CN110436942A - The preparation method of silicon dioxide coated nano sheet calcirm-fluoride composite granule - Google Patents
The preparation method of silicon dioxide coated nano sheet calcirm-fluoride composite granule Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62802—Powder coating materials
- C04B35/62805—Oxide ceramics
- C04B35/62807—Silica or silicates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
- C04B2235/445—Fluoride containing anions, e.g. fluosilicate
Abstract
The present invention relates to a kind of preparation methods of silicon dioxide coated nano calcirm-fluoride composite granule.It include: by nano calcium fluoride (CaF2) powder is added in suitable dehydrated alcohol and is stirred by ultrasonic, the suspension after dispersion is placed in and heats in magnetic stirring apparatus and quickly stirs, distilled water is poured into above-mentioned suspension, it is 8~10 that ammonium hydroxide control pH value, which is added dropwise, and ethyl orthosilicate is then slowly added dropwise.Continue to stir in magnetic stirring apparatus after dripping.Suspension after reaction is centrifuged, washes of absolute alcohol 3~5 times.Wet gel after centrifugation is added in n-butanol and distillation water mixed solution, after 30min is stirred by ultrasonic, is first removed the moisture in solution under 93 DEG C of oil bath heatings, then the dry powder under 117 DEG C of oil bath heatings, obtains with nanometer CaF2For core, SiO2For the CaF of shell2@SiO2Composite granule.Resulting silicon dioxide coated nano calcirm-fluoride composite granule, clad dense uniform are added in metal or ceramic matrix the greasy property that can not be reduced material mechanical performance and improve material.
Description
Technical field
The invention belongs to nano solid lubricant surface coating modification technical field of composite materials, and in particular to a kind of dioxy
The preparation method of SiClx cladding nano calcium fluoride composite granule.
Background technique
Disclosing the information of the background technology part, it is only intended to increase understanding of the overall background of the invention, without certainty
It is considered as recognizing or implying in any form that information composition has become existing skill well known to persons skilled in the art
Art.
Calcirm-fluoride (CaF2) it is a kind of good high temperature solid lubricant, researcher is applied in ceramic material system
Self-lubricating ceramic material is prepared, good friction reducing effect is obtained.The addition of solid lubricant can make cutter material have profit
Sliding and anti-attrition wear-resisting property, avoids the use of lubricating oil.But since the mechanical property of solid lubricant is poor, cause
The use reliability of self-lubricating ceramic material reduces.The improvement of mechanical property becomes the bottleneck of self-lubricating ceramic material research.It grinds
Study carefully that show directly to add micron-sized calcirm-fluoride larger to the Effect on Mechanical Properties of cutter, the mechanical property of cutter is greatly reduced.
Deng Jianxin et al. research discovery addition CaF2Al2O3/ TiC sintex has good lubrication and anti-attrition wear-resisting property, but its
Mechanical property has different degrees of reduction, CaF2Addition significantly reduce the mechanical property of sintex.Referring to Deng Jianxin,
Cao Tongkun, Ai Xing .Al2O3/TiC/CaF2Mechanism of Friction Reduction [J] mechanical engineering journal in self-lubrication ceramic tool cutting process,
2006,42(7).Nanotechnology is widely studied in the toughened and reinforced field of composite ceramics, and has been made progress, research shows that
Influence of the addition nano calcium fluoride to cutter material mechanical property is smaller, and referring to the bright east of clothing, Xu Chonghai, Chen Zhaoqiang wait nanometers
CaF2Influence [J] silicate journal to self-lubricating ceramic material mechanical property, 2014,42 (9).Chen Zhaoqiang is respectively with Al2O3/
TiC and Al2O3/ Ti (C, N) is that matrix is prepared for different CaF2@Al2O3The core-shell structure copolymer of content coats self-lubrication ceramic cutter material.
