The preparation method of the super nano diamond coating of ceramic cartridge
Technical field
The invention belongs to the method for ceramic cartridge surface modification, particularly relate to the preparation method of the super nano diamond coating that improves ceramic cartridge matrix overall performance.
Background technology
Super nano diamond coating is meant that grain-size is less than the tack diamond thin of 40nm in the rete.Compare with traditional diamond film, its surface is more smooth smooth, and hardness is substantially near (can reach 60GPa, and traditional diamond film being about 80GPa), but structure is different: it is with sp
3The carbon atom of hydridization accounts for most (sp
3The carbon atom of hydridization is greater than 75%), have in certain cancellated rete grain-size less than the carbon film of 40nm.
Ceramic cartridge is that a kind of engineering ceramic material that uses replaces traditional rubber, the iron and steel novel high-tech product as sealing member.Because the high strength of ceramic core, high rigidity, corrosion-resistant, high temperature resistant, the weather resistance of not having wearing and tearing, make water tap and oil gas valve use (life-span prolongs more than ten times than traditional product) in the various media midium or long terms, and can remain the tight no evaporating, emitting, dripping or leaking of liquid or gas of sealing, and switch is flexible, and feel is light.This The application of new technique has simultaneously changed the structure of traditional water tap valve, and spiral lifting, the extruding rubber seal in past reached the Water tap mode of operation of closing, and changes into moving handle and just can realizing quick open and close for 90 °.Can interrogate simultaneously velocity modulation water saving flow size arbitrarily, reach the purpose of water saving.
In new ceramics spool water tap, ceramic cartridge is the heart component of its performance of decision and characteristics, its size shape precision, surfaceness, material hardness, frictional coefficient, wear resistance and chemical stability have directly determined the sealing effectiveness (whether running prosperous water clock) of water tap, work-ing life and the nimble property of operation, thereby the preparation of ceramic core product and processing technology proposed extremely high requirement.GB requires to make ceramic cartridge must adopt the above Al of 95 porcelain
2O
3Material (to guarantee product hardness, wear resistance, solidity to corrosion), and must not be lower than work-ing life 200,000 times, (1.6MPa) can not have water clock under the interior normal hydraulic condition of usage period.
Commercially available ceramic cartridge has imported product (produce in Germany, Spain, Italy, Japan, Taiwan) and homemade goods two classes at present, class higher (price is more than 4,500 yuan even reach ten thousand yuan leading adapted, best can guarantee 50~600,000 foldings, 10 year usage period) all be inward cargo, the single-piece price is more than hundred yuan; Homemade goods (only can be used on the low-grade tap of dozens of yuan~hundreds of unit) is expensive sells two, 30 yuan of a slices, cheap only sells 1~2 yuan, cause the basic reason of this huge price differential to be that the quality of homemade spool and imported product compare at a distance of too far away, even majority does not reach the requirement of GB (GB/T18145-2000), main aspect comprises: valve core material hardness, wear resistance (have plenty of because the ceramics processing difference causes inadequately, have plenty of because manufacturer uses inferior materials and turns out substandard goods and selects for use common ceramics to cause), make that the life-span of valve is too short; Secondly spool face smooth finish, poor flatness, dimensional precision not high enough (since material density is low or machining technique inadequately precision cause), make that each parts of valve gap that is sealed and matched is big, easily cause water clock water.These technology shortcomings make that the qualification rate of homemade ceramic core water tap product is too low, finally cause promoting not smooth, the wasting of resources big (change after installing and using again material, manpower and water resources have all been caused huge waste) of work progress of water-saving ceramic core water tap.
Usually the technological approaches that improves the ceramic performance all is from the technology of preparing of stupalith and burns till product machining technique two aspects and comprehensively start with, comprises hardware technology conditions such as material prescription, moulding, agglomerating related process software engineering and corresponding material production equipment, machining apparatus.Because 95Al
2O
3The application of porcelain engineering materials has the history of decades, and its preparation technology is quite ripe, thereby the big major cause of product performance gap also is on the level and ability of relevant device both at home and abroad.Still remain the technical progress of domestic relevant device industry and the raising of national industrial aggregate level by China's problem of settling a dispute by the parties concerned themselves in this respect, this is long process.Another way is that the external sophisticated equipment of a large amount of introductions is made premium quality product, and this needs the support of substantial contribution also to be subjected to the restriction of technology barriers simultaneously, also can make the cost of homemade goods skyrocketing even can solve, and competitive power weakens.Consider that problem that homemade ceramic cartridge exists mainly is by material surface performance deficiency (hardness, wear resistance are not enough, and roughness is big).So if can be under the condition that does not change existing valve core material matrix, improve performance index such as its surface hardness, wear resistance, surfaceness by the process for modifying surface means, the performance of whole prod is improved significantly, thereby only is that the surface modification treatment operation of additional one fast, economical has promptly realized target that the product overall performance is improved.
Summary of the invention
The objective of the invention is to overcome above-mentioned the deficiencies in the prior art, provide a kind of to plane water tap ceramic cartridge surface modification, preparation method with the super nano diamond coating of the ceramic cartridge that improves performances such as ceramic cartridge surface hardness, wear resistance, surfaceness, water tap and oil gas valve can be used in the various media midium or long terms, and can remain the tight no evaporating, emitting, dripping or leaking of liquid or gas of sealing, switch is flexible, and feel is light.
