CN109137031B - Metal-based ceramic composite material - Google Patents
Metal-based ceramic composite material Download PDFInfo
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- CN109137031B CN109137031B CN201811045232.3A CN201811045232A CN109137031B CN 109137031 B CN109137031 B CN 109137031B CN 201811045232 A CN201811045232 A CN 201811045232A CN 109137031 B CN109137031 B CN 109137031B
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Abstract
A metal matrix ceramic composite material belongs to the technical field of composite materials. The method is characterized in that: the ceramic composite layer is coated on part or all of the surface of the metal part, and the ceramic composite layer comprises the following raw materials in parts by weight: 60-80 parts of nickel sulfate, 3-7 parts of cobalt sulfate, 1-3 parts of sodium tungstate, 5-9 parts of phosphoric acid, 3-6 parts of silicon carbide, 3-6 parts of titanium boride, 4.5-18 parts of boron nitride, 30-35 parts of citric acid, 9-18 parts of phosphorous acid and 0.7-1.5 parts of brightening agent. The preparation method is to use stainless steel as an anode and metal parts as a cathode to complete compounding under the current condition. After the composition is finished, the metal workpiece has a smooth surface but is anti-skid, and the metal workpiece is convenient to grasp after being made into a petroleum machine and is more convenient and accurate when operations such as butt joint, disassembly and the like are finished.
Description
Technical Field
A metal matrix ceramic composite material belongs to the technical field of composite materials.
Background
In the technical field of petroleum machinery, eccentric wear and corrosion phenomena are serious, and no surface treatment technology which can not only resist corrosion and wear but also has low cost exists at present aiming at the surface treatment process of the petroleum machinery. With the continuous consumption of petroleum resources, the environment for exploiting petroleum is more and more severe, and the requirements on the corrosion resistance and the friction resistance of petroleum equipment are higher and higher.
The conventional surface treatment technology is mainly an electroplating chromium technology, and the electroplating chromium has limited application because of strong pollution and low corrosion resistance. The tungsten alloy electroplating technology developed in recent years, such as iron-tungsten alloy, nickel-tungsten alloy, iron-nickel-tungsten alloy, nickel-tungsten-phosphorus alloy and the like, can be controlled to obtain amorphous alloy tungsten. Tungsten cannot be electrodeposited from aqueous solutions alone, but can be induced to co-deposit with iron group elements (iron, nickel, cobalt) to give tungsten alloys of the above kind. However, these kinds of plating have the defects of high brittleness (especially iron-tungsten alloy), micro cracks on the surface, pinholes in the thickness, and the like, and the wear resistance is inferior to that of the chromium plating layer, and the problems limit the application range.
There is also a cobalt nickel phosphorus electroplating technology, that is, a plating layer is added on parts such as a sucker rod by electroplating, so that high hardness can be formed, and in the prior art, a silicon carbide component is added in the plating solution to reduce brittleness of the plating layer. However, the surface smoothness of the traditional cobalt-nickel-phosphorus coating is too high, the anti-skid performance is poor, especially in the field of petroleum machinery, the coating is difficult to grasp when being operated after the surface is stained with oil, and the operation difficulty is increased when operations such as butt joint, disassembly and the like are completed.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art and provides the metal-based ceramic composite material with skid resistance, wear resistance and vibration resistance.
The technical scheme adopted by the invention for solving the technical problems is as follows: the metal matrix ceramic composite material comprises a metal part and is characterized in that: the surface of the metal part is covered with a ceramic composite layer, and the ceramic composite layer comprises the following raw materials in parts by weight: 60-80 parts of nickel sulfate, 3-7 parts of cobalt sulfate, 1-3 parts of sodium molybdate, 5-9 parts of phosphoric acid, 3-6 parts of silicon carbide, 3-6 parts of titanium boride, 4.5-18 parts of boron nitride, 30-35 parts of citric acid, 9-18 parts of phosphorous acid and 0.7-1.5 parts of brightening agent.
The invention aims to provide an anti-skid, wear-resistant and vibration-resistant metal-based ceramic composite material, wherein a raw material formula of a ceramic composite layer is compounded on the surface of a metal part in an electrochemical mode, so that the strength of the metal part can be greatly improved, the metal part has a long service life under severe vibration, is high in hardness and wear-resistant, and is most important, the surface of the metal part after compounding is smooth and anti-skid, and the metal part is convenient to grasp after being made into a petroleum machine, and is more convenient and accurate when butt joint, disassembly and other operations are completed.
