CN114250441A - Method for preparing bismuth-antimony alloy coating with uniform surface and stable combination by magnetron sputtering - Google Patents

Method for preparing bismuth-antimony alloy coating with uniform surface and stable combination by magnetron sputtering Download PDF

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CN114250441A
CN114250441A CN202111591854.8A CN202111591854A CN114250441A CN 114250441 A CN114250441 A CN 114250441A CN 202111591854 A CN202111591854 A CN 202111591854A CN 114250441 A CN114250441 A CN 114250441A
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bismuth
antimony
magnetron sputtering
preparing
alloy coating
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CN114250441B (en
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赵弘韬
李志刚
刘志鑫
韩福广
王艺
张楠
田波
李金凤
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Heilongjiang Atomic Energy Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
    • C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/18—Metallic material, boron or silicon on other inorganic substrates
    • C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling

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Abstract

A method for preparing a bismuth-antimony alloy coating with uniform surface and stable combination by utilizing magnetron sputtering relates to a method for preparing a bismuth-antimony alloy coating. The invention aims to solve the problems that the existing isotope target material preparation technology is complex, the preparation mode is single, the coating on the surface of the target material is not uniformly distributed, and the thickness and the binding force are difficult to control. The preparation method comprises the following steps: firstly, preparing a bismuth-antimony target; secondly, bias cleaning; thirdly, direct current magnetron sputtering. The method is used for preparing the bismuth-antimony alloy coating with uniform surface and stable combination by utilizing magnetron sputtering.

Description

Method for preparing bismuth-antimony alloy coating with uniform surface and stable combination by magnetron sputtering
Technical Field
The invention relates to a method for preparing a bismuth-antimony alloy coating.
Background
At present, a more comprehensive isotope production system is available in the world, but a plurality of facilities are seriously aged, the supply gap of medical isotopes in the future is large, and the establishment of a stable and safe supply system has important significance. The accelerator for producing isotope has high specific activity, short half-life period and general emission of proton, deuteron and beta+Or monoenergetic gamma rays, etc. Under the condition that the production of radioactive isotopes by a reactor cannot meet the requirements, an accelerator is imperative to replace the reactor to produce medical isotopes on a large scale. However, the isotope target preparation technology at the present stage mainly comprises vacuum evaporation, focused heavy ion beam sputtering, rolling, electroplating, centrifugal precipitation and the like. The above preparation techniques have more or less certain influence on isotope preparation, such as poor uniformity of electroplating targets, high impurity content, and poor uniformity and mechanical strength of targets prepared by centrifugal precipitation, wherein only part of materials can be prepared into electroplating solution. The target with uneven components influences the subsequent use of isotopes when other impurity nuclides are generated under the bombardment of an accelerator, and the coating with uneven surface and improper bonding strength can cause electrons to excessively bombard the substrate to generate new impurity nuclides or cause the coating to fall off in the use process, thereby greatly influencing the use efficiency of the substrate/coating. The preparation of isotope targets is one of the factors that have restricted the progress of the research, and there is an urgent need to solve the above problems.
Disclosure of Invention
The invention aims to solve the problems that the existing isotope target preparation technology is complex, the preparation method is single, the coating on the surface of the target is not uniformly distributed, and the thickness and the bonding force are difficult to control, and further provides a method for preparing a bismuth-antimony alloy coating with uniform surface and stable bonding by utilizing magnetron sputtering.
A method for preparing a bismuth-antimony alloy coating with uniform surface and stable combination by utilizing magnetron sputtering is carried out according to the following steps:
firstly, preparing a bismuth-antimony target:
ball-milling and mixing bismuth metal powder and antimony metal powder to obtain alloyed mixed powder, and preparing the alloyed mixed powder into a target material by adopting a pressure sintering process to obtain a bismuth-antimony target;
secondly, bias cleaning:
mounting a bismuth antimony target on a target position of a direct-current magnetron sputtering device, placing a pre-coating workpiece on a sample table of the direct-current magnetron sputtering device, closing a vacuum chamber, vacuumizing and introducing argon, preheating the pre-coating workpiece, and finally performing bias cleaning on the pre-coating workpiece;
thirdly, direct current magnetron sputtering:
after bias cleaning, introducing argon gas at the flow rate of 10 sccm/min-150 sccm/min to ensure that the working pressure in a vacuum chamber is 0.5 Pa-1.7 Pa, adjusting the target base distance to be 20 mm-150 mm, and performing direct current magnetron sputtering for 10 s-10000 s under the conditions that the temperature of a pre-coated workpiece is 30-150 ℃, the bias voltage is 10V-150V and the current is 0.2A-5A to obtain the bismuth-antimony alloy coating with uniform surface and stable combination.
