CN103205300B - Preparation method of wear-resistant self-repairing sulfur-metal nanoparticles - Google Patents
Preparation method of wear-resistant self-repairing sulfur-metal nanoparticles Download PDFInfo
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- CN103205300B CN103205300B CN201310133430.6A CN201310133430A CN103205300B CN 103205300 B CN103205300 B CN 103205300B CN 201310133430 A CN201310133430 A CN 201310133430A CN 103205300 B CN103205300 B CN 103205300B
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Abstract
The invention discloses a preparation method of wear-resistant self-repairing sulfur-metal nanoparticles. The preparation method comprises the following steps of: slowly adding a metal salt into a thiol compound of which the temperature is 60-150DEG C; vigorously stirring to obtain viscous fluid; and cooling the viscous fluid to obtain a solid namely the sulfur-metal nanoparticles. The sulfur-metal nanoparticles prepared by the method is small in diameter which is between 5 and 20 nm, has a good effect of repairing great abrasions including scratches and the like, can generate a full chemical reaction at a repaired part due to the small diameter, and also has a good effect of repairing fine abrasions including surface abrasions and the like; the surfaces of the sulfur-metal nanoparticles are provided with sulfur-bearing radicals, so that agglomeration of the nanoparticles cannot be generated easily, the metal nanoparticles can be kept in a monodisperse state in a short period or a long period of time, and the stability of the metal nanoparticles in oil phase media including lubricating oil and the like is lasting. The preparation method is simple and feasible, the purity of the product is high, and raw materials are easy to obtain and low in price.
Description
Technical field
The present invention relates to a kind of preparation method of metal nanoparticle, relate in particular to a kind of preparation method of sulphur-metal nanoparticle of the selfreparing of resistance to wearing, belong to technical field of nano material.
Background technology
Wearing and tearing, corrosion and fatigue are three kinds of principal modes that mechanical material lost efficacy, there is report to point out: whole world primary energy source nearly 1/3 is consumed in abrasion, also brings thus huge economy to lose: the U.S. exceedes 2,000 hundred million dollars because of the financial loss that wearing and tearing cause every year, and China also reaches approximately 60,000,000,000 yuans.In various fields, especially automobile manufacturing field, the energy that accounts for engine total energy 30% is consumed by frictionwork, and the utilization ratio of total energy is low, therefore, development is resistance to worn and is one of approach of improving energy efficiency, has great importance with metal self-repair technology.
Nano material has the characteristics such as specific surface area is large, diffustivity is high, easy-sintering, fusing point is low, hardness is larger, is added in lubricating oil, plays excellent antifriction antiwear effect.This nano material not only can form the easy film of shearing of one deck and reduce rubbing factor at friction surface, and can also friction surface necessarily be filled up and be repaired, and plays self-repair function, is highly suitable for the Working environment of heavy duty, low speed, high temperature.
At present, nano material anti-friction damage is focus and the difficult point of research both at home and abroad with the research of selfreparing aspect.Last century the eighties so far, on market, there is relevant product, as pacify resistance to metal antiwear agent and special wear-resisting engine copper facing protective material etc. of speeding, but still there is following shortcoming in the above-mentioned anti-wear agent that contains nano material: the one, and Surface Modification of Nanosized Materials not exclusively, easily produces the phenomenon that nanoparticle is reunited, the aggregate producing by reuniting can become the new source of wear of the metallic surfaces such as engine, thus further unstable wear; The 2nd, the stability in lubricated wet goods medium is not lasting, can only obtain the dispersion of short-term, and long-term static or can make nanoparticle generation agglomeration; The 3rd, repair is comparatively limited to, and the metal nanoparticle particle diameter that currently available technology prepares is generally larger, only for cut etc. compared with galling repairing effect better and poor compared with the repairing effect of finite wear to surface wear etc.; The 4th, in preparation process, easily introduce impurity, cause nano material product impure, purification operations complex steps.
Summary of the invention
The present invention seeks to provide in order to solve the problem that above-mentioned prior art exists a kind of preparation method of metal nanoparticle, specifically a kind of preparation method of sulphur-metal nanoparticle of the selfreparing of resistance to wearing, the inventive method adopts a step liquid phase synthesis process, and original position is prepared into the sulphur-metal nanoparticle of minor diameter on a large scale.Object of the present invention is achieved by the following technical programs:
The resistance to wear preparation method of sulphur-metal nanoparticle of selfreparing, comprises the steps:
1. sulfur alcohol compound is positioned in a container, heats up and maintain the temperature at 60 DEG C～150 DEG C;
2. taking metal-salt as source metal, metal-salt is joined in described container and stirred, stir speed (S.S.) is 400rpm～1500rpm, and temperature range is between 60 DEG C～150 DEG C;
3. by step 2. in mixture maintain the temperature under 60 DEG C～150 DEG C conditions and stir 1h～3h, reaction obtains sulphur-metal nanoparticle viscous fluid;
4. described sulphur-metal nanoparticle viscous fluid is placed to cooling 6h～10h under room temperature and obtained sulphur-metal nanoparticle solid, obtain sulphur-metal nanoparticle.
