CN1928038A - Nano solid lubricant with hollow cage-shape structure and preparation method thereof - Google Patents

Abstract

The present invention discloses one kind of hollow cage-shaped nanometer solid lubricant and its preparation process. Spherical nanometer MoO3 or WO3 particle is first prepared through an ultrasonic and chemical precipitation process and surface coated with S or Se, and hollow cage-shaped nanometer solid lubricant of IF-MoS2, IF-MoSe2, IF-WS2 or IF-WSe2 of particle size 40-100 nm is then prepared through further vulcanization or selenation reaction. This kind of solid lubricant may be used alone or as additive added into lubricant oil or grease to form composite lubricant oil or grease to reduce friction coefficient, reduce wear and raise extreme pressure resistance. At the same time, the solid lubricant can meet the lubricant requirement in high temperature, low temperature, high vacuum, high humidity, high corrosion, high radiation, high load and other harsh conditions.

Description

Nano solid lubricant with hollow cage-shape structure and preparation method thereof

Technical field:

The present invention relates to inorganic fullerene (IF) nano material and lubrication technology research field, exactly, it is a kind of with the prepared spherical MoO of " ultrasonic-chemical precipitation " method ₃Or WO ₃Nano particle is a precursor, the inorganic fullerene molybdenum disulfide (IF-MoS that obtains by chemical reaction ₂), two selenizing molybdenum (IF-MoSe ₂) or inorganic fullerene-like tungsten disulfide (IF-WS ₂), two selenizing tungsten (IF-WSe ₂) wait and have nano solid lubricant with hollow cage-shape structure and preparation method thereof.

Background technology:

50%～70% of the energy that the world today uses is consumed in useless friction aspect, and still is one of main reason of losing efficacy of mechanical means by the wearing and tearing that friction causes.Novel lubricating material by the Application and Development excellent performance is controlled friction, reduces wear, and improves lubricity and has become save energy and raw-material important measures.In real productive life, the application of lubricant improves efficient, life-span and the reliability of machine for reducing frictional dissipation, save energy, reduces machine maintenance work amount and idle cost etc. and has brought into play huge effect.As lubricant, generally be divided into two kinds of fluid and solids.Wherein, solid lubricant can satisfy the lubricating requirement under many special operation condition conditions such as vacuum, comparatively high temps, radiation and corrosion substantially, adapt to complex operating environment, for mechanical means realize to maximize, microminiaturized, at a high speed, heavy duty and automatically control etc. provide and provide powerful support for, and for realizing new technology and using novel material etc. and created favourable condition.

Traditional solid lubricant mainly is easy to realize that by matter is soft the laminate structure solid of interlayer slip constitutes, wherein MoS ₂, MoSe ₂And WS ₂, WSe ₂Deng being typical chalkogenide solid lubricant, has layered crystal structure.This class solid lubricant since the layer with layer between combine with more weak Van der Waals force, under lower shear action, be easy to the slippage between genetic horizon, have tribological property preferably; But when it uses under conditions such as comparatively high temps and high humidity, be easy to change into corresponding oxide compound and become abrasive particle, lubricity sharply descends.Continuous development along with modern industrial technology, especially at automobile, field such as aerospace and space technology, solution comprises that the lubrication problem under the special operation conditions such as high loading, high vacuum, very low temperature, severe radiation, deep-etching, high temperature and high pressure has caused people's extensive concern.Inorganic fullerene chalcogen compound (the IF-MX of hollow cage-shape structure ₂, wherein M=Mo, W, X=S, Se) and nano material has the characteristics of outstanding key few (unreactiveness is good) in surface and good springiness.This hollow cage-shape structure and snappiness make its lubricating system between friction pair be more prone to rolling resistance, and can also directly cause the minimizing of friction energy loss when the unsmooth contact of lubricated surface; The chemical stability of height is effectively avoided the formation of greasy filth, guarantees its secular lubricated usefulness.