Preferably, the raw materials of the ceramic composite layer comprise the following components in parts by weight: 66-80 parts of nickel sulfate, 5-6 parts of cobalt sulfate, 1.5-2 parts of sodium molybdate, 6-7.5 parts of phosphoric acid, 4-5 parts of silicon carbide, 4-5 parts of titanium boride, 4.8-10.8 parts of boron nitride, 32-33 parts of citric acid, 12-16 parts of phosphorous acid and 1-1.2 parts of brightening agent. The preferable weight part composition can achieve the best wear-resisting and anti-skid effects at the same time.
Preferably, the mass ratio of the nickel sulfate to the cobalt sulfate is 14-16: 1. The preferred mass ratio of the three main materials can achieve better vibration resistance and wear resistance.
More preferably, the mass ratio of the nickel sulfate to the cobalt sulfate is 15: 1. The most preferable mass ratio of the three main materials can achieve the best vibration resistance and wear resistance effects of the invention.
Preferably, the mass ratio of the phosphoric acid to the phosphorous acid is 1: 2-2.2. The preferred phosphoric acid and phosphorous acid have higher recombination efficiency and take less time to reach the same thickness of the recombination layer than the electrochemical recombination.
Preferably, the mass ratio of the silicon carbide to the titanium boride is 1:1, and the mass ratio of the total mass of the silicon carbide and the titanium boride to the boron nitride is 1: 0.8-0.9. The optimized proportion of the silicon carbide, the titanium boride and the boron nitride can achieve better wear-resisting and anti-skidding effects at the same time.
A preparation method of a metal matrix ceramic composite material is characterized by comprising the following steps: the method comprises the following steps:
1) mixing silicon carbide, titanium boride, boron nitride and phosphoric acid in a mixer at the rotating speed of 400-700 rpm for 20-40 min, adding the rest raw materials after the materials are mixed, adding water in an amount which is 4.5-7 times of the total mass of the raw materials, and uniformly stirring;
2) heating to 60-80 ℃ under the stirring condition, and then preserving heat; stainless steel is used as an anode, a metal part is used as a cathode, and power supplies are respectively connected; at a current density of 5A/dm2~12A/dm2Under the condition of (1), the compounding of the ceramic composite layer on the surface of the metal workpiece is completed.
In the preparation method, the silicon carbide, the titanium boride, the boron nitride and the phosphoric acid are mixed and then prepared into a solution together with other materials for electrochemical reaction, so that the metal-based ceramic composite material can be efficiently compounded under the high current density, and the excellent vibration resistance and the excellent anti-skid property of the material are ensured.
Preferably, the heating in the step 2) is carried out to 65-80 ℃, and the current density is 5A/dm2~11.5A/dm2. The optimal reaction conditions can be matched with the optimal formula of the invention to achieve the optimal effect of the invention.
Compared with the prior art, the invention has the beneficial effects that: the invention aims to provide an anti-skid, wear-resistant and anti-vibration metal-based ceramic composite material. After the metal-based ceramic composite layer with special proportion and formula is compounded on the surface of a metal part in an electrochemical mode by the preparation method, the strength of the metal part can be greatly improved, the metal part has a long service life under severe vibration, is high in hardness and wear-resistant, and is mainly flat and anti-skid in the surface after the compounding is finished, and the metal-based ceramic composite layer is convenient to grasp after being made into a petroleum machine and is more convenient and accurate to complete operations such as butt joint, disassembly and the like.
Detailed Description
The invention is further illustrated by the following specific examples, of which example 1 is the best mode of practice.
Example 1
1) Preparing 78 parts of nickel sulfate, 5.2 parts of cobalt sulfate, 1.7 parts of sodium molybdate, 6.8 parts of phosphoric acid, 4.5 parts of silicon carbide, 4.5 parts of titanium boride, 7.2 parts of boron nitride, 32.5 parts of citric acid, 14.3 parts of phosphorous acid and 1.1 parts of brightener;
2) after the materials are prepared, mixing silicon carbide, titanium boride, boron nitride and phosphoric acid in a mixing mill at the rotating speed of 600 rpm for 25min, adding the rest raw materials after mixing, then adding water with the amount of 5 times of the total mass of the raw materials, and uniformly stirring;
3) heating under stirringKeeping the temperature to 67 ℃; stainless steel is used as an anode, a steel pipe with the thickness of 4mm is used as a cathode, and power supplies are respectively connected; at a current density of 11.5A/dm2Under the condition of (1), the compounding of the ceramic composite layer on the surface of the metal workpiece is completed.
