CN106118138B - A kind of composite and preparation method of polarity macromolecular coating nano carbon SiClx - Google Patents
A kind of composite and preparation method of polarity macromolecular coating nano carbon SiClx Download PDFInfo
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M161/00—Lubricating compositions characterised by the additive being a mixture of a macromolecular compound and a non-macromolecular compound, each of these compounds being essential
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/04—Detergent property or dispersant property
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
Abstract
The present invention discloses a kind of method for preparing polarity macromolecular cladding nano SiC composite.First, by using the sorting of dimethyl sulfoxide (DMSO)/aqueous solution of Long carbon chain surfactant, so that nano SiC is together suspended in solution with surfactant, micron or larger sized SiC can not Effective Suspensions, reach from the mixed powder of micron SiC and nano SiC, high selectivity extracts the purpose of nano SiC.Then, by nano SiC, polarity macromolecular, weak polar solvent mixing and ball milling, the nano SiC material that polarity macromolecular coats is prepared.Sort nano SiC solvent toxicity is low, not volatile, reusable edible, no discharging of waste liquid, operation temperature is wide.Preparation flow simple and effective, cost are low, have extensive industrial applications prospect.
Description
Technical field
The present invention relates to the preparation method technical field of nano silicon carbide silicon composite, and in particular to a kind of polarity macromolecular
The preparation method of the composite of coating nano carbon SiClx, and the composite that thus method obtains.
Background technology
Nanometer additive is with a wide range of applications in lubrication and anti-attrition field.At present, Nanometer Copper (Zhou J, Wu Z,
Zhang Z,et al.Tribological behavior and lubricating mechanism of Cu
nanoparticles in oil[J].Tribology Letters,2000,8(4):213-218.) and nano nickel (Nan
F,Xu Y,Xu B,et al.Tribological Performance of Attapulgite Nano-fiber/
Spherical Nano-Ni as Lubricant Additive[J].Tribology Letters,2014,56(3):531-
Etc. 541.) research of metal mold lube oil additive has obtained suitable progress.The preparation cost of these nano metals is of a relatively high,
Density is about ten times of lubricating oil.In actual applications, how to prevent high density nano metal from coagulation and being grown up in lubricating oil,
It is urgent problem to be solved；Nanometer Copper and nano nickel are the catalyst of organic reaction, easily cause lubricating oil component and property to be sent out
Changing.On the other hand, Nano diamond (density 3.5g/cm3) etc. non-metal type lube oil additive also attract attention.So
And the preparation cost of Nano diamond is also higher.The hardness of carborundum (SiC) is slightly below diamond, and it is substantially low that it prepares cost
In diamond, and with anti-oxidant, corrosion-resistant, thermal conductivity is good and the characteristics such as thermal coefficient of expansion is low.Therefore, nano SiC is considered as
It is excellent lubricating oil added material.SiC density is 3.2g/cm3, about lubricate 4 times of oil density；Although its density is obvious
Less than metals such as Cu, Ni, but also need solve the problems, such as its stable dispersion in lubricating oil.
At present, the nano SiC preparation method reported mainly include laser ablation method (Shi W, Zheng Y, Peng H,
et al.Laser ablation synthesis and optical characterization of silicon
carbide nanowires[J].Journal of the American Ceramic Society,2000,83(12)：
3228-3230.), chemical vapor deposition method (Choi H J, Seong H K, Lee J C, et al.Growth and
modulation of silicon carbide nanowires[J].Journal of crystal growth,2004,269
(2)：472-478.), arc discharge method (Seeger T, Kohler-Redlich P, Ruehle M.Synthesis of
Nanometer-Sized SiC Whiskers in the Arc-Discharge[J].Advanced Materials,2000,
12(4)：279-282.), solvent-thermal method (Lu Q, Hu J, Tang K, et al.Growth of SiCnanorods at low
temperature[J].Applied physics letters,1999,75(4)：507-509.) etc..These methods generally relate to
And harsh reaction condition and complicated operating process, and production process is also possible to produce the gas harmful to environment and human body
And dust, preparation technology equipment investment are larger.