The invention has the beneficial effects that:
1. the invention aims at the needs of isotope targets, prepares the bismuth-antimony alloy coating with uniform and stable surface by magnetron sputtering, and the combination of the sputtering coating and the substrate is more stable, and particularly, the thickness of the bismuth-antimony alloy coating is 1.5-3.5 mu m, the binding force is 2.1-3.5N, and the surface distribution is uniform. Therefore, the coating prepared by the invention can be used for generating the bismuth-antimony isotope under electron bombardment under an electron accelerator, and solves the problems of complex and single preparation mode, uneven target surface and difficult control of thickness and bonding force of the existing isotope target;
2. the invention can also be used on the surface of materials, and can be used as a composite flame retardant to improve the safety of specific materials at high temperature. Oxides of bismuth and antimony both have flame retardant effects, and Bi2O3Effect ratio of (1) to Sb2O3Better, safe and nontoxicThe lethality of the smoke generated during combustion is extremely low, and the stability of the flame-retardant product is not influenced. When the two are compounded into alloy according to a certain proportion, stable oxide is generated under high-temperature oxidation, and the two have a certain synergistic effect at the same time, so that the flame retardant property of certain materials under specific conditions is improved greatly.
3. The process method adopts magnetron sputtering as a coating preparation technology, and the operation mode is simple and convenient.
Drawings
FIG. 1 is a diagram of an alumina object coated with a bismuth-antimony alloy coating prepared in the first example;
FIG. 2 is a 3D scan of the surface of the alumina coated with a bismuth-antimony alloy coating prepared in the first example;
FIG. 3 is a graph showing the thickness of a coating layer in alumina coated with a bismuth-antimony alloy coating layer prepared in the first example;
FIG. 4 is a critical load test chart of a coating layer in alumina coated with a bismuth-antimony alloy coating layer prepared in the first embodiment;
FIG. 5 is a diagram of a substance of aluminum oxide coated with a bismuth-antimony alloy coating layer prepared in example two;
FIG. 6 is a 3D scan of the surface of the aluminum oxide coated with the Bi-Sb alloy coating prepared in example II;
FIG. 7 is a graph showing the thickness of a coating layer in aluminum oxide coated with a bismuth-antimony alloy coating layer prepared in example two;
FIG. 8 is a critical load test chart of a coating layer in alumina coated with a bismuth-antimony alloy coating layer prepared in example two;
FIG. 9 is a diagram of a substance of aluminum oxide coated with a bismuth-antimony alloy coating layer prepared in example III;
FIG. 10 is a 3D scan of the surface of the alumina coated with the Bi-Sb alloy coating prepared in the third example;
FIG. 11 is a graph showing the thickness of a coating layer in aluminum oxide coated with a bismuth-antimony alloy coating layer prepared in example III;
FIG. 12 is a critical load test chart of a coating layer in alumina coated with a bismuth-antimony alloy coating layer prepared in the third example;
FIG. 13 is a diagram of a bismuth antimony alloy coated alumina object prepared in example four;
FIG. 14 is a 3D scan of the surface of the aluminum oxide coated with the bismuth-antimony alloy coating prepared in example four;
FIG. 15 is a graph showing the thickness of a coating layer in aluminum oxide coated with a bismuth-antimony alloy coating layer prepared in example four;
FIG. 16 is a critical load test chart of the coating layer in the alumina coated with the bismuth-antimony alloy coating layer prepared in the fourth example.
