation of the present invention;
Fig. 3 is the surface topography map that praseodymium ion of the present invention injects praseodymium doped titanium nitride coating;
Fig. 4 cultivates vascular endothelial cell after 6 days in the praseodymium doped titanium nitride coating injected of praseodymium ion of the present invention to sprawl and shape appearance figure.
[embodiment]
Below in conjunction with drawings and Examples, the present invention is described in further detail.
Referring to Fig. 1 to Fig. 4, a kind of method of preparing praseodymium doped titanium nitride coating on medical titanium alloy surface of the present invention, comprises the following steps:
1) circular disc test specimen that the medical titanium alloy rod that is 25mm using diameter cuts into φ 25mm × 2mm, as matrix, immerses ultrasonic cleaning in acetone after surface degreasing, polishing, finally adopts dehydration of alcohol.
2) medical titanium alloy good pre-treatment is put into magnetron sputtering ion plating equipment as body material.As shown in Figure 1; magnetic-controlled sputtering coating equipment at least comprises vacuum chamber B4, platter B1, Ti target 3, well heater 2; matrix be placed in can the platter B1 of rotation on; distance between platter B1 and Ti target 3 can regulate; Ti target 3 is all equipped with mechanical transmission protective cover with platter B1; be convenient to control the process of plated film; and well heater 2 is above platter B1; to sample direct heating; can make like this thermoreceptor reflect more accurately the actual temperature of sample, be conducive to the preparation of coating.
3) adopt φ 50 × 10mm disc-shaped Ti target 3 as Ti source, target face and platter B1 plane are miter angle, by first forming Ti basic unit at medical titanium alloy matrix surface, can effectively improve the bonding force of the titanium nitride coating of deposition subsequently, and by adjusting target power, the flow of argon gas is controlled the sputtering raste of target, coating deposition can be by adjusting sample and target apart from controlled, adopt high-purity argon gas as main ionization of gas, ensure effective glow discharging process.Wherein, in coating process, vacuum chamber B4 temperature is 400 DEG C, and the plated film time is 90min.
4) as shown in Figure 2,, after preparing splash coating and finishing, close whole magnetron sputtering equipment.Wait specimen temperature is down to after room temperature, open vacuum chamber B4, to proceed to the sample of titanium nitride coating on the platter A6 of plasma immersion formula ion implanter, platter A6 is vertical with ion implantation direction, platter A6 can rotation, ensure ion implantation evenly, platter A6 relies on water-cooled to lower the temperature.Using the bar-shaped praseodymium target 5 of φ 10 × 40mm is ion source, regulates vacuum tightness to 2 × 10 of vacuum chamber A7
-3pa, discharge power supply set of frequency is 8Hz, and arc voltage is set to 70KV, and the arc current of generation is 1.1A, and deceleration voltage of supply is set to 1.3KV, and accelerating power source voltage is set to 30KV, and the ion implantation time is 0.5～1h.
Under above-mentioned processing condition, can prepare the praseodymium doped titanium nitride coating that the good praseodymium ion of bonding force injects at titanium alloy alloy surface.In coating, titanium nitride is crystalline structure after measured, and crystal preferred orientation is (200), and praseodymium exists with oxide form, and as shown in Figure 3, the praseodymium doped titanium nitride coating that AFM detection display praseodymium ion injects is very smooth.
Measure discovery by electrochemistry experiment; the praseodymium doped titanium nitride coating that praseodymium ion injects is better than titanium nitride coating at blood plasma resistance to corrosion; open circuit potential and anti-corrosion current potential are higher, have effectively protected the mechanical property of the medical titanium alloy material using in blood environment.Hemolytic experiment detects to be found, the praseodymium doped titanium nitride coating that praseodymium ion injects is extremely low to the degree of damage of hemocyte, almost negligible, proves that this special coating can effectively reduce the destruction of various titanium alloy parts machining profiles to hemocyte.Use vascular endothelial cell to carry out cell adhesion and the cell proliferation experiment of long period, as shown in Figure 4, in the praseodymium doped titanium nitride coating of injecting at praseodymium ion, endotheliocyte can be bred in a large number, prove that the praseodymium doped titanium nitride coating that praseodymium ion injects does not form harm to the existence of cell, and endothelial cell morphology presents typical fusiformis, the complete close contact of Growth of Cells, titanium nitride coating is conducive to wound healing more relatively, endothelial tissue is shaped, and has also increased new option for the kind of tissue engineering bracket material.
In sum, the present invention injects resistance to corrosion and the cell compatibility of praseodymium raising medical titanium alloy at blood plasma in titanium nitride coating.By ion implantation praseodymium, reduce the roughness of titanium nitride coating, titanium nitride coating is also significantly reduced erythrocytic destructiveness.The praseodymium doped titanium nitride coating that praseodymium ion injects does not cause the untoward reaction of vascular endothelial cell, and cell proliferation is good, shows that this novel praseodymium doped titanium nitride coating has good cell compatibility.
Above content is in conjunction with concrete preferred implementation further description made for the present invention; can not assert that the specific embodiment of the present invention only limits to this; for general technical staff of the technical field of the invention; without departing from the inventive concept of the premise; can also make some simple deduction or replace, all should be considered as belonging to the present invention and determine scope of patent protection by submitted to claims.