Work as CaF2@Al2O3When content is 10vo1.%, Al2O3/TiC/CaF2@Al2O3Cutter material comprehensive mechanical property is best, bending resistance
Intensity is 662MPa, fracture toughness 6.34MPa.m1/2, hardness 16.86GPa.Content CaF corresponding to addition2Cutter material
Material is compared, and above-mentioned performance is respectively increased 19.06%, 36.93% and 12.25%.Work as CaF2@Al2O3When content is 10vo1.%,
Al2O3/Ti(C,N)/CaF2@Al2O3Cutter material comprehensive mechanical property is best, bending strength 680MPa, and fracture toughness is
6.50MPa.m1/2, hardness 17.29GPa, content CaF corresponding to addition2Cutter material compare, the above performance is respectively increased
12.21%, 29.48%, 14.50%.It is ground referring to old according to the cladding self-lubrication ceramic cutter development of strong core-shell structure copolymer and its cutting ability
Study carefully [D] .2016.
But current coated with silica method is only applicable to micron order material mostly；Coat nanometer materials when, often because
It is serious for agglomeration, it is unable to reach expected effect.
Summary of the invention
Can significantly improve material friction performance for solid lubricant calcirm-fluoride but material mechanical performance is caused to reduce,
And the technical problem that nanoscale calcirm-fluoride is easy to reunite, covered effect is poor, the present invention provides a kind of silicon dioxide coated nano fluorine
The preparation method for changing calcium composite granule, prepares the CaF with core-shell structure2@SiO2Composite granule.
To realize the above-mentioned technical purpose, The technical solution adopted by the invention is as follows:
A kind of preparation method of silicon dioxide coated nano calcirm-fluoride composite granule, comprising:
Nano calcium fluoride powder is dispersed in alcoholic solution, water, ammonium hydroxide, ethyl orthosilicate is sequentially added to it, makes positive silicon
Suspension centrifugation, washing after reaction is obtained wet gel by acetoacetic ester hydrolytie polycondensation under ammonia-catalyzed；
By wet gel be added n-butanol and distillation water mixed solution in, be uniformly mixed, then first at low temperature remove moisture,
Dry powder at high temperature again to get with nanometer CaF2For core, SiO2For the CaF of shell2@SiO2Composite granule.
It is larger to sintex Effect on Mechanical Properties for addition solid lubricant, it proposes particle surface coating modification
Design of material thought introduces self-lubrication ceramic Tool Design field, and design is prepared for not only having self-lubricating capacities but also has preferable power
The core-shell structure copolymer for learning performance coats self-lubrication ceramic cutter.
The application research discovery: from present using coated with silica micron order compound it is different, to nano calcium fluoride into
Row cladding when, the agglomeration of nano-scale is serious, for this purpose, the application pass through to coated powder agglomeration Producing reason,
The system research of influence factor etc. and large scale experiment are groped to find: making coated composite powder by the dry coated powder of azeotropic method
The reunion of body is greatly improved, and the application silica forms one layer of uniform cladding on nano calcium fluoride surface
Layer, compared with the coated by titanium dioxide layer of chondritic, above structure is more conducive to improve the mechanical property of self-lubricating material and rub
Wipe polishing machine.
The difference of decentralized medium can generate certain influence to the partial size and pattern for coating product.Therefore, in some implementations
In example, the specific steps that nano calcium fluoride powder is dispersed in alcoholic solution are as follows: disperse anhydrous second for suitable dispersing agent
In alcoholic solution, then nano calcium fluoride powder is added in the ethanol solution containing dispersing agent, ultrasonic disperse simultaneously quickly stirs
It mixes to get prepared composite granule good dispersion should not reunite.
Do not make special restriction in the application to the type of dispersing agent, effectively disperses as long as can be realized nano calcium fluoride
.In some embodiments, the dispersing agent is ethylene bis stearamide EBS, glyceryl tristearate HTG, polyethylene pyrrole
Pyrrolidone PVP or polyethylene glycol PEG, so that nano calcium fluoride has preferable dispersibility in alcoholic solvent.