The commercial run that low cost prepares SiC is to heat in resistance furnace quartz sand with petroleum coke, is allowed to carbon occurs hot
Reduction reaction, generation block SiC；Then, by grinding technics block SiC can be made to be broken into SiC powder.But polishing
The problem of size distribution is wide be present in the SiC powder of preparation, wherein there is larger amount of micron SiC to be coexisted with nano SiC, the big day of one's doom
The use of the latter processed, hinder prepare with scale and the application of nano SiC.
The content of the invention
The present invention provides a kind of preparation method of polarity macromolecular cladding nano SiC composite.Add for existing nanometer
The problems such as adding agent to prepare cost high, dispersion stabilization difference in lubricating oil, there is provided one kind can be in lubricating oil compared with stable dispersion
Nano SiC composite process of preparing.In the powder coexisted first from nano SiC and micron SiC, selective extraction
Prepare nano SiC；Then, by poles such as the water-soluble cellulose of nano SiC Surface coating low-density, water-soluble lignins
Property macromolecular so that the apparent density of nano SiC composite reduces, and reaching strengthens its Investigation of stabilized dispersion of nano in oil systems are lubricated
Purpose.This technique have the characteristics that it is easy to operate, inexpensive, can be mass-produced, whole flow process is as shown in Figure 1.
Specifically, the preparation method of polarity macromolecular cladding nano SiC composite of the present invention, it includes following
Step：
(1) mixed powder of nano SiC and micron SiC is chosen as raw material, by it with sorting solution according to 1g：2~
10mL ratio is sufficiently mixed, and stands 6~24h；Wherein, preferable mixed proportion is 1g：5mL.
It is used sorting solution be by the dimethyl sulfoxide (DMSO) containing Long carbon chain body structure surface active agent saturated solution, two
Methyl sulfoxide and water press 1：0~2：0~3 volume ratio, the mixed solution being formulated；
Used surfactant has linear long carbon-chain structure, and the wherein carbon number of carbochain is 12~32.For example,
In the anionic surfactant such as DBSA, cetyl benzenesulfonic acid, palmitic acid, the sodium salt of oleic acid or sylvite
One or more of mixtures；Or it is DTAC, OTAC, octadecyl three
In the cationic surface active agents such as methyl bromide ammonium, tridodecylmethylammonium ammonium chloride, stearalkonium chloride
One or more of mixtures.Wherein, preferable surfactant is enuatrol.
Specifically, the well-mixed method described in step (1) is ultrasound and/or vibration.It is described super in the case of preferable
Acoustic frequency and time are 5~6kHz, 8~12min；Frequency of oscillation and time are 200~400r/min, 150~200min.
(2) upper suspension after step (1) is stood is separated with lower floor solid phase, and lower floor's solid phase is micrometer silicon carbide
Silicon.For upper suspension after centrifugation or filtering, obtained solid phase is nano SiC；Liquid phase is sorting solvent, can be repeated for nanometer
The sorting of carborundum.Specifically, the centrifugation rotating speed carried out is 2000~5000r/min, centrifugation time is 20~
40min。
(3) nano SiC obtained in step (2) is mixed with polarity macromolecular and weak polar solvent, carries out wet ball grinding
Processing.
Specifically, polarity macromolecular is the one or more in water-soluble cellulose, water-soluble lignin；Wherein, preferably
Water-soluble cellulose for carboxymethyl cellulose, the sodium salt of carboxymethyl cellulose, sylvite, magnesium salts, calcium salt；Preferable water-soluble wood
Quality is lignosulfonates, such as：Sodium salt, sylvite, magnesium salts, the calcium salt of lignin sulfonic acid, and described lignin sulfonic acid
The graft copolymer of the monomer such as salt and oxirane, acrylamide, styrene, acrylic acid, maleic anhydride.
Specifically, weak polar solvent is the alcohol that the carbon chain lengths such as ethanol, methanol, isopropanol, n-butanol are 1~6, Huo Zhebing
The carbon chain lengths such as ketone, butanone, metacetone are 3~6 ketone, or one or more in ethyl acetate, ethyl butyrate.
Specifically, the mass ratio of nano SiC, polarity macromolecule polyalcohol, weak polar solvent is 1：0.5~3：1~4；
Specifically, rotational speed of ball-mill is 50~600r/min, Ball-milling Time is 4~48h, nano SiC and polarity macromolecular
The mass ratio of gross mass and mill ball is 1：5~20.
(4) by the product drying process after ball milling, the nano composite material of polarity macromolecular coated Si/C is obtained.