At IF-MX ₂Preparation and the invention as solid lubricant in, the method and apparatus of the disclosed production of CN01817955 IF nanoparticles, be under preset temperature, to make the metal oxide vaporization, and with inert support with the vaporization the burning logistics deliver to conversion zone, simultaneously first and second reagents are sent into conversion zone.Therefore the metal oxide of vaporization and first reagent interact, and change into metal suboxide nanoparticles in gas phase; The metal suboxide nanoparticles of condensing in gas phase and second reagent interact, and generate the IF nanoparticles of pure phase basically.CN200410020424 discloses and has a kind ofly issued biochemical reaction in nitrogen atmosphere and certain temperature then by at first coating S or Se at the microparticle surfaces of ball shaped nano W or nanometer Mo, finally synthesizes even IF-MoS on the surface of Mo or W particulate ₂, MoSe ₂Or WS ₂, WSe ₂The nucleocapsid structure of lubricated shell receives preparation methods.CN200510050405 discloses a kind of IF-MoS ₂Preparation method and application, it is a main raw material with sodium sulphite and ammonium molybdate, the polyoxyethylene glycol aqueous solution is at first prepared MoS as dispersion agent ₃, then in quartz tube furnace under the argon atmospher, hydrogen desulfurization under 500～1000 ℃ of temperature, and be incubated 5～10 hours, obtained IF-MoS ₂Nano particle.But these existing inventions all relate to complicated making processes, prepare a large amount of, high-purity IF-MX with lower cost ₂Also be difficult to realize.

The present invention is a kind of with Sodium orthomolybdate (Na ₂MoO ₄) or sodium wolframate (Na ₂WO ₄) be main raw material, at first utilize " ultrasonic-chemical precipitation " method to prepare spherical MoO ₃Or WO ₃Nano particle, direct and reaction of Salmon-Saxl acquisition IF-MX under certain temperature and nitrogen atmosphere then ₂(M=Mo, W; X=S, Se) the convenient preparation method of nano solid lubricant, it is fit in enormous quantities at low cost and prepared in high purity IF-MX ₂(M=Mo, W; X=S Se), thereby has remedied the deficiency of existing patented technology.

Summary of the invention:

The objective of the invention is to utilize " ultrasonic-chemical precipitation " method to prepare spherical MoO ₃Or WO ₃Nano particle coats through the surface of sulphur (S) or selenium (Se) again and sulphur (selenium) is changed, and prepares a kind of inorganic fullerene (IF) nano particle powder with hollow cage-shape structure in large quantity, and median size is 40～100nm; Provide a kind of and can satisfy practical application request, reduce frictional coefficient significantly, alleviate component wear, be applicable to the nano solid lubricant of severe rugged environments such as comparatively high temps, very low temperature, high vacuum, the high radiation of high burn into and high rotating speed.And provide its preparation method.

Nano solid lubricant with hollow cage-shape structure of the present invention is at prepared spherical MoO ₃Or WO ₃The coated with uniform S of nano particle or Se make coating layer S or Se and MoO then under nitrogen atmosphere and certain temperature ₃Or WO ₃Sulfuration or selenylation reaction take place, thereby prepare IF-MoS ₂, IF-MoSe ₂Or IF-WS ₂, IF-WSe ₂Nano solid lubricant.

Described MoO ₃Or WO ₃Ball shaped nano particle median size is 30～60nm, and it is coated S or Se layer, and the solvent of S or Se is a certain proportion of dithiocarbonic anhydride (CS ₂) and tetracol phenixin (CCl ₄) mixing solutions; The MoO of S or Se layer will be coated with ₃Or WO ₃Sulfuration or selenylation reaction take place in nano particle under certain nitrogen atmosphere.