In some embodiments, the ethyl orthosilicate and nanometer CaF2The mass ratio of powder are as follows: 3~6mL:1~2g.Step
Suddenly the dosage of ethyl orthosilicate (TEOS) described in (3) is in terms of Si contained therein, Si and CaF2Molar ratio be 0.5~4:1.
SiO2It is very little then cladding not exclusively, SiO2Too many CaF2It is added in matrix and goes, the mechanical properties decrease of material can be caused, because
This, it is necessary to select suitable Si and CaF2Molar ratio.The present invention has found by many experiments, as Si and CaF2Molar ratio=
It is more appropriate when 0.5~4:1.It is further preferred that Si and CaF2Molar ratio=1~2:1, particularly preferred Si and CaF2Rub
You are than being 1:1.Not only it can guarantee that covered effect was best, but also make CaF obtained2@SiO2Mechanical property does not drop after being added in matrix
It is low.
In some embodiments, the concentration of the ammonium hydroxide is 23~28wt%, and it is 8~10 that ammonium hydroxide control pH value, which is added dropwise,.Ammonia
For water as basic catalyst other than starting to control the effect of granulation diameter, it also inhibits hydrolysis, facilitates polycondensation reaction generation, that is, generates
The particle of regular shape.
Research is found: with the increase of ethyl orthosilicate rate of addition, CaF2@SiO2The partial size of composite granule incrementally increases,
But after rate of addition reaches a certain level, maximum particle diameter declines with the increase of drop rate.Therefore, in some implementations
In example, the rate of addition of the ethyl orthosilicate is 0.05~0.3mL/min, prepared CaF2@SiO2The partial size of composite granule
Uniformly, good dispersion.
The moisture in wet gel can be effectively removed using azeotropic distillation, but different solvents are to CaF after distillation2@SiO2Shape
Looks and dispersibility have larger impact.The application research discovery: using n-butanol and distilled water as azeotropic solvent, in the mistake of distillation
The moisture of gel surface can be effectively removed in Cheng Zhong, the formation of hard agglomeration when avoiding heat treatment.In some embodiments
In, the volume ratio of the n-butanol and distilled water is 6~6.1:4~4.5, effectively improves the rate of distillation, improves CaF2@
SiO2The dispersibility of composite granule.
In some embodiments, the low temperature is 93~95 DEG C, and the high temperature is 117~118 DEG C.Firstly, at low temperature
By the moisture removal in wet gel, then, at relatively high temperatures, azeotropic solvent is evaporated off, forms loose powder.
The present invention also provides the silicon dioxide coated nano calcirm-fluoride composite granules of any above-mentioned method preparation.
The present invention also provides above-mentioned silicon dioxide coated nano calcirm-fluoride composite granules to prepare self-lubrication ceramic material
Application in material.
The beneficial effects of the present invention are:
(1) present invention is by heterogeneous nucleation process in nanometer CaF2It carries out surface and coats one layer of SiO2Shell.This method technique
Process is simple, and equipment requirement is low, highly-safe.Obtained clad dense uniform is tested, with CaF2Be tightly combined, be not easy to take off
It falls, there is certain bond strength, composite granule good dispersion should not reunite.Coated powder is added to ceramics or Metal Substrate
The wetability between solid lubricant and matrix can not only be improved in body, increase the interface bond strength of the two, and improved
CaF2Mechanical property, improve the mechanical property and friction and wear behavior of self-lubricating material.
(2) operating method of the application it is simple, it is at low cost, have universality, be easy to large-scale production.
Detailed description of the invention
The accompanying drawings constituting a part of this application is used to provide further understanding of the present application, and the application's shows
Meaning property embodiment and its explanation are not constituted an undue limitation on the present application for explaining the application.