The principle that the present invention is sorted to nano SiC and micron SiC：
Partial oxidation can occur in natural environment and polarity is presented for surface of SiC.When it is in Longer-chain surfactants
When in solution, the polar group of surfactant can be adsorbed in the polar surfaces of SiC particles, and by nonpolar Long carbon chain direction
Solution.The Long carbon chain of the Brownian movement Surfactant of solvent molecule is collided, and be may be such that and is adsorbed in nano SiC surface
The nano SiC that surfactant molecule is adsorbed together with it is in the lump suspended state into solution.By comparison, surfactant
Suction-operated on the micron SiC surface more relatively low than surface, is not enough to be suspended.Therefore, micron SiC is formed in solution bottom
Precipitation.Upper suspension and lower sediment are separated, the separation of nano SiC and micron SiC can be achieved.
Using radius as r, exemplified by density is ρ spherical SiC, the difference of this suspension effect is illustrated：
Fig. 2 gives absorption schematic diagram of the surfactant in different-grain diameter surface of SiC.If surfactant is in SiC tables
Adsorption density in the unit area in face is a, then surfactant is in the adsorbance total amount of surface of SiC：A=4a π r2.Such as
Upper described, more in the surfactant molecule of surface of SiC absorption, the suspension effect suffered by it is stronger.It is absorption to define m
The buoyancy coefficient that surfactant is applied to unit mass SiC：
From above formula, the particle diameter r of buoyancy coefficient m and SiC suffered by the SiC of unit mass are in inverse ratio.When SiC grain
When footpath D1 differs n times with D2, buoyancy coefficient m suffered by the big particle diameter SiC of unit mass is small particle SiC n/mono-.With
Particle diameter increases, and the buoyancy effect that surfactant gives the SiC of unit mass will reduce.Therefore, can be from nano SiC and micron
Nano SiC is sub-elected in SiC mixed powder.
Generally, the non-polar group of the surfactant with Long carbon chain can not be fully extended in aqueous, and be dissolved
Degree is very low, causes the collision effect of solvent molecule Brownian movement very limited to " lifting " effect of nano SiC.If from third
The non-polar organic solvents such as ketone, ether replace water as solvent, though contribute to the stretching, extension of Long carbon chain surfactant in the solution,
But the effumability and inflammability of these organic solvents can cause the problems such as health safety, disaster hidden-trouble.The present invention
The mixed solvent being made into using nontoxic and high boiling dimethyl sulfoxide (DMSO) and water, the solubility of surfactant is remarkably improved,
So that its long-chain is fully extended in the solution, the effumability and inflammability of organic solvent are not only avoid, and can prepare
Recycled in technique, reduce discharging of waste liquid, reduce process costs.
The present invention prepares the principle of polarity macromolecular cladding nano SiC nano composite material：
Cellulose and lignin are two kinds of natural macromoleculars most abundant in nature.After cellulose is by chemical modification,
Water miscible polarity macromolecular can be generated；Such as carboxymethyl cellulose, carboxymethyl cellulose salt etc..Fig. 3 is carboxymethyl cellulose
Salt loses the structural formula after metal ion.The structure of lignin is relative complex, and its basic monomer structure is as shown in figure 4, main bag
(a) coniferyl alcohol, (b) sinapinic alcohol, (c) are included to hydroxyl cinnamyl alcohol.Natural lignin is chemically modified to can obtain water-soluble lignin.Than
Such as, lignosulfonates etc..
The SiO of partial oxidation generation polarity can occur in natural environment for nano SiC surface2.When polarity macromolecular is with receiving
In weak polar solvent during common ball milling, being slightly soluble in the polarity macromolecular of liquid phase medium can be adsorbed in uniformly and firmly and receive rice SiC
Rice SiC surface is simultaneously wound repeatedly to it.
Polarity macromolecular is insoluble in lubricating oil, and the composite construction of its composition with nano SiC can be good in oil systems are lubricated
It is good to keep.The density of water-soluble cellulose is about 1.6g/cm3, the density of water-soluble lignin is about 1.3~1.5g/cm3.Cause
This, the apparent density of polarity macromolecular cladding nano SiC composite construction is less than SiC, can be shown in oil systems are lubricated higher
Dispersion stabilization.On the other hand, the backbone tool for the polarity macromolecular firmly adsorbed on nano SiC surface and wound repeatedly
There is good pliability, the mutual supplement with each other's advantages of " soft shell stone " can be formed with nano SiC, avoids high hardness nanocomposite under the conditions of extreme pressure
SiC directly contacts with surface of friction pair, is advantageous to improve " nanometer ball " performance, has weight for improving lubrication reduction abrasion
Want meaning.