Detailed Description
The first embodiment is as follows: the embodiment of the invention relates to a method for preparing a bismuth-antimony alloy coating with uniform surface and stable combination by magnetron sputtering, which comprises the following steps:
firstly, preparing a bismuth-antimony target:
ball-milling and mixing bismuth metal powder and antimony metal powder to obtain alloyed mixed powder, and preparing the alloyed mixed powder into a target material by adopting a pressure sintering process to obtain a bismuth-antimony target;
secondly, bias cleaning:
mounting a bismuth antimony target on a target position of a direct-current magnetron sputtering device, placing a pre-coating workpiece on a sample table of the direct-current magnetron sputtering device, closing a vacuum chamber, vacuumizing and introducing argon, preheating the pre-coating workpiece, and finally performing bias cleaning on the pre-coating workpiece;
thirdly, direct current magnetron sputtering:
after bias cleaning, introducing argon gas at the flow rate of 10 sccm/min-150 sccm/min to ensure that the working pressure in a vacuum chamber is 0.5 Pa-1.7 Pa, adjusting the target base distance to be 20 mm-150 mm, and performing direct current magnetron sputtering for 10 s-10000 s under the conditions that the temperature of a pre-coated workpiece is 30-150 ℃, the bias voltage is 10V-150V and the current is 0.2A-5A to obtain the bismuth-antimony alloy coating with uniform surface and stable combination.
The beneficial effects of the embodiment are as follows:
1. the embodiment aims at the needs of isotope targets, prepares the bismuth-antimony alloy coating with uniform surface and stable combination by magnetron sputtering, and the combination of the sputtering coating and a substrate is more stable, particularly the thickness of the bismuth-antimony alloy coating is 1.5-3.5 mu m, the binding force is 2.1-3.5N, and the surface distribution is uniform. Therefore, the coating prepared by the embodiment can be used for generating bismuth-antimony isotopes under electron bombardment under an electron accelerator, and solves the problems of complex and single preparation mode, uneven target surface and difficult control of thickness and bonding force of the existing isotope target;
2. the embodiment can also be used on the surface of materials, and can be used as a composite flame retardant to improve the safety of specific materials at high temperature. Oxides of bismuth and antimony both have flame retardant effects, and Bi2O3Effect ratio of (1) to Sb2O3Better, safe and nontoxic, has little lethality of smoke generated during combustion, and does not influence the stability of the flame-retardant product. When the two are compounded into alloy according to a certain proportion, stable oxide is generated under high-temperature oxidation, and the two have a certain synergistic effect at the same time, so that the flame retardant property of certain materials under specific conditions is improved greatly.
3. The process method of the embodiment adopts magnetron sputtering as a coating preparation technology, and the operation mode is simple and convenient.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the grain diameters of the bismuth metal powder and the antimony metal powder in the step one are both 30-90 mu m; the mass ratio of the bismuth metal powder to the antimony metal powder in the first step is 1 (0.1-2). The rest is the same as the first embodiment.
The third concrete implementation mode: this embodiment is different from the first or second embodiment in that: the purities of the bismuth metal powder and the antimony metal powder in the step one are both 99.99%. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the difference between this embodiment mode and one of the first to third embodiment modes is: the ball milling in the step one is carried out by adopting a steel ball milling tank for ball milling and mixing, adding grinding balls according to the ball material mass ratio of (2.7-3.3): 1, sealing, opening a vacuum valve, vacuumizing for 20-30 min, and then carrying out ball milling and mixing for 40-50 min by utilizing a planetary ball mill under the conditions that the rotating speed is 260-300 r/min and the inversion frequency is 32-45 Hz. The others are the same as the first to third embodiments.
The fifth concrete implementation mode: the difference between this embodiment and one of the first to fourth embodiments is: the pressure sintering process in the step one is to perform pressure sintering for 4-7 min under the conditions of argon atmosphere, pressure of 200-320 MPa and sintering temperature of 860-970 ℃. The rest is the same as the first to fourth embodiments.
The sixth specific implementation mode: the difference between this embodiment and one of the first to fifth embodiments is: and the precoated workpiece in the second step is polished 304 stainless steel, polished 316 stainless steel or polished aluminum oxide. The rest is the same as the first to fifth embodiments.
The seventh embodiment: the difference between this embodiment and one of the first to sixth embodiments is: and the precoating workpiece in the second step is a pretreated precoating workpiece. The others are the same as the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment differs from one of the first to seventh embodiments in that: the pretreatment specifically comprises the steps of polishing the surface by using a grinding wheel or abrasive paper to remove pollutants, then respectively ultrasonically cleaning by using acetone, absolute ethyl alcohol and deionized water, and finally drying. The rest is the same as the first to seventh embodiments.