Fig. 1 is the nanometer CaF of the embodiment of the present invention2Transmission electron microscope (TEM) photo of material powder.
Fig. 2 is CaF prepared by the embodiment of the present invention 32@SiO2The TEM photo of coated powder.
Fig. 3 is CaF prepared by the embodiment of the present invention 62@SiO2The TEM photo of coated powder.
Fig. 4 is CaF prepared by comparative example 1 of the present invention2@SiO2The TEM photo of coated powder.
Fig. 5 is CaF prepared by the embodiment of the present invention 32@SiO2The HRTEM picture of coated powder.
Specific embodiment
It is noted that following detailed description is all illustrative, it is intended to provide further instruction to the application.Unless another
It indicates, all technical and scientific terms used in this application have logical with the application person of an ordinary skill in the technical field
The identical meanings understood.
It should be noted that term used herein above is merely to describe specific embodiment, and be not intended to restricted root
According to the illustrative embodiments of the application.As used herein, unless the context clearly indicates otherwise, otherwise singular
Also it is intended to include plural form, additionally, it should be understood that, when in the present specification using term "comprising" and/or " packet
Include " when, indicate existing characteristics, step, operation, device, component and/or their combination.
As background technique is introduced, for solid lubricant calcirm-fluoride can significantly improve material friction performance but
The problem of causing material mechanical performance to reduce.Therefore, the present invention proposes a kind of silicon dioxide coated nano calcirm-fluoride (CaF2@
SiO2) composite granule preparation method, steps are as follows:
(1) the nanometer CaF of 1~6g is weighed2Powder is added in the alcoholic solution containing dispersing agent, after 30~60min of ultrasonic disperse
It is placed in heating water bath in magnetic stirring apparatus and quickly stirs, temperature is maintained between 35~45 DEG C.
(2) 2.5~15mL distilled water is added in Xiang Shangshu solution, is added appropriate ammonium hydroxide and is adjusted pH to 8~10.
(3) ethyl orthosilicate (TEOS) is slowly added dropwise in Xiang Shangshu mixed solution, is added dropwise to complete rear continuous heating and quickly stirs
Mix 4-12h.
(4) obtained suspension is centrifuged 10~30min, washes of absolute alcohol is used after centrifugation, is continued 3~5 times.
(5) wet gel after centrifugation is added in n-butanol and the solution of distilled water 6:4~4.5,30min is stirred by ultrasonic
Afterwards, after first removing the moisture in solution under 93 DEG C of oil bath heatings, dry powder, is obtained to receive under 117 DEG C of oil bath heatings
Rice CaF2For core, SiO2For the CaF of shell2@SiO2Composite granule.
It is preferred according to the present invention, nanometer CaF described in step (1)2Diameter of particle be 10~60nm.
It is preferred according to the present invention, NH in ammonium hydroxide described in step (2)3Content be 23~28wt%.It is further excellent
Recruiting and saving pH value is 8~9.
Preferred according to the present invention, dispersing agent described in step (2) has ethylene bis stearamide (EBS), three stearic acid
Glyceride (HTG), polyvinylpyrrolidone (PVP) and polyethylene glycol (PEG) etc.；Further preferred dispersing agent is polyethylene pyrrole
Pyrrolidone (PVP).
Preferred according to the present invention, ethyl orthosilicate (TEOS) described in step (3) is the body of ethyl orthosilicate and water
Product ratio are as follows: 2.5~4:2~4mL；Ethyl orthosilicate additive amount and nanometer CaF2The ratio of powder are as follows: 3~7mL:1~2g.