Beneficial effect
First, raw material used in the present invention is mixed using the nano SiC and micron SiC of the low cost process such as polishing preparation
Powder is closed, has cost low, flow is simple, is easy to the features such as large-scale production.Cellulose and the lignin content in nature
It is abundant.Used covering material carboxymethyl cellulose, carboxymethyl cellulose salt and water-soluble lignin, belong to environment friend
Good material, cost are relatively low.
2nd, the mixed solvent that the present invention is configured to using nontoxic and high boiling dimethyl sulfoxide (DMSO) with water, can make surface live
Property agent solubility improve tens times, not only the absorption to SiC particles is more abundant, and improves the efficiency of separation, while solvent
Not volatile, safe operation, Applicable temperature is wider.
3rd, the apparent density of polarity macromolecular cladding nano SiC composite construction is less than SiC, and coagulation is not easy in lubricating oil.
These macromolecules form firm winding arrangement in nano SiC outer layer, can strengthen the pliability of nano composite structure, prevent pole
Nano SiC contacts with the direct of friction surface under the conditions of pressure, reduces and caused may wear.
Brief description of the drawings
Fig. 1：The operational flowchart of the method for the invention.
Fig. 2：Absorption schematic diagram of the Long carbon chain surfactant in different-grain diameter surface of SiC.
Fig. 3：The structure chart of carboxymethyl cellulose.
Fig. 4：The basic monomer structure chart of lignin.
Fig. 5：The mixed powder raw material granularity distribution map of nano SiC and micron SiC.
Fig. 6：The nano SiC particle size distribution figure prepared using enuatrol/dimethyl sulfoxide (DMSO)/aqueous solution sorting.
Fig. 7：Nano SiC ESEM (SEM) shape appearance figure prepared using enuatrol/dimethyl sulfoxide (DMSO)/aqueous solution sorting.
Fig. 8：The Raman spectrogram of sodium carboxymethylcellulose.
Fig. 9：The Raman spectrogram of the sodium carboxymethylcellulose cladding nano SiC nano composite material of preparation.
Figure 10：The nano SiC particle size distribution figure prepared using enuatrol/dimethyl sulfoxide (DMSO) saturated solution sorting.
Figure 11：Nano SiC ESEM (SEM) pattern prepared using enuatrol/dimethyl sulfoxide (DMSO) saturated solution sorting
Figure.
Figure 12：The Raman spectrogram of the sodium carboxymethylcellulose cladding nano SiC nano composite material of preparation.
Figure 13：The Raman spectrogram of sodium lignin sulfonate.
Figure 14：The Raman spectrogram of the sodium lignin sulfonate cladding nano SiC nano composite material of preparation.
Figure 15：The Raman spectrogram of the sodium lignin sulfonate cladding nano SiC nano composite material of preparation.
Embodiment
Following non-limiting examples can make one of ordinary skill in the art be more fully understood the present invention, but not with
Any mode limits the present invention.
The operational flowchart of the method for the invention, such as Fig. 1.The SiC raw materials used in following all embodiments are nanometer
SiC and micron SiC mixture, it is as shown in Figure 5 purchased from Qingzhou Heng Tai micro mists Co., Ltd, its size distribution.Dimethyl sulfoxide (DMSO)
(analysis is pure), enuatrol (chemistry is pure), absolute ethyl alcohol (analysis is pure), sodium carboxymethylcellulose (analysis is pure) are purchased from Chinese medicines group
Learn reagent Co., Ltd.Sodium lignin sulfonate (chemistry is pure) is purchased from Shanghai fuzz Chemical Co., Ltd..Lube base oil
(HVI400SN), steam turbine oil (TSA32) is provided by Dalian lubricating oil research and development centre of CNPC.Use Malvern granularity
Analyzer Z90 tests the size distribution of nano SiC.Using the shape of QUNATA200FEG SEM measure nano SiC
Looks.Ball milling is carried out using QM-3SP4 planetary ball mills (Nanjing Univ. Instrument Factory).It is micro- common using Horiba JYXplorA
The drawing of the composite construction of burnt Raman spectrometer measure sodium carboxymethylcellulose, sodium lignin sulfonate and the two cladding nano SiC
Graceful spectrum, excitation wavelength 532nm.
