CN115652401A - Plasma polishing solution for laser additive manufacturing of titanium alloy workpiece and preparation and application thereof - Google Patents
Plasma polishing solution for laser additive manufacturing of titanium alloy workpiece and preparation and application thereof Download PDFInfo
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- CN115652401A CN115652401A CN202211386233.0A CN202211386233A CN115652401A CN 115652401 A CN115652401 A CN 115652401A CN 202211386233 A CN202211386233 A CN 202211386233A CN 115652401 A CN115652401 A CN 115652401A
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Abstract
The invention relates to a plasma polishing solution for laser additive manufacturing of a titanium alloy workpiece, and preparation and application thereof, and belongs to the technical field of metal surface treatment. A plasma polishing solution for laser additive manufacturing of a titanium alloy workpiece is characterized in that: the plasma polishing solution is an aqueous solution and consists of the following components: methanesulfonic acid 500-750ml/L, NH 2 SO 4 1-3g/L, 1-7ml/L of sulfosalicylic acid and 5-10g/L of sodium chloride. The plasma polishing solution is green and environment-friendly, the raw materials are easy to obtain, and the processing environment is not polluted; the required voltage is lower when plasma polishing is carried out, the energy consumption of production is effectively reduced, and the method is suitable for the development direction of green manufacturing, so that the method is favorable for popularization. The plasma polishing solution is used for polishing the special-shaped titanium alloy workpiece manufactured by laser additive manufacturing, and the weight loss rate of the sampleThe surface roughness of the titanium alloy can be effectively reduced, the overall glossiness is improved, and the surface of a high-quality titanium alloy workpiece is obtained.
Description
Technical Field
The invention relates to a plasma polishing solution for laser additive manufacturing of a titanium alloy workpiece, and preparation and application thereof, and belongs to the technical field of metal surface treatment.
Background
The laser additive manufacturing technology has the advantages of high forming speed, high material utilization rate, capability of integrally forming complex parts and the like, and is widely applied to manufacturing metal workpieces which are difficult to manufacture through a traditional method or a traditional manufacturing method and have high cost at present. Metals applied to the additive manufacturing technology mainly comprise titanium, nickel, aluminum and the like, wherein titanium alloy is widely concerned by people due to the advantages of light weight, high strength, good toughness, corrosion resistance, high heat resistance and the like, and the additive manufacturing of titanium alloy is also widely applied in the fields of aerospace, navigation, petrochemical industry, human implants, biomedical engineering and the like. However, in these fields, the requirements for the surface quality of titanium alloy parts are also increasing, and it is very important to improve the surface treatment technology of additive manufacturing titanium alloy.
However, since titanium alloys have poor machinability and easily form an oxide film on the surface of a substrate, surface finishing is generally performed by a method such as mechanical polishing or chemical polishing.
The mechanical polishing method relies on the grinding and rolling action of very fine polishing powder to remove a very thin layer of metal from the ground surface of the sample. The mechanical polishing operation method is simple, but consumes manpower, and can not realize uniform leveling of all parts of the special-shaped titanium alloy workpiece with a complex structure or polishing dead angles such as curved surfaces, corners, grids and the like, and the application range is greatly limited. Chemical polishing is a method for eliminating grinding marks, eroding and flattening a sample by selectively dissolving uneven areas on the surface of the sample through the chemical etching action of a chemical reagent. The chemical polishing equipment is simple, can process thin pipes, parts with deep holes and complex shapes, has high production efficiency, and is an effective way for improving the surface quality of the titanium alloy and improving the processing efficiency. However, most of the components of the polishing solution for chemical polishing are strong corrosive acidic solutions, which can react violently during the operation process, and have certain danger to operators, and the generated toxic substances or irritant gases are easily volatilized into the air, thus causing harm to the environment.
Based on this, plasma polishing is receiving increasing attention. The main technical point of plasma polishing is that under high temperature and high pressure, electrons can escape from atomic nuclei, the atomic nuclei form positively charged ions, when the ions reach a certain amount, the ions can become plasma state, the energy of the plasma state is very large, and when the plasma and an object to be polished rub against each other, the object can reach the effect of surface brightness in a hectare. No scratch is generated during plasma polishing, and the polishing effect is good. The processed workpiece has bright and beautiful surface, bright color and dazzling brightness, can prevent the workpiece from being rusted, keeps and improves the luster of the surface of the workpiece, and plays a role in cleaning the workpiece and the grinding tool. Meanwhile, the plasma polishing is simple in operation and high in automation degree, and is a polishing method capable of efficiently improving the surface quality of the titanium alloy.