Example 2
1) The components by weight portion are as follows: 75.6 parts of nickel sulfate, 5.4 parts of cobalt sulfate, 1.5 parts of sodium molybdate, 6.2 parts of phosphoric acid, 5 parts of silicon carbide, 5 parts of titanium boride, 8 parts of boron nitride, 32 parts of citric acid, 12.4 parts of phosphorous acid and 1 part of brightener;
2) after the materials are prepared, mixing silicon carbide, titanium boride, boron nitride and phosphoric acid in a mixing mill at the rotating speed of 500 rpm for 30min, adding the rest raw materials after the materials are mixed, adding water with the amount of 6 times of the total mass of the raw materials, and uniformly stirring;
3) heating to 65 ℃ under stirring and then preserving heat; stainless steel is used as an anode, a steel pipe with the thickness of 4mm is used as a cathode, and power supplies are respectively connected; at a current density of 11.5A/dm2Under the condition of (1), the compounding of the ceramic composite layer on the surface of the metal workpiece is completed.
Example 3
1) The components by weight portion are as follows: 80 parts of nickel sulfate, 5 parts of cobalt sulfate, 2 parts of sodium molybdate, 7 parts of phosphoric acid, 4 parts of silicon carbide, 4 parts of titanium boride, 7.2 parts of boron nitride, 33 parts of citric acid, 15.4 parts of phosphorous acid and 1.2 parts of brightener;
2) after the materials are prepared, mixing silicon carbide, titanium boride, boron nitride and phosphoric acid in a mixer at the rotating speed of 600 rpm for 25min, adding the rest raw materials after the materials are mixed, and then adding water with the amount of 5.5 times of the total mass of the raw materials and uniformly stirring;
3) heating to 68 ℃ under stirring and then preserving heat; stainless steel is used as an anode, a steel pipe with the thickness of 4mm is used as a cathode, and power supplies are respectively connected; at a current density of 11A/dm2Under the condition of (1), the compounding of the ceramic composite layer on the surface of the metal workpiece is completed.
Example 4
1) The components by weight portion are as follows: preparing 66 parts of nickel sulfate, 5 parts of cobalt sulfate, 2 parts of sodium molybdate, 6 parts of phosphoric acid, 5 parts of silicon carbide, 4 parts of titanium boride, 10.8 parts of boron nitride, 32 parts of citric acid, 16 parts of phosphorous acid and 1 part of brightener;
2) after the materials are prepared, mixing silicon carbide, titanium boride, boron nitride and phosphoric acid in a mixer at the rotating speed of 500 rpm for 28min, adding the rest raw materials after the materials are mixed, and then adding water with the amount of 5.6 times of the total mass of the raw materials and uniformly stirring;
3) heating to 66 ℃ under stirring and then preserving heat; stainless steel is used as an anode, a steel pipe with the thickness of 4mm is used as a cathode, and power supplies are respectively connected; at a current density of 12A/dm2Under the condition of (1), the compounding of the ceramic composite layer on the surface of the metal workpiece is completed.
Example 5
1) The components by weight portion are as follows: 80 parts of nickel sulfate, 6 parts of cobalt sulfate, 1.5 parts of sodium molybdate, 7.5 parts of phosphoric acid, 4 parts of silicon carbide, 5 parts of titanium boride, 4.8 parts of boron nitride, 33 parts of citric acid, 12 parts of phosphorous acid and 1.2 parts of brightener;
2) after the materials are prepared, mixing silicon carbide, titanium boride, boron nitride and phosphoric acid in a mixing mill at the rotating speed of 600 rpm for 35min, adding the rest raw materials after the materials are mixed, adding water which is 5 times of the total mass of the raw materials, and uniformly stirring;
3) heating to 67 ℃ under stirring and then preserving heat; stainless steel is used as an anode, a steel pipe with the thickness of 4mm is used as a cathode, and power supplies are respectively connected; at a current density of 11A/dm2Under the condition of (1), the compounding of the ceramic composite layer on the surface of the metal workpiece is completed.
Example 6
1) Preparing 60 parts of nickel sulfate, 3 parts of cobalt sulfate, 3 parts of sodium molybdate, 5 parts of phosphoric acid, 6 parts of silicon carbide, 3 parts of titanium boride, 18 parts of boron nitride, 30 parts of citric acid, 18 parts of phosphorous acid and 0.7 part of brightener;
2) after the materials are prepared, mixing silicon carbide, titanium boride, boron nitride and phosphoric acid in a mixer at the rotating speed of 400rpm for 40min, adding the rest raw materials after the materials are mixed, adding water with the weight 7 times of the total weight of the raw materials, and uniformly stirring;
3) heating to 60 ℃ under stirring and then preserving heat; stainless steel is used as an anode, a steel pipe with the thickness of 4mm is used as a cathode, and power supplies are respectively connected; at a current density of 10A/dm2Under the condition of (1), the compounding of the ceramic composite layer on the surface of the metal workpiece is completed.