Embodiment 1
(1) preparation of nanometer silicon carbide：
First, by the DMSO saturated solutions, pure DMSO, deionized water of enuatrol according to 1：1：2 volume ratio is mixed, and is obtained
To sorting solution；
2nd, take 40mL to sort solution, add 8g SiC raw material powder；Carry out 10min ultrasound (5.5kHz) and 180min
Shaking table vibrates (300r/min), SiC powder is uniformly dispersed in the solution；Then, 8h is stood.
3rd, in the mixed liquor after standing 70~80% upper liquid is transferred out of, is centrifuged (4000r/min；30min)
Or filtering-backwash separation, the solid phase isolated after drying, obtain nano SiC；Its size distribution and ESEM pattern
As difference as shown in Figure 6, Figure 7.The prepared product of graphical results confirmation is nano SiC.
Dimethyl sulfoxide (DMSO)-the aqueous solution isolated is reclaimed, continues on for sorting.
4th, remaining subnatant in the mixed liquor after standing and solid content are removed, is centrifuged or filtered-backwashed point
From obtaining the powder based on micron SiC after drying.
Dimethyl sulfoxide (DMSO)-the aqueous solution isolated is reclaimed, continues on for sorting.
(2) preparation of sodium carboxymethylcellulose cladding nano SiC：
5th, take nano SiC 6g produced above and the mass mixings such as sodium carboxymethylcellulose is carried out, add the anhydrous second of 12g
Alcohol, carry out 8h ball-milling treatment；
6th, the product after ball milling is dried, obtains the composite of sodium carboxymethylcellulose cladding nano SiC, determine it
Raman spectrum.Excitation source is the 532nm exciting lights that can excite fluorescence and Raman signal simultaneously.Fig. 8 is not carry out any fluorescence
The original Raman spectrum of the sodium carboxymethylcellulose of background subtraction, observe that it has obvious fluorescence signal.Fig. 9 is carboxymethyl
Sodium cellulosate coats the Raman spectrum of nano SiC composite.As Raman shift increases, spectral line background intensity gradually increases,
Show there is the obvious component of fluorescence signal in sample, this is caused by the sodium carboxymethylcellulose of silicon carbide.In figure
780 and 955cm-1The absworption peak at place is respectively the horizontal optics (TO) and vertical optics (LO) pattern feature peak of nano SiC；Due to carboxylic first
The translucency of base sodium cellulosate clad is preferable, therefore nano SiC characteristic signal can be detected in the lump.This result shows institute
It is the composite construction that sodium carboxymethylcellulose coats nano SiC to detect material.
(3) the dispersion stabilization contrast in lube base oil：
The nano SiC that sodium carboxymethylcellulose prepared by nano SiC and step 6 prepared by step 3 coats is compound
Material, respectively with 1g：150ml ratio is added in 150ml lube base oils (HVI400SN), and fully vibration makes its uniform
Stood after scattered；After 20 days, the lubrication oil systems of addition sodium carboxymethylcellulose cladding nano SiC composite do not occur substantially
Change, still keeps dispersed lighttight suspended state；Add half of the lubrication oil systems in its container of nano SiC
Highly there is obvious layering in place, and upper strata is limpider, and lower floor is the deeper suspended state of color.This comparing result shows, of the invention
The composite of sodium carboxymethylcellulose cladding nano SiC prepared by methods described, has more preferable dispersion stabilization.
Embodiment 2
(1) preparation of nanometer silicon carbide：
The first, the dimethyl sulfoxide (DMSO) saturated solution of 500mL enuatrols and 100gSiC raw materials powder mix to (the two ratio is
5mL：1g), 10min ultrasound (5.5kHz) and 180min shaking table vibration (300r/min) are carried out, makes SiC powder in the solution
It is uniformly dispersed；Then, 8h is stood.