Further, the mol ratio of described sulfur alcohol compound and metal-salt is (5～10): 1 in the present invention.
Further, the purity of described sulfur alcohol compound is calculated in mass percent >=98% in the present invention.
Further, sulfur alcohol compound is Dodecyl Mercaptan, 16 mercaptan, dithioglycol, benzyl sulfhydrate or tert-dodecyl mercaptan in the present invention.
Further, described metal-salt is the chemical pure inorganic salt containing Fe metal ion, Zn metal ion, Ni metal ion, Cu metal ion or Ag metal ion in the present invention.
The inventive method adopts a step liquid phase synthesis process, and original position is prepared into the sulphur-metal nanoparticle of minor diameter on a large scale, and its application is implemented its remarkable technique effect is mainly reflected in:
(1) that the diameter of the metal nanoparticle that the sulphur-metal nanoparticle making by the present invention and traditional method make is compared is little, between 5nm～20nm, not only good compared with galling repairing effect for cut etc., and because its particle diameter is less and sufficient chemical reaction can occur in repair place, surface wear etc. is also had to good effect compared with the reparation of finite wear;
(2) sulphur-surfaces of metal nanoparticles making by the present invention has abundant sulfur-containing group, comparatively complete, the difficult phenomenon that produces nanoparticle reunion of surface modification, can not only obtain the dispersion of short-term and the stability in lubricated wet goods oil-phase medium is lasting, can keep chronically metal nanoparticle monodisperse status, do not occur to reunite or assemble, and high temperature resistant, stable in properties, has chemical high reactivity;
(3) the inventive method is simple, avoids traditional method in reaction process, to add solvent or other materials, and product purity is high, no coupling product pollute, environmental protection, and starting material be easy to get, cheap.
Below just by reference to the accompanying drawings, the specific embodiment of the present invention is described in further detail, so that technical solution of the present invention is easier to understand, grasp.
Brief description of the drawings
Fig. 1 is transmission electron microscope (TEM) photo of sulphur-metal nanoparticle of preparing in the inventive method embodiment.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment, the present invention will be described, for embodiment product of the present invention or method are made to generality illustrate, contribute to understand better the present invention, but can't limit the scope of the invention.Experimental technique described in following embodiment, if no special instructions, is ordinary method; Described material, if no special instructions, all can obtain from commercial channels.
The preparation method who the invention provides a kind of sulphur-metal nanoparticle of the selfreparing of resistance to wearing, it comprises the steps:
1. sulfur alcohol compound is positioned in a container, heats up and maintain the temperature at 60 DEG C～150 DEG C;
2. taking metal-salt as source metal, metal-salt is joined in described container and stirred, stir speed (S.S.) is 400rpm～1500rpm, and temperature range is between 60 DEG C～150 DEG C;
3. by step 2. in maintaining the temperature under 60 DEG C～150 DEG C conditions of mixture stir 1h～3h, reaction obtains sulphur-metal nanoparticle viscous fluid;
4. described sulphur-metal nanoparticle viscous fluid is placed to cooling 6h～10h under room temperature and obtained sulphur-metal nanoparticle solid, obtain sulphur-metal nanoparticle.
Step 1. in, described sulfur alcohol compound should be liquid state at normal temperatures, and be to be also liquid state when temperature is increased to 60 DEG C～150 DEG C, particularly, sulfur alcohol compound of the present invention includes but not limited to Dodecyl Mercaptan, 16 mercaptan, dithioglycol, benzyl sulfhydrate or tert-dodecyl mercaptan, certainly, as known to the skilled person, also comprise the homologue of above-claimed cpd.The purity of the present invention's sulfur alcohol compound used is calculated in mass percent >=98%, with reduce impurity primer, that sulphur-metal nanoparticle product purity is handed over is high, reduce by product and generate.
Step 2. in, described metal-salt includes but not limited to the chemical pure inorganic salt containing the metal ion such as Fe, Zn, Ni, Cu or Ag.Concrete, as known to the skilled person, the nitrate, nitrite, carbonate, vitriol, sulphite, the phosphoric acid salt that comprise above-mentioned metal ion, and corresponding oxyhydroxide, subsalt, acid salt etc.Metal ion content in described metal-salt is identical with the metal content in the sulphur-metal nanoparticle that will obtain.Particularly, the mol ratio of described sulfur alcohol compound and metal-salt is (5～10): 1, if the valence state of metal is+n that the mol ratio of sulfur alcohol compound and metal-salt should be greater than n in the metal inorganic salt that step is used in 2..Metal-salt is joined in the process of described container, be in stirring described sulfur alcohol compound, added lentamente on a small quantity in batches.Described container comprises that the laboratories such as beaker commonly use reaction kit.