The specific implementation method nine: the present embodiment differs from the first to eighth embodiments in that: vacuumizing and introducing argon in the second step, specifically vacuumizing to 2 multiplied by 10-2Pa～2×10-3Pa, then introducing argon to stabilize the pressure at 0.1-5.0 Pa. The other points are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the present embodiment differs from one of the first to ninth embodiments in that: and the bias cleaning in the second step is to perform ion bombardment glow cleaning on the precoated workpiece for 10-20 min under the condition that the negative bias is 10-150V. The other points are the same as those in the first to ninth embodiments.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows:
a method for preparing a bismuth-antimony alloy coating with uniform surface and stable combination by utilizing magnetron sputtering is carried out according to the following steps:
firstly, preparing a bismuth-antimony target:
ball-milling and mixing bismuth metal powder and antimony metal powder to obtain alloyed mixed powder, and preparing the alloyed mixed powder into a target material by adopting a pressure sintering process to obtain a bismuth-antimony target;
the mass ratio of the bismuth metal powder to the antimony metal powder is 1: 1;
secondly, bias cleaning:
mounting a bismuth antimony target on a target position of a direct-current magnetron sputtering device, placing a pre-coating workpiece on a sample table of the direct-current magnetron sputtering device, closing a vacuum chamber, vacuumizing and introducing argon, preheating the pre-coating workpiece, and finally performing bias cleaning on the pre-coating workpiece;
thirdly, direct current magnetron sputtering:
after bias cleaning, argon is introduced at a flow rate of 60scc/min to ensure that the working pressure in a vacuum chamber is 0.5Pa, the target base distance is adjusted to be 50mm, and under the conditions that the temperature of a precoated workpiece is 50 ℃, the bias voltage is 60V and the current is 0.4A, direct-current magnetron sputtering is carried out for 4500s, so that the aluminum oxide with the surface being coated with the bismuth-antimony alloy coating is obtained.
The grain diameters of the bismuth metal powder and the antimony metal powder in the step one are both 30-90 mu m.
The purities of the bismuth metal powder and the antimony metal powder in the step one are both 99.99%.
And the ball milling in the step one is carried out by adopting a steel ball milling tank for ball milling and mixing, adding grinding balls according to the ball material mass ratio of 2.7:1, sealing, opening a vacuum valve, vacuumizing for 20min, and then carrying out ball milling and mixing for 45min by utilizing a planetary ball mill under the conditions that the rotating speed is 265r/min and the inversion frequency is 40 Hz.
The pressure sintering process in the step one is to perform pressure sintering for 5min under the conditions of argon atmosphere, pressure of 260MPa and sintering temperature of 900 ℃.
And the precoated workpiece in the second step is polished aluminum oxide.
And the precoating workpiece in the second step is a pretreated precoating workpiece.
The pretreatment specifically comprises the steps of polishing the surface with sand paper to remove pollutants, then respectively ultrasonically cleaning with acetone, absolute ethyl alcohol and deionized water for 20min, and finally drying in a drying oven at the temperature of 60 ℃ for 60 min.
Vacuumizing and introducing argon in the second step, specifically vacuumizing to 2 multiplied by 10-3Pa, then argon gas was introduced to stabilize the pressure at 0.1 Pa.
And the bias cleaning in the second step is to perform ion bombardment glow cleaning on the pre-coating workpiece for 12min under the condition that the negative bias is 50V.
Example two:
a method for preparing a bismuth-antimony alloy coating with uniform surface and stable combination by utilizing magnetron sputtering is carried out according to the following steps:
firstly, preparing a bismuth-antimony target:
ball-milling and mixing bismuth metal powder and antimony metal powder to obtain alloyed mixed powder, and preparing the alloyed mixed powder into a target material by adopting a pressure sintering process to obtain a bismuth-antimony target;
the mass ratio of the bismuth metal powder to the antimony metal powder is 1: 1.2;
secondly, bias cleaning:
mounting a bismuth antimony target on a target position of a direct-current magnetron sputtering device, placing a pre-coating workpiece on a sample table of the direct-current magnetron sputtering device, closing a vacuum chamber, vacuumizing and introducing argon, preheating the pre-coating workpiece, and finally performing bias cleaning on the pre-coating workpiece;
thirdly, direct current magnetron sputtering:
after bias cleaning, introducing argon gas at the flow rate of 75sccm/min to ensure that the working pressure in the vacuum chamber is 0.6Pa, adjusting the target base distance to be 80mm, and performing direct current magnetron sputtering for 3500s under the conditions that the temperature of the pre-coating workpiece is 60 ℃, the bias voltage is 80V and the current is 0.3A to obtain the aluminum oxide with the surface coated with the bismuth-antimony alloy coating.