Several plasma polishing solutions disclosed in the prior art mainly adopt low-concentration inorganic salt aqueous solutions such as sodium sulfate, ammonium sulfate, sodium citrate, hydrofluoride and the like, and the polishing process is green and environment-friendly. But active components in the plasma polishing solution are continuously lost in the polishing process, gas and insoluble precipitates are generated at the same time, and the newly configured polishing solution needs to be replaced at regular time; and the voltage applied during plasma polishing is usually over 300V, so that the production cost is greatly increased. Therefore, the development of a plasma polishing solution which has good polishing effect, easily obtained raw materials, low energy consumption and renewable solution and can meet the processing requirement is urgently needed on the basis of environmental protection.
Disclosure of Invention
The invention aims to overcome the defects of the existing laser additive manufacturing titanium alloy plasma polishing solution and polishing process, and provides the plasma polishing solution and the polishing method which have the advantages of low preparation cost, strong stability, environmental friendliness, renewable solution, capability of effectively protecting a titanium alloy matrix and ideal surface flattening and smoothing effect and are suitable for laser additive manufacturing of special-shaped titanium alloy workpieces with processing dead angles such as curved surfaces, corners and grids.
A plasma polishing solution for laser additive manufacturing of a titanium alloy workpiece is an aqueous solution and comprises the following components:
preferably, the plasma polishing solution for laser additive manufacturing of the titanium alloy workpiece consists of the following components:
preferably, the plasma polishing solution for laser additive manufacturing of the titanium alloy workpiece consists of the following components:
the invention also aims to provide a preparation method of the plasma polishing solution for the laser additive manufacturing of the titanium alloy workpiece.
A process for preparing the plasma polishing liquid used to prepare Ti-alloy workpiece by laser additive includes proportionally mixing methanesulfonic acid and NH 2 SO 4 And (3) placing sulfosalicylic acid and sodium chloride into deionized water, and uniformly mixing to obtain the polishing solution.
The invention further aims to provide a method for performing plasma polishing by using the plasma polishing solution for the laser additive manufacturing of the titanium alloy workpiece.
A plasma polishing method for laser additive manufacturing of a titanium alloy workpiece comprises the steps of carrying out ultrasonic cleaning and oil removal on the laser additive manufacturing titanium alloy workpiece in acetone, and then cleaning and drying the workpiece by using deionized water; firstly, putting the polishing solution into an electrolytic bath, heating the electrolytic bath to enable the temperature of the solution to reach 95 ℃, then taking the titanium alloy workpiece as an anode and graphite as a cathode to be soaked in the polishing solution together for polishing, cleaning and drying.
Preferably, the polishing temperature is 95 ℃.
Preferably, the polishing time is 120s.
Preferably, the polishing voltage is 270V to 300V, and more preferably, the polishing voltage is 280V.
Preferably, the method comprises a polishing solution regeneration step, specifically: adding NaOH 25-50g/L into polishing solution containing titanium ions, filtering to remove titanium precipitate, and adding 38% hydrochloric acid 70-200ml/L.
Preferably, the polishing solution is a new polishing solution prepared or a polishing solution regenerated.
The invention has the beneficial effects that;
the plasma polishing solution is green and environment-friendly, the raw materials are easy to obtain, and the processing environment is not polluted; the voltage required by plasma polishing is lower, the energy consumption of production is effectively reduced, and the method is suitable for the development direction of green manufacturing, so that the method is beneficial to popularization. The plasma polishing process for the surface of the titanium alloy manufactured by the additive manufacturing method is simple in implementation process and wide in application range, is suitable for manufacturing the titanium alloy product with a regular shape by the additive manufacturing method, and is still suitable for complex titanium alloy products with pipelines, inner holes or inner flow passages with different diameters. The additive manufacturing titanium alloy plasma polishing solution can be recycled for multiple times on the premise of replenishing mother liquor, and is high in efficiency. The plasma polishing solution is used for polishing the special-shaped titanium alloy workpiece manufactured by laser additive manufacturing, the weight loss rate of the sample is low, the surface roughness of the titanium alloy can be effectively reduced, the overall glossiness is improved, and the surface of the high-quality titanium alloy workpiece is obtained.
Drawings
FIG. 1 is an SEM image of the surface morphology of a titanium alloy workpiece after simple pretreatment in laser additive manufacturing.
FIG. 2 is an SEM image of the surface topography of a titanium alloy workpiece manufactured by laser additive manufacturing in example 5 after being treated by the plasma polishing solution and the polishing method provided by the invention.