MoO among the present invention ₃Or WO ₃Ball shaped nano particulate preparation method is: the hydrochloric acid (HCl) or the 3mol/l nitric acid (HNO that at room temperature prepare 3mol/l with deionized water respectively ₃) Sodium orthomolybdate (Na of solution and 0.3～0.5mol/l ₂MoO ₄) sodium wolframate (Na of solution or 0.3～0.5mol/l ₂WO ₄) solution.Get dehydrated alcohol or methyl alcohol and Na ₂MoO ₄Solution or Na ₂WO ₄Solution is 1: 1～4 mixing by volume, under ultrasonic and churned mechanically synergy, slowly splashes into HCl or HNO by dropping funnel in reaction system ₃Solution is to pH ≈ 1.0, and then keeps ultrasonic and stirred 15～30 minutes.After question response finishes, isolate reactant, and reactant is washed 3 times, use absolute ethanol washing again 2 times with deionized water by whizzer.Dry 4-6h under 80 ℃ in vacuum drying oven calcines 1-3h then under 400～500 ℃ in resistance furnace, obtaining median size is the spherical MoO of 30～60nm ₃Or WO ₃Nano particle.

MoO among the present invention ₃Or WO ₃Ball shaped nano particulate S or Se method for coating are: be 1: 0.5～1 CS with volume ratio ₂And CCl ₄For mixed solution is a solvent, make mixing solutions in every liter of ratio of dissolving in the Se of 180～350 S that restrain or 150～280 grams; And then press MO ₃(M=W Mo) with S or Se mol ratio is 1: 3～4 ratio, with an amount of MoO ₃Or WO ₃Nano particle joins in the mixing solutions, behind mechanical stirring 15～20min, places ultrasonic cleaner ultra-sonic dispersion 20～30min under the room temperature, passes through underpressure distillation again, removes solvent and can obtain the MoO that the surface coats S or Se ₃Or WO ₃Composite granule.

The MoO that S or Se coat among the present invention ₃Or WO ₃The sulfuration of composite granule or the processing method of selenylation reaction are: with the MoO of S or Se coating ₃Or WO ₃Composite granule places the vulcanization reaction chamber, reaction chamber is evacuated to below the 1Pa again, slowly charges into exsiccant hydrogen to 0.02～0.06MPa then in reaction chamber, then reaction chamber is heated to 450 ℃～700 ℃, and temperature rise rate is 10 ℃ of min ^-1, cool to room temperature behind constant temperature 30～90min with the furnace and take out, obtain the MoS of IF type ₂, MoSe ₂Or WS ₂, WSe ₂Nano solid lubricant.

Nano solid lubricant of the present invention has the IF structure of hollow cage shape, and particle diameter is the nano particle of 40～100nm, has good elasticity.Under low load condition, can make the sliding friction between test specimen change rolling resistance into, thereby reduce the frictional coefficient between even part significantly; And there is unsaturated outstanding key hardly in the surface of nano particle, make it have good unreactiveness, bonding does not take place in the atoms metal with friction surface under the not really high situation of load, surface of friction pair there is not corrosive nature, and avoided forming " greasy filth " with abrasive dust or self, frictional force reduces between even part thereby make; Under high load conditions, these nano particles can be filled the pit on test specimen surface on the one hand, play smooth-flat-surface, are easy to form transfer film at test specimen rat place simultaneously, significantly improve the anti-extreme pressure energy, thereby can obviously reduce the frictional coefficient between even part.Especially under severe rugged environments such as comparatively high temps, very low temperature, high vacuum, high humidity, the high radiation of high burn into and high rotating speed, these nano solid lubricants are compared the advantage of having more with other lubricants.

Compare with existing IF structure nano solid lubricant technology of preparing, operational path of the present invention is simple and direct, is easy to realize in enormous quantities, high purity and low-cost preparation.