The grain diameters of the bismuth metal powder and the antimony metal powder in the step one are both 30-90 mu m.
The purities of the bismuth metal powder and the antimony metal powder in the step one are both 99.99%.
And the ball milling in the step one is carried out by adopting a steel ball milling tank for ball milling and mixing, adding grinding balls according to the ball-to-material mass ratio of 2.9:1, sealing, opening a vacuum valve, vacuumizing for 23min, and then carrying out ball milling and mixing for 41min by utilizing a planetary ball mill under the conditions that the rotating speed is 273r/min and the inversion frequency is 36 Hz.
The pressure sintering process in the step one is to perform pressure sintering for 6min under the conditions of argon atmosphere, the pressure of 290MPa and the sintering temperature of 950 ℃.
And the precoated workpiece in the second step is polished aluminum oxide.
And the precoating workpiece in the second step is a pretreated precoating workpiece.
The pretreatment specifically comprises the steps of polishing the surface with sand paper to remove pollutants, then respectively ultrasonically cleaning with acetone, absolute ethyl alcohol and deionized water for 25min, and finally drying in a drying oven at the temperature of 80 ℃ for 60 min.
Vacuumizing and introducing argon in the second step, specifically vacuumizing to 9 x 10-3Pa, then argon gas was introduced to stabilize the pressure at 0.2 Pa.
And the bias cleaning in the second step is to perform ion bombardment glow cleaning on the pre-coated workpiece for 10min under the condition that the negative bias is 100V.
Example three:
a method for preparing a bismuth-antimony alloy coating with uniform surface and stable combination by utilizing magnetron sputtering is carried out according to the following steps:
firstly, preparing a bismuth-antimony target:
ball-milling and mixing bismuth metal powder and antimony metal powder to obtain alloyed mixed powder, and preparing the alloyed mixed powder into a target material by adopting a pressure sintering process to obtain a bismuth-antimony target;
the mass ratio of the bismuth metal powder to the antimony metal powder is 1: 1.5;
secondly, bias cleaning:
mounting a bismuth antimony target on a target position of a direct-current magnetron sputtering device, placing a pre-coating workpiece on a sample table of the direct-current magnetron sputtering device, closing a vacuum chamber, vacuumizing and introducing argon, preheating the pre-coating workpiece, and finally performing bias cleaning on the pre-coating workpiece;
thirdly, direct current magnetron sputtering:
after bias cleaning, introducing argon gas at the flow rate of 90sccm/min to ensure that the working pressure in the vacuum chamber is 0.7Pa, adjusting the target base distance to be 90mm, and performing direct current magnetron sputtering for 4000s under the conditions that the temperature of the pre-coating workpiece is 40 ℃, the bias voltage is 120V and the current is 0.6A to obtain the aluminum oxide with the surface coated with the bismuth-antimony alloy coating.
The grain diameters of the bismuth metal powder and the antimony metal powder in the step one are both 30-90 mu m.
The purities of the bismuth metal powder and the antimony metal powder in the step one are both 99.99%.
And the ball milling in the step one is carried out by adopting a steel ball milling tank for ball milling and mixing, grinding balls are added according to the ball material mass ratio of 3:1, a vacuum valve is opened after sealing, vacuum pumping is carried out for 26min, and then the ball milling and mixing are carried out for 46min by utilizing a planetary ball mill under the conditions that the rotating speed is 273r/min and the inversion frequency is 37 Hz.
The pressure sintering process in the step one is to perform pressure sintering for 6min under the conditions of argon atmosphere, pressure of 290MPa and sintering temperature of 900 ℃.
And the precoated workpiece in the second step is polished aluminum oxide.
And the precoating workpiece in the second step is a pretreated precoating workpiece.
The pretreatment specifically comprises the steps of polishing the surface with sand paper to remove pollutants, then respectively ultrasonically cleaning with acetone, absolute ethyl alcohol and deionized water for 20min, and finally drying in a drying oven at the temperature of 60 ℃ for 60 min.