FIG. 3 is a graph showing the relationship between the polishing time and the surface roughness and the thinning rate of the titanium alloy workpiece in example 3.
FIG. 4 is a graph showing the relationship between the polishing voltage and the surface roughness and the thinning rate of a titanium alloy workpiece in example 4.
Detailed Description
The following non-limiting examples are presented to enable those of ordinary skill in the art to more fully understand the present invention and are not intended to limit the invention in any way.
The test methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
The plasma polishing solution for manufacturing the special-shaped titanium alloy workpiece by laser additive manufacturing comprises the following components in percentage by weight:
preferably, the plasma polishing solution suitable for laser additive manufacturing of the special-shaped titanium alloy workpiece comprises the following components in percentage by weight:
further preferably, the plasma polishing solution suitable for laser additive manufacturing of the special-shaped titanium alloy workpiece comprises the following components in percentage by weight:
a plasma polishing solution and a polishing method for manufacturing a special-shaped titanium alloy workpiece by laser additive manufacturing further comprise the following process steps:
(1) Pretreatment: ultrasonic cleaning and degreasing are carried out on the titanium alloy workpiece manufactured by the laser additive manufacturing in acetone solution, and then deionized water is used for cleaning and drying the workpiece.
(2) Preparing a plasma polishing solution: the polishing liquid used for plasma polishing is the polishing liquid described in claim 1: 610-640ml/L of methanesulfonic acid (analytically pure), 1.7-2.3g/L of NH 2 SO 4 (analytically pure), 3.1-4.9ml/L sulfosalicylic acid (analytically pure), 6.6-8.4g/L sodium chloride are proportionally added and mixed evenly to prepare 1L solution.
(3) Plasma polishing: firstly, the evenly mixed polishing solution is put into an electrolytic bath, and the electrolytic bath is heated to ensure that the temperature of the solution reaches 95 ℃. Then, the titanium alloy workpiece is taken as a positive electrode, graphite is taken as a negative electrode, the titanium alloy workpiece and the graphite are immersed in the solution together, polishing is carried out for 120s at the temperature of 95 ℃, and the voltage is controlled to be 270-300V.
(4) And (3) post-treatment: and taking out the treated titanium alloy sample, cleaning and drying.
Example 1
And performing plasma polishing treatment on the TC4 titanium alloy workpiece with the length, the width and the height of 8mm and 20mm respectively and the height of 3 mm.
(1) Pretreatment: ultrasonic cleaning and degreasing are carried out on the titanium alloy workpiece manufactured by the laser additive manufacturing in an acetone solution, and then deionized water is used for cleaning and drying the part.
(2) Preparing a plasma polishing solution: according to the polishing liquid provided by the present invention, 610ml of methanesulfonic acid (analytical grade), 1.7g of NH 2 SO 4 (analytically pure), 3.1ml of sulfosalicylic acid (analytically pure), 6.6g of sodium chloride were added in proportion and mixed well to prepare a 1L solution.
(3) Plasma polishing: firstly, the evenly mixed polishing solution is put into an electrolytic bath, and the electrolytic bath is heated to enable the temperature of the solution to reach 95 ℃. Then, the titanium alloy workpiece is taken as a positive electrode, graphite is taken as a negative electrode, the titanium alloy workpiece and the graphite are immersed in the solution together, and the solution is polished for 110s at the temperature of 95 ℃, and the voltage is controlled to be 270V.
(4) And (3) post-treatment: and ultrasonically cleaning the special-shaped titanium alloy workpiece subjected to the plasma polishing treatment for 5min by using absolute ethyl alcohol, taking out, drying, and observing the surface of the sample.
The surface roughness of the special-shaped titanium alloy workpiece manufactured by laser additive manufacturing is obviously reduced and the weight loss is less measured before and after the plasma polishing treatment. The roughness is reduced from 10.385um to 1.943um, and the weight loss rate of the sample is 5.173%.
Example 2
And performing plasma polishing treatment on the TC4 titanium alloy workpiece with the length, the width and the height of 8mm and 20mm respectively and the height of 3 mm.
(1) Pretreatment: ultrasonic cleaning and degreasing are carried out on the titanium alloy workpiece manufactured by the laser additive manufacturing in an acetone solution, and then deionized water is used for cleaning and drying the part.