Solution of the present invention is: a kind of preparation method of super nano diamond coating of ceramic cartridge is characterized in may further comprise the steps:
(a) plane water tap ceramic cartridge is soaked with soak solution,
(b) with diadust suspension ultrasonic grinding matrix surface,
(c) ceramic cartridge is put into the super nano diamond coating of microwave plasm reaction cavity growth; Wherein feeding the reactant gas source gas flow in the reaction chamber is 500~800mL/min, and gaseous tension is 10000~13000Pa, and the ceramic cartridge temperature is controlled at 600~1000 ℃, and keeps 4~5h.
Adopt the main reason of solution of the present invention to be: at first, the temperature height of chemical vapour deposition diamond (600~1000 ℃) helps the high strength bond (can form thick diffusion layer) of diamond film on matrix; Secondly, super Nano diamond wear resistance in all material is best, hardness is maximum, and frictional coefficient and thermal expansivity are little, but self-lubricating, chemical stability is good, and is nontoxic, hydrophobicity is strong, with its plating in Al
2O
3Matrix surface can not only improve the rub resistance polishing machine, and can further improve its biological chemistry inertia, solidity to corrosion and sliding; The 3rd, because adamantine forming core merit is big, sedimentary diamond coatings is wanted preferentially to grow at the fault location forming core of ceramic cartridge matrix surface, it is extremely smooth smooth to add super nano-diamond film surface, thereby can guarantee that the film surface roughness is lower than the original substrate surface, and further improve stopping property, sliding and the wear resistance of whole valve products.Comprehensive above the analysis improved performance and the quality that has homemade ceramic cartridge now with super nano diamond coating technology, more all is a very good approach from all many-sides such as technology, economy and practicality.
Soak solution can adopt acid soak solution or alkaline soak solution in the solution of the present invention.
Ultrasonic grinding diadust fineness is 0.5-40 μ m in the solution of the present invention.
Reactant gas source is the mixed gas of methane and argon gas in the solution of the present invention, and wherein methane concentration is 1%~2%; Or the mixed gas of methane, argon gas and hydrogen, wherein methane concentration is 1%~2%, density of hydrogen is 15%~18%.
In the solution of the present invention in the microwave plasm reaction cavity ceramic cartridge temperature be controlled at 800~900 ℃.
The ultrasonic grinding matrix surface adopts ultrasonic grinding processing 20min in the ultrasonic generator in the solution of the present invention.
The present invention has the following advantages:
(1) the growth temperature height of super nano-diamond membrane (600~1000 ℃) is beneficial to film base interfacial layer and forms the super nano diamond coating bonding strength height that grows.
(2) the super nano diamond coating wear resistance of Sheng Chenging is best, hardness is maximum, and frictional coefficient and thermal expansivity are little, but self-lubricating, chemical stability is good, and is nontoxic, and hydrophobicity is strong, can improve the overall performance of ceramic cartridge water tap, prolong work-ing life more than ten times.
(3) the super nano diamond coating that deposits is smooth smooth, need not polish.
(4) this ceramic cartridge method of modifying is fast and convenient, and cost is lower.
Embodiment
Embodiment 1:
Plane water tap ceramic cartridge is put into 90 ℃ of 10mol/l salpeter solution etching 12h, take out water and rinse well; Place the alcohol suspension that is placed with 0.5 μ m diadust again, handle 20min with the ultrasonic generator ultrasonic grinding; With ethanolic soln sample is cleaned up, dries up then, be positioned in the microwave plasm reaction cavity, vacuumize, open microwave generator, the pilot-gas flow is 500~800mL/min, and working gas is CH
4And Ar, CH
4Concentration 1%~2% is elevated to 1200W~1300W to microwave power again, and gaseous tension keeps 10000~13000Pa, 800~900 ℃ of ceramic cartridge temperature, and keep 4~5h, reduce microwave power at last gradually and slowly sample is reduced to room temperature.
Embodiment 2:
Plane water tap ceramic cartridge is put into surface etch 5min in the fusion KOH of 420 ℃ of retort furnaces, taken out water and rinse well; Place the alcohol suspension that is placed with 0.5 μ m diadust again, handle 20min with the ultrasonic generator ultrasonic grinding; With ethanolic soln sample is cleaned up, dries up then, the process of growth of super nano diamond coating is with embodiment 1 after being positioned in the microwave plasm reaction cavity.
Embodiment 3:
Use acid (or alkali) etching and ultrasonic grinding to handle (as described in embodiment 1 or embodiment 2) plane water tap ceramic cartridge, be positioned in the microwave plasm reaction cavity in, vacuumize, open microwave generator, the pilot-gas flow is 500~800mL/min, and working gas is CH
4, Ar and H
2Gas mixture, CH
4Concentration 1%~2%, H
2Concentration 15%~18% is elevated to 1200W~1300W to microwave power again, and gaseous tension keeps 10000~13000Pa, 700~800 ℃ of ceramic cartridge temperature, and keep 4~5h, reduce microwave power at last gradually and slowly sample is reduced to room temperature.