Vacuumizing and introducing argon in the second step, specifically vacuumizing to 8.8 multiplied by 10-3Pa, then argon gas was introduced to stabilize the pressure at 0.6 Pa.
And the bias cleaning in the second step is to perform ion bombardment glow cleaning on the pre-coating workpiece for 20min under the condition that the negative bias is 90V.
Example four:
a method for preparing a bismuth-antimony alloy coating with uniform surface and stable combination by utilizing magnetron sputtering is carried out according to the following steps:
firstly, preparing a bismuth-antimony target:
ball-milling and mixing bismuth metal powder and antimony metal powder to obtain alloyed mixed powder, and preparing the alloyed mixed powder into a target material by adopting a pressure sintering process to obtain a bismuth-antimony target;
the mass ratio of the bismuth metal powder to the antimony metal powder is 1: 1.25;
secondly, bias cleaning:
mounting a bismuth antimony target on a target position of a direct-current magnetron sputtering device, placing a pre-coating workpiece on a sample table of the direct-current magnetron sputtering device, closing a vacuum chamber, vacuumizing and introducing argon, preheating the pre-coating workpiece, and finally performing bias cleaning on the pre-coating workpiece;
thirdly, direct current magnetron sputtering:
after bias cleaning, introducing argon gas at a flow rate of 85sccm/min to ensure that the working pressure in the vacuum chamber is 0.9Pa, adjusting the target base distance to be 60mm, and performing direct current magnetron sputtering for 2700s under the conditions that the temperature of the pre-coating workpiece is 150 ℃, the bias voltage is 100V and the current is 0.5A to obtain the aluminum oxide with the surface coated with the bismuth-antimony alloy coating.
The grain diameters of the bismuth metal powder and the antimony metal powder in the step one are both 30-90 mu m.
The purities of the bismuth metal powder and the antimony metal powder in the step one are both 99.99%.
And the ball milling in the step one is carried out by adopting a steel ball milling tank for ball milling and mixing, adding grinding balls according to the ball-material mass ratio of 3.1:1, sealing, opening a vacuum valve, vacuumizing for 27min, and then carrying out ball milling and mixing for 47min by utilizing a planetary ball mill under the conditions that the rotating speed is 275r/min and the inversion frequency is 43 Hz.
The pressure sintering process in the step one is to perform pressure sintering for 4min under the conditions of argon atmosphere, pressure of 300MPa and sintering temperature of 900 ℃.
And the precoated workpiece in the second step is polished aluminum oxide.
And the precoating workpiece in the second step is a pretreated precoating workpiece.
The pretreatment specifically comprises the steps of polishing the surface with sand paper to remove pollutants, then respectively ultrasonically cleaning with acetone, absolute ethyl alcohol and deionized water for 20min, and finally drying in a drying oven at the temperature of 100 ℃ for 100 min.
Vacuumizing and introducing argon in the second step, specifically vacuumizing to 2.6 multiplied by 10-3Pa, then argon gas was introduced to stabilize the pressure at 0.5 Pa.
And the bias cleaning in the second step is to perform ion bombardment glow cleaning on the pre-coating workpiece for 18min under the condition that the negative bias is 150V.
In the first to fourth embodiments, a plurality of aluminum oxides with bismuth-antimony alloy coatings on the surfaces are prepared simultaneously, and in order to facilitate the subsequent coating thickness test, the thickness test specimen needs to be wound on the surface of the substrate through a polyimide adhesive tape, so that the surface of the aluminum oxide is partially coated with the bismuth-antimony alloy coating, and the surface of the aluminum oxide is partially not coated with a thin film.
FIG. 1 is a diagram of an alumina object coated with a bismuth-antimony alloy coating prepared in the first example; FIG. 2 is a 3D scan of the surface of the alumina coated with a bismuth-antimony alloy coating prepared in the first example; as can be seen, the coating surfaces are all on the same horizontal plane and fluctuate between 100nm, meeting the requirement of uniformity.