2nd, 70~80% upper liquid in the mixed liquor after standing is transferred out of, is centrifuged (4000r/min；
30min) or filtering-backwash separation, the solid phase isolated after drying, obtain nano SiC；Its size distribution and scanning electricity
Mirror X rays topographs difference is as shown in Figure 10, Figure 11.Graphical results show that prepared product is nano SiC.
The dimethyl sulphoxide solution isolated is reclaimed, continues on for sorting.
3rd, remaining subnatant in the mixed liquor after standing and solid content are removed, is centrifuged or filtered-backwashed point
From obtaining the powder based on micron SiC after drying.
The dimethyl sulphoxide solution isolated is reclaimed, continues on for sorting.
(2) preparation of sodium carboxymethylcellulose cladding nano SiC：
4th, take nano SiC 6g produced above to be mixed with sodium carboxymethylcellulose 5g, add 12g absolute ethyl alcohols,
Carry out 8h ball-milling treatment；
5th, the product after ball milling is dried, obtains the composite of sodium carboxymethylcellulose cladding nano SiC.Exciting light
Source is the 532nm exciting lights that can excite fluorescence and Raman signal simultaneously.Figure 12 is the carboxylic first for not carrying out any fluorescence background subtraction
Base sodium cellulosate coats the original spectrogram of composite of nano SiC.As Raman shift increases, spectral line background intensity gradually increases
Add, show the component for having fluorescence signal stronger in sample, this is caused by the sodium carboxymethylcellulose of silicon carbide cladding.
Because the translucency of sodium carboxymethylcellulose clad is good, the horizontal optics (TO) and vertical optics (LO) pattern feature of nano SiC
Peak is also detected in the lump.This result shows that detected material coats the composite construction of nano SiC for sodium carboxymethylcellulose.
(3) the dispersion stabilization contrast in lube base oil：
Sodium carboxymethylcellulose prepared by nano SiC and step 6 prepared by step 4 coats the compound of nano SiC
Material is respectively with 1g：150ml ratio is added in 150ml steam turbine oils (TSA32), and fully vibration is quiet after making its dispersed
Put；After 20 days, the lubrication oil systems of addition sodium carboxymethylcellulose cladding nano SiC composite do not occur significant change, still
Keep dispersed lighttight suspended state；By comparison, add nano SiC lubrication oil systems its container five/
Occurs obvious layering at three height, upper strata is limpider, and lower floor is the deeper suspended state of color.This comparing result shows, this hair
The composite of sodium carboxymethylcellulose cladding nano SiC prepared by bright methods described has preferably stable dispersiveness.
Embodiment 3
(1) preparation of nanometer silicon carbide：
First, by the DMSO saturated solutions, pure DMSO, deionized water of enuatrol according to 1：1：2 volume ratio is mixed, and is obtained
To sorting solution；
2nd, take 40mL to sort solution, add 8gSiC raw material powder；Carry out 10min ultrasound (5.5kHz) and shaking for 180min
Bed vibration (300r/min), makes SiC powder be uniformly dispersed in the solution；Then, 8h is stood.
3rd, in the mixed liquor after standing 70~80% upper liquid is transferred out of, is centrifuged (4000r/min；30min)
Or filtering-backwash separation, the solid phase isolated after drying, obtain nano SiC；Its size distribution and ESEM pattern
As difference as shown in Figure 6, Figure 7.The prepared product of graphical results confirmation is nano SiC.
Dimethyl sulfoxide (DMSO)-the aqueous solution isolated is reclaimed, continues on for sorting.
4th, remaining subnatant in the mixed liquor after standing and solid content are removed, is centrifuged or filtered-backwashed point
From obtaining the powder based on micron SiC after drying.
Dimethyl sulfoxide (DMSO)-the aqueous solution isolated is reclaimed, continues on for sorting.
(2) preparation of sodium lignin sulfonate cladding nano SiC：
5th, take nano SiC 6g produced above to be mixed with sodium lignin sulfonate 4g, add 12g absolute ethyl alcohols, enter
Row 8h ball-milling treatment；
6th, the product after ball milling is dried, obtains the composite of sodium lignin sulfonate cladding nano SiC.Excitation source
To excite the 532nm exciting lights of fluorescence and Raman signal simultaneously.Figure 13 is the sulfomethylated lignin for not carrying out any fluorescence background subtraction
The original Raman spectrum of sour sodium.As Raman shift increases, spectral line background intensity gradually increases, and shows that its fluorescence signal is very bright
It is aobvious.Figure 14 is the original Raman spectrum of composite that sodium lignin sulfonate coats nano SiC；Wherein, the horizontal stroke of nano SiC is not observed
Optics (TO) and vertical optics (LO) pattern feature peak.This is due to that nano SiC is poor and fluorescence signal is obvious by translucency
Caused by sodium lignin sulfonate fully coats.This result shows that detected material coats answering for nano SiC for sodium lignin sulfonate
Close structure.