Embodiment:

Embodiment 1: spherical MoO ₃Or WO ₃The preparation of nano particle

Be equipped with spherical MoO with " ultrasonic-chemical precipitation " legal system ₃Or WO ₃, suitably select ethanol or methanol content, HCl or HNO in the synergistic mode of sonic oscillation and mechanical stirring, ethanol or the methanol-water reaction system ₃Solution usage, the sedimentary mode of washing of reactant and calcining temperature and time etc., can prepare spherical MoO with better single dispersion characteristics ₃Or Wo ₃Nano particle.

(1) spherical MoO ₃The preparation of nano particle

At room temperature prepare the HCl solution of 3mol/l and the Na of 0.5mol/l respectively with deionized water ₂MoO ₄Solution.Get the Na of 500ml dehydrated alcohol and 1500ml ₂MoO ₄The solution thorough mixing slowly splashes into the HCl solution of 400ml in reaction system by dropping funnel under ultrasonic and churned mechanically synergy, pH ≈ 1.0, and then keep ultrasonic and stirred 20 minutes.Isolate reactant by whizzer, and reactant is washed 3 times, use absolute ethanol washing again 2 times with deionized water.Dry 6h under 80 ℃ in vacuum drying oven calcines 2h then under 450 ℃ in resistance furnace, obtaining about 95 gram median sizes is the spherical MoO of 60nm ₃Nano particle.

(2) spherical WO ₃The preparation of nano particle

At room temperature prepare the HCl solution of 3mol/l and the Na of 0.5mol/l respectively with deionized water ₂WO ₄Solution.Get the Na of 500ml ethanol and 1500ml ₂WO ₄The solution thorough mixing slowly splashes into the HCl solution of 400ml in reaction system by dropping funnel under ultrasonic and churned mechanically synergy, and then keep ultrasonic and stirred 30 minutes.Isolate reactant by whizzer, and reactant is washed 3 times, use absolute ethanol washing again 2 times with deionized water.Dry 6h under 80 ℃ in vacuum drying oven calcines 2h then under 500 ℃ in resistance furnace, obtaining about 160 gram median sizes is the spherical WO of 40nm ₃Nano particle.

Embodiment 2:MoO ₃Or WO ₃The S of nano grain surface or Se coat

(1) MoO ₃Or WO ₃The S of nano grain surface coats

Get the CS of 500ml respectively ₂CCl with 500ml ₄Make mixed solvent, the S powder of 320g is joined in the mixed solvent, constantly stir and make it to dissolve fully; And then to the MoO that wherein adds 470g ₃The WO of nano particle or 750g ₃Nano particle, fully stir 20min after, place ultrasonic cleaner ultra-sonic dispersion 30min, pass through underpressure distillation at last, remove the MoO that solvent can obtain about 790g S coating ₃Composite granule, or the WO of about 1070g S coating ₃Composite granule.

(2) MoO ₃Or WO ₃The Se of nano grain surface coats

Get the CS of 500ml respectively ₂CCl with 500ml ₄Make mixed solvent, the Se powder of 240g is joined in the mixed solvent, constantly stir and make it to dissolve fully; And then to the MoO that wherein adds 140g ₃The WO of nano particle or 230g ₃Nano particle, fully stir 30min after, place ultrasonic cleaner ultra-sonic dispersion 30min, pass through underpressure distillation at last, remove the MoO that solvent can obtain about 380g Se coating ₃Composite granule, or the WO of about 470g Se coating ₃Composite granule.

Embodiment 3: vulcanization reaction prepares IF type MoS ₂Or WS ₂The nano particle powder

A certain amount of surface is coated the MoO of S ₃Or WO ₃Composite granule places the vulcanization reaction chamber, reaction chamber is evacuated to below the 1Pa again, to wherein charging into exsiccant hydrogen lentamente to 0.06Mpa, then reaction chamber is heated to 600 ℃ then, and temperature rise rate is 10 ℃ of min ^-1, constant temperature 30min.Cool to room temperature then with the furnace, promptly obtain the MoS of IF type ₂Or WS ₂The nano particle powder.