Example 7
1) Preparing 80 parts of nickel sulfate, 7 parts of cobalt sulfate, 1 part of sodium molybdate, 9 parts of phosphoric acid, 3 parts of silicon carbide, 6 parts of titanium boride, 4.5 parts of boron nitride, 35 parts of citric acid, 9 parts of phosphorous acid and 1.5 parts of brightener;
2) after the materials are prepared, mixing silicon carbide, titanium boride, boron nitride and phosphoric acid in a mixer at the rotating speed of 700 rpm for 20min, adding the rest raw materials after the materials are mixed, and then adding water with the amount of 4.5 times of the total mass of the raw materials and uniformly stirring;
3) heating to 70 ℃ under stirring and then preserving heat; stainless steel is used as an anode, a steel pipe with the thickness of 4mm is used as a cathode, and power supplies are respectively connected; at a current density of 10A/dm2Under the condition of (1), the compounding of the ceramic composite layer on the surface of the metal workpiece is completed.
Comparative example 1
The raw material ratio and the preparation process were the same as in example 1, except that the raw materials were not added with a corresponding amount of sodium molybdate.
Comparative example 2
The raw material ratio and the preparation process were the same as in example 1, except that the raw materials were not added with titanium boride and boron nitride in corresponding amounts.
Comparative example 3
The raw material proportioning and the preparation process are the same as those of the example 1, except that all the raw materials are directly added with water and stirred uniformly in the step 2).
The results of the performance test of the metal matrix ceramic composite materials prepared in the respective examples and comparative examples are shown in table 1.
TABLE 1 Performance test results for Metal-based ceramic composites
The method for determining the anti-skid properties in table 1 is: lifting the ceramic composite steel pipe prepared in the embodiment or the comparative example by using the same metal clip, hanging a weight at the lower end of the steel pipe, and recording the mass of the hung weight when the steel pipe begins to slide; the larger the mass of the hung weight when the steel pipe starts to slide, the better the anti-skid performance is.
The foregoing is directed to preferred embodiments of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow. However, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention are within the protection scope of the technical solution of the present invention.
Claims (7)
1. A metal matrix ceramic composite comprising a metallic article characterized by: the ceramic composite layer is coated on part or all of the surface of the metal part, and the ceramic composite layer comprises the following raw materials in parts by weight: 60-80 parts of nickel sulfate, 3-7 parts of cobalt sulfate, 1-3 parts of sodium molybdate, 5-9 parts of phosphoric acid, 3-6 parts of silicon carbide, 3-6 parts of titanium boride, 4.5-18 parts of boron nitride, 30-35 parts of citric acid, 9-18 parts of phosphorous acid and 0.7-1.5 parts of brightening agent;
the preparation method comprises the following steps:
1) mixing silicon carbide, titanium boride, boron nitride and phosphoric acid in a mixing mill at the rotating speed of 400-700 rpm for 20-40 min, adding the rest raw materials after the materials are mixed, adding water in an amount which is 4.5-7 times of the total mass of the raw materials, and uniformly stirring;
2) heating to 60-80 ℃ under the stirring condition, and then preserving heat; stainless steel is used as an anode, a metal part is used as a cathode, and power supplies are respectively connected; at a current density of 5A/dm2~12A/dm2Under the condition of (1), the compounding of the ceramic composite layer on the surface of the metal workpiece is completed.
2. The metal matrix ceramic composite of claim 1, wherein: the ceramic composite layer comprises the following raw materials in parts by weight: 66-80 parts of nickel sulfate, 5-6 parts of cobalt sulfate, 1.5-2 parts of sodium molybdate, 6-7.5 parts of phosphoric acid, 4-5 parts of silicon carbide, 4-5 parts of titanium boride, 4.8-10.8 parts of boron nitride, 32-33 parts of citric acid, 12-16 parts of phosphorous acid and 1-1.2 parts of brightening agent.
3. The metal matrix ceramic composite of claim 1, wherein: the mass ratio of the nickel sulfate to the cobalt sulfate is 14-16: 1.
4. The metal matrix ceramic composite of claim 1, wherein: the mass ratio of the nickel sulfate to the cobalt sulfate is 15: 1.
5. The metal matrix ceramic composite of claim 1, wherein: the mass ratio of the phosphoric acid to the phosphorous acid is 1: 2-2.2.
6. The metal matrix ceramic composite of claim 1, wherein: the mass ratio of the silicon carbide to the titanium boride is 1:1, and the mass ratio of the total mass of the silicon carbide and the titanium boride to the boron nitride is 1: 0.8-0.9.
7. The metal matrix ceramic composite of claim 1, wherein: in the step 2), the heating is carried out to 65-80 ℃, and the current density is 5A/dm2~11.5A/dm2。
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