(3) the dispersion stabilization contrast in lube base oil：
The composite wood of sodium lignin sulfonate cladding nano SiC prepared by nano SiC and step 6 prepared by step 3
Material is respectively with 1g：150ml ratio is added in 150ml lube base oils (HVI400SN), and fully vibration makes it uniformly divide
Stood after dissipating；After 20 days, substantially becoming do not occur in the lubrication oil systems of addition sodium lignin sulfonate cladding nano SiC composite
Change, still keep dispersed lighttight suspended state；By comparison, the lubrication oil systems of nano SiC are added in its container about
Half highly locates obvious layering occur, and upper strata is limpider, and lower floor is the deeper suspended state of color.This comparing result table
Bright, the composite of sodium lignin sulfonate cladding nano SiC prepared by the method for the invention has more preferable dispersion stabilization.
Embodiment 4
(1) preparation of nanometer silicon carbide：
The first, the dimethyl sulfoxide (DMSO) saturated solution of 500mL enuatrols and 100gSiC raw materials powder mix to (the two ratio is
5mL：1g), 10min ultrasound (5.5KHz) and 180min shaking table vibration (300r/min) are carried out, makes SiC powder in the solution
It is uniformly dispersed；Then, 8h is stood.
2nd, 70~80% upper liquid in the mixed liquor after standing is transferred out of, is centrifuged (4000r/min；
30min) or filtering-backwash separation, the solid phase isolated after drying, obtain nano SiC；Its size distribution and scanning electricity
Mirror X rays topographs difference is as shown in Figure 8, Figure 9.Graphical results show that prepared product is nano SiC.
The dimethyl sulphoxide solution isolated is reclaimed, continues on for sorting.
3rd, remaining subnatant in the mixed liquor after standing and solid content are removed, is centrifuged or filtered-backwashed point
From obtaining the powder based on micron SiC after drying.
The dimethyl sulphoxide solution isolated is reclaimed, continues on for sorting.
(2) preparation of sodium lignin sulfonate cladding nano SiC：
5th, take nano SiC 6g produced above to be mixed with sodium lignin sulfonate 12g, add 18g absolute ethyl alcohols, enter
Row 8h ball-milling treatment；
6th, the product after ball milling is dried, obtains the composite of sodium lignin sulfonate cladding nano SiC.Excitation source
For the 532nm exciting lights of fluorescence and Raman signal can be excited simultaneously.Figure 15 is the composite wood that sodium lignin sulfonate coats nano SiC
Original Raman spectrum is expected, wherein being difficult to the characteristic peak for observing nano SiC.This is due to that nano SiC is poor and glimmering by translucency
Caused by the obvious sodium lignin sulfonate of optical signal fully coats.This result shows that detected material coats for sodium lignin sulfonate
The composite construction of nano SiC.
(3) the dispersion stabilization contrast in lube base oil：
The composite wood of sodium lignin sulfonate cladding nano SiC prepared by nano SiC and step 6 prepared by step 3
Material is respectively with 1g：150ml ratio is added in 150ml steam turbine oils (TSA32), and fully vibration is quiet after making its dispersed
Put；After 20 days, the lubrication oil systems of addition sodium lignin sulfonate cladding nano SiC composite do not occur significant change, still protect
Hold dispersed lighttight suspended state；By comparison, the lubrication oil systems of nano SiC are added 3/5ths of its container
Highly there is obvious layering in place, and upper strata is limpider, and lower floor is the deeper suspended state of color.This result shows side of the present invention
The composite of sodium lignin sulfonate cladding nano SiC prepared by method has more preferable dispersion stabilization.