(2) Preparing a plasma polishing solution: according to the polishing solution provided by the invention, 620ml of methanesulfonic acid (analytically pure), 1.9g of NH are preferably used 2 SO 4 (analytically pure), 3.7ml of sulfosalicylic acid (analytically pure), 7.2g of sodium chloride were added in proportion and mixed well to prepare a 1L solution.
(3) Plasma polishing: firstly, the evenly mixed polishing solution is put into an electrolytic bath, and the electrolytic bath is heated to enable the temperature of the solution to reach 95 ℃. Then, the titanium alloy workpiece is taken as a positive electrode, graphite is taken as a negative electrode, the titanium alloy workpiece and the graphite are immersed in the solution together, polishing is carried out for 120s at the temperature of 95 ℃, and the voltage is controlled to be 280V.
(4) And (3) post-treatment: and ultrasonically cleaning the special-shaped titanium alloy workpiece subjected to the plasma polishing treatment for 5min by using absolute ethyl alcohol, taking out, drying, and observing the surface of the sample.
The surface roughness of the special-shaped titanium alloy workpiece manufactured by laser additive manufacturing is obviously reduced and the weight loss is less measured before and after the plasma polishing treatment. The roughness is reduced from 9.745um to 1.328um, and the weight loss rate of the sample is 5.253 percent.
Example 3
And performing plasma polishing treatment on the TC4 titanium alloy workpiece with the length, the width and the height of 8mm and 20mm respectively and the height of 3 mm.
(1) Pretreatment: ultrasonic cleaning and degreasing are carried out on the titanium alloy workpiece manufactured by the laser additive manufacturing in an acetone solution, and then deionized water is used for cleaning and drying the part.
(2) Preparing a plasma polishing solution: according to the polishing solution provided by the invention, 630ml of methanesulfonic acid (analytical grade), 2.1g of NH 2 SO 4 (analytically pure), 4.3ml of sulfosalicylic acid (analytically pure), 7.8g of sodium chloride in a ratioThe mixture was added and mixed well to prepare a 1L solution.
(3) Plasma polishing: firstly, the evenly mixed polishing solution is put into an electrolytic bath, and the electrolytic bath is heated to enable the temperature of the solution to reach 95 ℃. Then, the titanium alloy workpiece is used as a positive electrode, graphite is used as a negative electrode, and the titanium alloy workpiece and the graphite are immersed in the solution together, and polished at the temperature of 95 ℃ for 110s, 120s, 130s and 140s, and the voltage is controlled to be 290V.
(4) And (3) post-treatment: and ultrasonically cleaning the special-shaped titanium alloy workpiece subjected to the plasma polishing treatment for 5min by using absolute ethyl alcohol, taking out, drying, and observing the surface of the sample.
The surface roughness and the weight loss rate of the special-shaped titanium alloy workpiece manufactured by laser additive manufacturing are measured before and after the plasma polishing treatment and change along with the polishing time. The polishing time is 110s-140s, the roughness is respectively reduced from 10.115um to 2.012um, 1.633um, 1.481um and 1.572um, and the weight loss rate of the sample is 4.093%, 5.227%, 5.981% and 6.327%.
Example 4
And performing plasma polishing treatment on the TC4 titanium alloy workpiece with the length, the width and the height of 8mm and 20mm respectively and the height of 3 mm.
(1) Pretreatment: ultrasonic cleaning and degreasing are carried out on the titanium alloy workpiece manufactured by the laser additive manufacturing in an acetone solution, and then deionized water is used for cleaning and drying the part.
(2) Preparing a plasma polishing solution: according to the polishing solution provided by the invention, 630ml of methanesulfonic acid (analytically pure), 2.1g of NH 2 SO 4 (analytically pure), 4.3ml of sulfosalicylic acid (analytically pure), 7.8g of sodium chloride were added in proportion and mixed well to prepare a 1L solution.
(3) Plasma polishing: firstly, the evenly mixed polishing solution is put into an electrolytic bath, and the electrolytic bath is heated to enable the temperature of the solution to reach 95 ℃. Then, the titanium alloy workpiece is taken as a positive electrode, graphite is taken as a negative electrode, the titanium alloy workpiece and the graphite are immersed in the solution together, polishing is carried out for 130s at the temperature of 95 ℃, and the voltage is controlled to be 270V, 280V, 290V and 300V respectively.
(4) And (3) post-treatment: and ultrasonically cleaning the special-shaped titanium alloy workpiece subjected to the plasma polishing treatment for 5min by using absolute ethyl alcohol, taking out, drying, and observing the surface of the sample.