Embodiment 4: selenylation reaction prepares IF type MoSe ₂Or WSe ₂The nano particle powder

A certain amount of surface is coated the MoO of Se ₃Or WO ₃Composite granule places the vulcanization reaction chamber, reaction chamber is evacuated to below the 1Pa again, to wherein charging into exsiccant hydrogen lentamente to 0.05Mpa, then reaction chamber is heated to 680 ℃ then, and temperature rise rate is 10 ℃ of min ^-1, constant temperature 60min.Cool to room temperature then with the furnace, promptly obtain the MoSe of IF type ₂Or WSe ₂The nano particle powder.

Claims (2)

1, nano solid lubricant with hollow cage-shape structure is characterized in that: with Sodium orthomolybdate (Na ₂MoO ₄) or sodium wolframate (Na ₂WO ₄) be main raw material, at first prepare MoO by " ultrasonic-chemical precipitation " method ₃Or WO ₃The ball shaped nano particle coats S or Se on its surface then, behind over cure or selenylation reaction, obtains to have the IF-MoS of hollow cage-shape structure ₂, IF-MoSe ₂Or IF-WS ₂, IF-WSe ₂The nano particle powder.

2, a kind of preparation method of nano solid lubricant with hollow cage-shape structure is characterized in that:

(a) MoO ₃Or WO ₃Ball shaped nano particulate preparation: with Na ₂MoO ₄Or Na ₂WO ₄Be main raw material, adopt " ultrasonic-chemical precipitation " method, prepare spherical MoO with single dispersion characteristics ₃Or WO ₃Nano particle; At room temperature prepare the HCl solution of 3mol/l or the HNO of 3mol/l respectively ₃The Na of solution and 0.3～0.5mol/1 ₂MoO ₄The Na of solution or 0.3～0.5mol/l ₂WO ₄Solution is got dehydrated alcohol or methyl alcohol and above-mentioned Na ₂MoO ₄Or Na ₂WO ₄Solution is pressed 1: 1～4 volume ratio thorough mixing, slowly splashes into above-mentioned HCl solution or HNO in sonic oscillation and mechanical stirring synergy downhill reaction system ₃Solution is to pH ≈ 1.0, keep ultrasonic then and stirred 15～30 minutes, isolate reactant by whizzer, and with deionized water with reactant washing 3 times, use absolute ethanol washing again 2 times, dry 4-6h under 80 ℃ in vacuum drying oven calcines 1-3h then under 400～500 ℃ in resistance furnace, obtaining median size is the spherical MoO of 30～60nm ₃Or WO ₃Nano particle;

(b) MoO ₃Or WO ₃The S of nano particle or Se coat: be 1: 0.5～1 CS with volume ratio ₂And CCl ₄Mixed solution is a solvent, to wherein every liter dissolve in 180～350 the gram S or 150～280 the gram Se make mixing solutions; And then according to MoO ₃Or WO ₃With S or Se mol ratio be 1: 3～4 amount, with MoO ₃Or WO ₃Nano particle joins in the mixing solutions, behind mechanical stirring 15～20min, places ultrasonic cleaner ultra-sonic dispersion 20～30min, passes through underpressure distillation again, removes solvent and can obtain the MoO that the surface has coated S or Se ₃Or WO ₃The composite particles powder;

(c) MoO of S or Se coating ₃Or WO ₃The sulfuration of composite particles powder or selenizing: with the MoO of S or Se coating ₃Or WO ₃Composite granule places the vulcanization reaction chamber, reaction chamber is evacuated to below the 1Pa again, slowly charges into exsiccant hydrogen to 0.02～0.06MPa then in reaction chamber, then reaction chamber is heated to 450 ℃～700 ℃, and temperature rise rate is 10 ℃ of min ^-1, constant temperature 30～90min; Cool to room temperature then with the furnace, can obtain the MoS of hollow cage-shape structure ₂, MoSe ₂Or WS ₂, WSe ₂The nano solid lubricant granular powder.