Claims (10)
1. a kind of preparation method of the composite of polarity macromolecular coating nano carbon SiClx, it is characterised in that including following step
Suddenly：
(1) using nano SiC and the mixed powder of micron SiC as raw material, by it with sorting solution according to 1g：2~10mL ratio
Example is stood after being sufficiently mixed；
The compound method of described sorting solution is, by the saturated solution of the dimethyl sulfoxide (DMSO) containing surfactant, dimethyl
Sulfoxide and water press 1：0~2：0~3 volume ratio mixing；Wherein, described surfactant has linear long carbon-chain structure,
Carbon number is 12~32；
(2) upper suspension after step (1) is stood is separated with lower floor solid phase, and upper suspension is through centrifuging or filtering
Afterwards, nano SiC is obtained；
(3) nano SiC obtained in step (2) is subjected to wet ball grinding processing with polarity macromolecular and weak polar solvent, done
After dry, the composite of polarity macromolecular coating nano carbon SiClx is obtained；Wherein：It is described nano SiC, polarity macromolecular, weak
The mass ratio of polar solvent is 1：0.5~3：1~4；Described polarity macromolecular is in water-soluble cellulose, water-soluble lignin
One or more of mixtures；Described weak polar solvent be carbon chain lengths be 1~6 alcohol, carbon chain lengths be 3~6 ketone,
One or more of mixtures in ethyl acetate, ethyl butyrate.
2. preparation method according to claim 1, it is characterised in that described surfactant is selected from detergent alkylate sulphur
Acid, cetyl benzenesulfonic acid, palmitic acid, oleic acid sodium salt or sylvite in one or more of mixtures；Or selected from 12
Alkyl trimethyl ammonium chloride, OTAC, Cetyltrimethylammonium bromide, tridodecylmethylammonium chlorination
One or more of mixtures in ammonium, stearalkonium chloride.
3. preparation method according to claim 2, it is characterised in that described surfactant is enuatrol.
4. preparation method according to claim 1, it is characterised in that described centrifugation rotating speed is 2000~5000r/
Min, centrifugation time are 20~40min.
5. preparation method according to claim 1, it is characterised in that the well-mixed method described in step (1) is super
Sound and/or vibration.
6. preparation method according to claim 5, it is characterised in that step (1) ultrasound condition is carried out for 5~6kHz
8~12min, oscillating condition are that 200~400r/min carries out 150~200min.
7. preparation method according to claim 1, it is characterised in that the time of repose described in step (1) is 6~24h.
8. preparation method according to claim 1, it is characterised in that the rotational speed of ball-mill described in step (3) is 50~600r/
Min, Ball-milling Time are 4~48h.
9. preparation method according to claim 1, it is characterised in that nano SiC and carboxymethyl cellulose described in step (3)
The gross mass of element and the mass ratio of mill ball are 1：5~20.
10. the composite of the polarity macromolecular coating nano carbon SiClx obtained using preparation method described in claim 1.
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| EP1052653A2 (en) * | 1999-05-13 | 2000-11-15 | Shin-Etsu Chemical Co., Ltd. | Conductive powder and making process |
| CN101530913A (en) * | 2009-04-14 | 2009-09-16 | 蔡育成 | Stirred reacting and grinding processing method for production of high purity alpha-aluminum oxide, silicon carbide micron, nanometer grade powder material |
| CN101928000A (en) * | 2010-08-31 | 2010-12-29 | 中平能化集团易成新材料有限公司 | Purification method of high-purity sub-nanometer silicon carbide micro powder |
| CN102120576A (en) * | 2011-01-25 | 2011-07-13 | 西安通鑫半导体辅料有限公司 | Method for recycling silicon carbide micropowder from waste mortar produced by cutting silicon wafer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP1052653A2 (en) * | 1999-05-13 | 2000-11-15 | Shin-Etsu Chemical Co., Ltd. | Conductive powder and making process |
| CN101530913A (en) * | 2009-04-14 | 2009-09-16 | 蔡育成 | Stirred reacting and grinding processing method for production of high purity alpha-aluminum oxide, silicon carbide micron, nanometer grade powder material |
| CN101928000A (en) * | 2010-08-31 | 2010-12-29 | 中平能化集团易成新材料有限公司 | Purification method of high-purity sub-nanometer silicon carbide micro powder |
| CN102120576A (en) * | 2011-01-25 | 2011-07-13 | 西安通鑫半导体辅料有限公司 | Method for recycling silicon carbide micropowder from waste mortar produced by cutting silicon wafer |
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