The coating thickness was measured using a Bruker step profiler under closed conditions, a probe weight of 3mg, a probe glide distance of 1500 μm, and a step range of 6.5 μm. FIG. 3 is a graph showing the thickness of a coating layer in alumina coated with a bismuth-antimony alloy coating layer prepared in the first example; as can be seen, the height of the upper and lower steps is 2.13 μm, i.e., the distance between the upper surface of the coating and the upper surface of the substrate is 2.13 μm, and the thickness of the coating is 2.13. mu.m.
FIG. 4 is a critical load test chart of a coating layer in alumina coated with a bismuth-antimony alloy coating layer prepared in the first embodiment; it can be seen from the figure that when the critical load is loaded to 3.04, the coating is scratched, and the sound wave receiver receives the acoustic signal, i.e. the membrane-based bonding force is measured to be 3.04N.
FIG. 5 is a diagram of a substance of aluminum oxide coated with a bismuth-antimony alloy coating layer prepared in example two; FIG. 6 is a 3D scan of the surface of the aluminum oxide coated with the Bi-Sb alloy coating prepared in example II; as can be seen, the coating surfaces are all on the same horizontal plane and fluctuate between 300nm, meeting the requirement of uniformity.
The coating thickness was measured using a Bruker step profiler under closed conditions, a probe weight of 3mg, a probe glide distance of 1500 μm, and a step range of 6.5 μm. FIG. 7 is a graph showing the thickness of a coating layer in aluminum oxide coated with a bismuth-antimony alloy coating layer prepared in example two; as can be seen, the height of the upper and lower steps is 1.60 μm, i.e., the distance between the upper surface of the coating and the upper surface of the substrate is 1.60 μm, and the thickness of the coating is 1.60 μm.
FIG. 8 is a critical load test chart of a coating layer in alumina coated with a bismuth-antimony alloy coating layer prepared in example two; it can be seen from the figure that when the critical load is loaded to 3.46N, the coating is scratched, and the sound wave receiver receives the acoustic signal, i.e. the membrane-based bonding force is measured to be 3.46N.
FIG. 9 is a diagram of a substance of aluminum oxide coated with a bismuth-antimony alloy coating layer prepared in example III; FIG. 10 is a 3D scan of the surface of the alumina coated with the Bi-Sb alloy coating prepared in the third example; as can be seen, the coating surfaces are all on the same horizontal plane and fluctuate between 400nm, meeting the requirement of uniformity.
The coating thickness was measured using a Bruker step profiler under closed conditions, a probe weight of 3mg, a probe glide distance of 1500 μm, and a step range of 6.5 μm. FIG. 11 is a graph showing the thickness of a coating layer in aluminum oxide coated with a bismuth-antimony alloy coating layer prepared in example III; as can be seen, the height of the upper and lower steps is 2.53 μm, i.e., the distance between the upper surface of the coating and the upper surface of the substrate is 2.53 μm, and the thickness of the coating is 2.53. mu.m.
FIG. 12 is a critical load test chart of a coating layer in alumina coated with a bismuth-antimony alloy coating layer prepared in the third example; it can be seen from the figure that when the critical load is loaded to 3.15N, the coating is scratched, and the sound wave receiver receives the acoustic signal, i.e. the membrane-based bonding force is measured to be 3.15N.
FIG. 13 is a diagram of a bismuth antimony alloy coated alumina object prepared in example four; FIG. 14 is a 3D scan of the surface of the aluminum oxide coated with the bismuth-antimony alloy coating prepared in example four; as can be seen from the figure, the coating layers are coated on the two sides, the coating layer is not coated in the middle, the surfaces of the coating layers are all on the same horizontal plane, the fluctuation is 200nm from top to bottom, and the requirement of uniformity is met.
The coating thickness was measured using a Bruker step profiler under closed conditions, a probe weight of 3mg, a probe glide distance of 1500 μm, and a step range of 6.5 μm. FIG. 15 is a graph showing the thickness of a coating layer in aluminum oxide coated with a bismuth-antimony alloy coating layer prepared in example four; as can be seen, the height of the upper and lower steps is 1.40 μm, i.e., the distance between the upper surface of the coating and the upper surface of the substrate is 1.40 μm, and the thickness of the coating is 1.40 μm.
FIG. 16 is a critical load test chart of a coating layer in alumina coated with a bismuth-antimony alloy coating layer prepared in example four; it can be seen from the figure that when the critical load is loaded to 3.24N, the coating lacerated sonic receiver receives the acoustic signal, i.e. the membrane-based bonding force is measured to be 3.24N.