The surface roughness and the weight loss rate of the special-shaped titanium alloy workpiece manufactured by laser additive manufacturing are measured before and after plasma polishing treatment and change along with the polishing voltage. The polishing voltage is 270V, 280V, 290V and 300V, the roughness is respectively reduced to 1.971um, 1.239um, 1.636um and 1.929um from 9.984um, and the weight loss rate of the sample is 5.643%, 5.579%, 6.342% and 7.314%.
Example 5
And performing plasma polishing treatment on the TC4 titanium alloy workpiece with the length, the width and the height of 8mm and 20mm respectively and the height of 3 mm.
(1) Pretreatment: ultrasonic cleaning and degreasing are carried out on the titanium alloy workpiece manufactured by the laser additive manufacturing in an acetone solution, and then deionized water is used for cleaning and drying the part.
(2) The polishing solution obtained in example 1 was subjected to regeneration: according to the polishing solution regeneration method provided by the invention, 40g of NaOH (analytically pure) is added into the titanium-loaded polishing solution and stirred, the titanium precipitate is removed by suction filtration, and 100ml of 38% hydrochloric acid is added and stirred uniformly.
(3) Plasma polishing: firstly, putting the regenerated polishing solution into an electrolytic bath, and heating the electrolytic bath to enable the temperature of the solution to reach 95 ℃. Then, the titanium alloy workpiece as a positive electrode and graphite as a negative electrode were immersed in the solution together, polished at 95 ℃ for 110s, and the voltage was controlled at 270V.
(4) And (3) post-treatment: and ultrasonically cleaning the special-shaped titanium alloy workpiece subjected to the plasma polishing treatment for 5min by using absolute ethyl alcohol, taking out, drying, and observing the surface of the sample.
The surface roughness of the special-shaped titanium alloy workpiece manufactured by laser additive manufacturing is obviously reduced and the weight loss is less measured before and after the plasma polishing treatment. The roughness is reduced from 10.125um to 1.436um, and the weight loss rate of the sample is 5.427%.
The surface of the laser additive manufacturing special-shaped titanium alloy workpiece treated by the plasma polishing solution and the polishing method is subjected to roughness measurement, and scanning electron microscope morphology analysis, and the results show that the special-shaped titanium alloy treated by the plasma polishing solution and the polishing method has the advantages of obviously reduced surface roughness, improved glossiness, smaller sample weight loss rate, no polishing lines and smooth and mirror-like surface.
Claims (8)
1. A plasma polishing solution for laser additive manufacturing of a titanium alloy workpiece is characterized in that: the plasma polishing solution is an aqueous solution and consists of the following components:
2. the polishing solution according to claim 1, wherein: the plasma polishing solution consists of the following components:
3. the polishing solution according to claim 1, wherein: the plasma polishing solution consists of the following components:
4. a method for producing the polishing liquid according to claim 1, characterized in that: proportionally mixing methanesulfonic acid and NH 2 SO 4 And (3) placing sulfosalicylic acid and sodium chloride into deionized water, and uniformly mixing to obtain the polishing solution.
5. A plasma polishing method for manufacturing a titanium alloy workpiece by laser additive manufacturing is characterized by comprising the following steps: ultrasonic cleaning and degreasing are carried out on a titanium alloy workpiece manufactured by laser material increase in acetone, and then the workpiece is cleaned and dried by deionized water; firstly, putting the polishing solution into an electrolytic bath, heating the electrolytic bath to enable the temperature of the solution to reach 95 ℃, then taking the titanium alloy workpiece as an anode and graphite as a cathode to be soaked in the polishing solution together for polishing, cleaning and drying.
6. The method of claim 5, wherein: the polishing temperature is 95 ℃; the polishing time was 120s; the polishing voltage is 270-300V.
7. The method of claim 5, wherein: the method comprises a polishing solution regeneration step, and specifically comprises the following steps: adding NaOH 25-50g/L into polishing solution containing titanium ions, filtering to remove titanium precipitate, and adding 38% hydrochloric acid 70-200ml/L.
8. The method of claim 5, wherein: the polishing solution is a new polishing solution obtained by preparation or a polishing solution obtained by regeneration.
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| CN202211386233.0A CN115652401A (en) | 2022-11-07 | 2022-11-07 | Plasma polishing solution for laser additive manufacturing of titanium alloy workpiece and preparation and application thereof |
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| CN202211386233.0A CN115652401A (en) | 2022-11-07 | 2022-11-07 | Plasma polishing solution for laser additive manufacturing of titanium alloy workpiece and preparation and application thereof |
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