Claims (5)
1. a method of preparing praseodymium doped titanium nitride coating on medical titanium alloy surface, is characterized in that, comprises the following steps:
1) on medical titanium alloy surface, adopt the method for magnetron sputtering to prepare titanium nitride coating, wherein, the thickness of the titanium nitride coating preparing is 500nm-2 μ m;
2) will transfer to the medical titanium alloy of titanium nitride coating in the vacuum chamber A (7) of PIC method in plasma immersion ion implanter, two ends in this vacuum chamber A (7) are respectively equipped with praseodymium target (5) and platter A (6), be fixed on platter A (6) with the medical titanium alloy of titanium nitride coating upper, regulating the vacuum tightness of vacuum chamber A (7) is 10
-4-10
-3pa, negative electrode uses praseodymium target (5) to be used as ion source, the rotating speed of adjusting sample dish A (6) is 8～35 revs/min, and rely on water-cooled to lower the temperature to platter A (6), then carry out at normal temperatures praseodymium ion injection, prepare praseodymium doped titanium nitride coating on medical titanium alloy surface, wherein, the acceleration voltage of praseodymium ion is 30KV～80KV, and injection length is 0.5～1h.
2. a kind of method of preparing praseodymium doped titanium nitride coating on medical titanium alloy surface according to claim 1, is characterized in that step 1) in, on medical titanium alloy surface, adopt the method for magnetron sputtering to prepare titanium nitride coating, comprise the following steps:
A) by immersing ultrasonic cleaning in acetone after medical titanium alloy surface degreasing, polishing, finally adopt dehydration of alcohol;
B) the good medical titanium alloy of pre-treatment is transferred in the vacuum chamber B (4) of magnetron sputtering ion plating equipment, the platter B (1) being provided with in this vacuum chamber B (4), well heater (2) and Ti target (3), well heater (2) and platter B (1) are successively set on the upper surface in vacuum chamber B (4) from top to bottom, be arranged on the lower surface in vacuum chamber B (4) as the Ti target (3) in Ti source, and the angle of the lower surface of the Ti emission of ions direction of Ti target (3) and platter B (1) is acute angle, on the wall of vacuum chamber B (4), be also provided with the outlet of entrance and the waste of argon gas and nitrogen,
C) regulating the vacuum tightness of vacuum chamber B (4) is 1 × 10
-3～1 × 10
-4pa, meanwhile, the rotating speed of adjusting sample dish B (1) is 10～30 revs/min;
D) open the intake valve of argon gas, regulate argon flow amount to 5～15sccm, vacuum chamber B (4) air pressure is adjusted to 4.2～8.6mTorr, Ti target power output is 15～150W, first the good medical titanium alloy of pre-treatment is carried out the deposition of 1～10min titanium simple substance, obtain Ti simple substance layer at medical titanium alloy, open again the gas valve of nitrogen, regulate nitrogen flow to 4～10sccm, on the Ti of medical titanium alloy simple substance layer, generate titanium nitride coating, wherein, in the coating process of titanium nitride coating, vacuum chamber B (4) temperature is 200～800 DEG C, the plated film time is 90～300min.
3. a kind of method of preparing praseodymium doped titanium nitride coating on medical titanium alloy surface according to claim 2, is characterized in that, step c) in, adopt molecular pump to make vacuum tightness to 1 × 10 of vacuum chamber B (4)
-4pa.
4. a kind of method of preparing praseodymium doped titanium nitride coating on medical titanium alloy surface according to claim 2, it is characterized in that, steps d) in, the angle of the lower surface of the Ti emission of ions direction of Ti target (3) and platter B (1) is 45 degree.
5. a kind of method of preparing praseodymium doped titanium nitride coating on medical titanium alloy surface according to claim 1, is characterized in that step 2) in, adopting mechanical pump and molecular pump to make the vacuum tightness of vacuum chamber A (7) is 1 × 10
-3-1 × 10
-4pa.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109778132A (en) * | 2019-03-26 | 2019-05-21 | 天津师范大学 | A kind of Cu/Zn injects the preparation method and application of TiN package titanium alloy altogether |
| CN112899618A (en) * | 2021-05-08 | 2021-06-04 | 中南大学湘雅医院 | Coating with catalytic capability on surface of intravascular stent and preparation method thereof |
| CN113502452A (en) * | 2021-07-12 | 2021-10-15 | 深圳市阿尔法材料科技有限公司 | TaN-rare earth composite coating and preparation method thereof |
| CN115652272A (en) * | 2022-09-27 | 2023-01-31 | 暨南大学 | N and Cu ion implantation titanium alloy modified coating and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109778132A (en) * | 2019-03-26 | 2019-05-21 | 天津师范大学 | A kind of Cu/Zn injects the preparation method and application of TiN package titanium alloy altogether |
| CN112899618A (en) * | 2021-05-08 | 2021-06-04 | 中南大学湘雅医院 | Coating with catalytic capability on surface of intravascular stent and preparation method thereof |
| CN112899618B (en) * | 2021-05-08 | 2021-07-16 | 中南大学湘雅医院 | Coating with catalytic capability on surface of intravascular stent and preparation method thereof |
| CN113502452A (en) * | 2021-07-12 | 2021-10-15 | 深圳市阿尔法材料科技有限公司 | TaN-rare earth composite coating and preparation method thereof |
| CN115652272A (en) * | 2022-09-27 | 2023-01-31 | 暨南大学 | N and Cu ion implantation titanium alloy modified coating and preparation method and application thereof |
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