Step 3. in, when the metal-salt of step in 2. add complete after, container can be placed on to water-bath, oil bath or other heat above heating instrument and are incubated, and stir 1h～3h in the time that stir speed (S.S.) is 400rpm～1500rpm, make the acid producing in reaction process fully wave and shed with gas form.The experiment proved that in above-mentioned stir speed (S.S.) be in the whipping process of 400rpm～1500rpm intensity, reactant is that metal-salt and sulfur alcohol compound fully react.
Step 4. in, place at ambient temperature, i.e. cooling 6h～10h under 25 DEG C of left and right conditions, be preferably 8h.Certainly, according to the concrete size of required sulphur-metal nanoparticle, concrete cooling time and cooling temperature are adjustable, all, within protection domain of the present invention, adopt the inventive method can make the minor diameter sulphur-metal nanoparticle of particle diameter at 5nm～20nm.
To sum up, first, metal nanoparticle diameter that the sulphur-metal nanoparticle making by the present invention and traditional method make is smaller, between 5nm～20nm, not only good compared with galling repairing effect for cut etc., and because its particle diameter is less and sufficient chemical reaction can occur in repair place, as the replacement(metathesis)reaction occurring between metal, or combination reaction of metal and organo-functional group, alloying reaction, precipitation conversion reaction etc., this also has good effect to surface wear etc. compared with the reparation of finite wear; Secondly, sulphur-the surfaces of metal nanoparticles making by the present invention has abundant sulfur-containing group, comparatively complete, the difficult phenomenon that produces nanoparticle reunion of surface modification, can not only obtain the dispersion of short-term and the stability in lubricated wet goods oil-phase medium is lasting, can be chronically, conventionally more than two years, the stable metal nanoparticle monodisperse status that keeps, does not occur to reunite or assemble, and high temperature resistant, stable in properties, has chemical high reactivity; The inventive method is simple again, avoids traditional method in reaction process, to add solvent or other materials, and product purity is high, no coupling product pollute, environmental protection, and starting material be easy to get, cheap.
[
embodiment 1]
Taking cupric chloride as metal source, 100g cupric chloride is slowly joined and fills 900ml temperature in the hexadecyl mercaptan beaker of 60 DEG C, mixing liquid is stirred energetically, and stir speed (S.S.) is 1500 rpm, emits a large amount of sour gas in reaction process, after stirring 1h, substantially no longer include air release, it is thick that the solution in reaction vessel beaker becomes black, and then by room temperature cooling placement of viscous fluid, after 8h, thick product becomes black solid, obtains sulphur-metal nanoparticle.Fig. 1 is transmission electron microscope (TEM) photo of the carbon nano-particles for preparing in the present embodiment 1, can see that nanoparticle is uniformly dispersed, and diameter is 5nm～20nm.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, do not departing under the prerequisite of the technology of the present invention principle; can also make some improvement and modification, these improve and modification also should be considered as protection scope of the present invention.。
Claims (1)
1. the resistance to wear preparation method of sulphur-metal nanoparticle of selfreparing, is characterized in that comprising the steps:
1. sulfur alcohol compound is positioned in a container, heats up and maintain the temperature at 60 DEG C～150 DEG C;
2. taking metal-salt as source metal, metal-salt is joined in described container and stirred, stir speed (S.S.) is 400rpm～1500rpm, temperature range is between 60 DEG C～150 DEG C, the mol ratio of described sulfur alcohol compound and metal-salt is (5～10): 1, the purity of described sulfur alcohol compound is calculated in mass percent >=and 98%, described sulfur alcohol compound is Dodecyl Mercaptan, 16 mercaptan, dithioglycol, benzyl sulfhydrate or tert-dodecyl mercaptan, described metal-salt is chemical pure containing Fe metal ion, Zn metal ion, Ni metal ion, the inorganic salt of Cu metal ion or Ag metal ion,
3. by step 2. in mixture maintain the temperature under 60 DEG C～150 DEG C conditions and stir 1h～3h, reaction obtains sulphur-metal nanoparticle viscous fluid;
4. described sulphur-metal nanoparticle viscous fluid is placed to cooling 6h～10h under room temperature and obtained sulphur-metal nanoparticle solid, obtain sulphur-metal nanoparticle.
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