Claims (10)

1. A method for preparing a bismuth-antimony alloy coating with uniform surface and stable combination by utilizing magnetron sputtering is characterized by comprising the following steps:
firstly, preparing a bismuth-antimony target:
ball-milling and mixing bismuth metal powder and antimony metal powder to obtain alloyed mixed powder, and preparing the alloyed mixed powder into a target material by adopting a pressure sintering process to obtain a bismuth-antimony target;
secondly, bias cleaning:
mounting a bismuth antimony target on a target position of a direct-current magnetron sputtering device, placing a pre-coating workpiece on a sample table of the direct-current magnetron sputtering device, closing a vacuum chamber, vacuumizing and introducing argon, preheating the pre-coating workpiece, and finally performing bias cleaning on the pre-coating workpiece;
thirdly, direct current magnetron sputtering:
after bias cleaning, introducing argon gas at the flow rate of 10 sccm/min-150 sccm/min to ensure that the working pressure in a vacuum chamber is 0.5 Pa-1.7 Pa, adjusting the target base distance to be 20 mm-150 mm, and performing direct current magnetron sputtering for 10 s-10000 s under the conditions that the temperature of a pre-coated workpiece is 30-150 ℃, the bias voltage is 10V-150V and the current is 0.2A-5A to obtain the bismuth-antimony alloy coating with uniform surface and stable combination.
2. The method for preparing the bismuth-antimony alloy coating with uniform surface and stable combination by magnetron sputtering according to claim 1, wherein the grain sizes of the bismuth metal powder and the antimony metal powder in the step one are both 30 μm to 90 μm; the mass ratio of the bismuth metal powder to the antimony metal powder in the first step is 1 (0.1-2).
3. The method for preparing the bismuth-antimony alloy coating with uniform surface and stable combination by magnetron sputtering as claimed in claim 1, wherein the purity of the bismuth metal powder and the purity of the antimony metal powder in the step one are both 99.99%.
4. The method for preparing the bismuth-antimony alloy coating with uniform surface and stable combination by magnetron sputtering according to claim 1, wherein the ball milling in the step one is performed by a steel ball milling tank, grinding balls are added according to a ball-material mass ratio of (2.7-3.3): 1, a vacuum valve is opened after sealing, vacuum pumping is performed for 20-30 min, and then a planetary ball mill is used for ball milling and mixing for 40-50 min under the conditions that the rotating speed is 260-300 r/min and the inversion frequency is 32-45 Hz.
5. The method for preparing the bismuth-antimony alloy coating with uniform and stable surface by magnetron sputtering according to claim 1, wherein the pressure sintering process in the step one is carried out for 4-7 min under the conditions of argon atmosphere, pressure of 200-320 MPa and sintering temperature of 860-970 ℃.
6. The method of claim 1, wherein the pre-coated workpiece in step two is polished 304 stainless steel, polished 316 stainless steel or polished aluminum oxide.
7. The method for preparing the bismuth-antimony alloy coating with uniform and stable surface by magnetron sputtering according to claim 1, wherein the pre-coated workpiece in the second step is a pre-coated workpiece after pretreatment.
8. The method for preparing the bismuth-antimony alloy coating with uniform and stable surface by magnetron sputtering according to claim 7, wherein the pretreatment comprises polishing the surface with a grinding wheel or sand paper to remove pollutants, ultrasonic cleaning with acetone, absolute ethyl alcohol and deionized water, and drying.
9. The method for preparing the bismuth-antimony alloy coating with uniform surface and stable combination by magnetron sputtering as claimed in claim 1, wherein the step two is vacuumized and argon is introduced, specifically, vacuumized to 2 x 10-2Pa～2×10-3Pa, then introducing argon to stabilize the pressure at 0.1-5.0 Pa.
10. The method for preparing the bismuth-antimony alloy coating with uniform and stable surface by magnetron sputtering according to claim 1, wherein the bias cleaning in the second step is ion bombardment glow cleaning for 10-20 min on the pre-coated workpiece under the condition that the negative bias is 10-150V.
CN202111591854.8A 2021-12-23 2021-12-23 Method for preparing bismuth-antimony alloy coating with uniform surface and stable combination by utilizing magnetron sputtering Active CN114250441B (en)

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