It is preferred according to the present invention, the dosage of ethyl orthosilicate (TEOS) described in step (3) in terms of Si contained therein,
Si and CaF2Molar ratio be 0.5~4:1.SiO2It is very little then cladding not exclusively, SiO2Too many CaF2It is added in matrix and goes then
It can cause the mechanical properties decrease of material, therefore, it is necessary to select suitable Si and CaF2Molar ratio.The present invention is by a large amount of real
It issues after examination and approval now, as Si and CaF2Molar ratio=0.5~4:1 when it is more appropriate.It is further preferred that Si and CaF2Molar ratio=1
~2:1, particularly preferred Si and CaF2Molar ratio be 1:1.Not only it can guarantee that covered effect was best, but also make CaF obtained2@SiO2
Mechanical property does not reduce after being added in matrix.
Preferred according to the present invention, the rate of addition of ethyl orthosilicate described in step (3) is 0.05~0.3mL/
min。
Preferred according to the present invention, the centrifugal speed of suspension described in step (4) is 4000~6000r/min.
The present invention using ethyl orthosilicate (TEOS) hydrolysis, condensation reaction be prepared be sheet cladded type CaF2
Nanometer grade powder material product, clad are by Nano-meter SiO_22Composition, clad is complete, finer and close, and is wrapped by particle knot
Close securely, it is uncoated on mono-dispersed nano SiO2It is few.The present invention is by a large amount of research it was unexpectedly observed that TEOS exists first
Alkaline condition issues raw hydrolysis, generates silanol, the hydroxyl and CaF of silanol2Hydrogen bond is formed between the hydroxyl on surface, is being heated
Under the conditions of, the hydroxyl and CaF of silanol2Condensation reaction, final SiO occur for the hydroxyl on surface2And CaF2Between with chemical bonds,
So being firmly combined, it is not easy to be destroyed.
It is illustrated below by way of technical solution of the specific embodiment to the application.
Embodiment 1
(1) the nanometer CaF of 1.5g is weighed2Powder is added to the dehydrated alcohol of pyrrolidones containing polyethylene of dispersing agent (PVP)
In solution (PVP0.6g, ethyl alcohol 300mL), ultrasonic disperse 30min is placed on heating water bath in magnetic stirring apparatus and quickly stirs,
Temperature is maintained at 35 DEG C.
(2) 6mL distilled water is added in Xiang Shangshu solution, adjusts pH to 8.5 appropriate ammonium hydroxide is added.
(3) ethyl orthosilicate (TEOS) of 6mL, rate of addition 0.1mL/min is slowly added dropwise in Xiang Shangshu mixed solution.Drop
Continuous heating and 5h is quickly stirred after the completion of adding.
(4) obtained suspension is centrifuged under the conditions of 4000r/min 25min, washes of absolute alcohol is used after centrifugation, continued
3 times.
(5) cleaning is completed to be added to wet gel in the solution of n-butanol and distilled water 6:4, after 30min is stirred by ultrasonic, first
Under 93 DEG C of oil bath heatings, after under 117 DEG C of oil bath heatings dry powder, obtain with nanometer CaF2For core, SiO2For shell
CaF2@SiO2Composite granule.
Embodiment 2
(1) the nanometer CaF of 1.5g is weighed2Powder is added to the dehydrated alcohol of pyrrolidones containing polyethylene of dispersing agent (PVP)
In solution (PVP0.6g, ethyl alcohol 300mL), ultrasonic disperse 30min is placed on heating water bath in magnetic stirring apparatus and quickly stirs,
Temperature is maintained between 35 DEG C or so.
(2) 3mL distilled water is added in Xiang Shangshu solution, adjusts pH to 8.5 appropriate ammonium hydroxide is added.
(3) ethyl orthosilicate (TEOS) of 2.5mL, rate of addition 0.2mL/min is slowly added dropwise in Xiang Shangshu mixed solution.
It is added dropwise to complete rear continuous heating and quickly stirs 5h.
(4) obtained suspension is centrifuged under the conditions of 5000r/min 25min, washes of absolute alcohol is used after centrifugation, continued
5 times.
(5) cleaning is completed to be added to wet gel in the solution of n-butanol and distilled water 6:4, after 30min is stirred by ultrasonic, first
Under 93 DEG C of oil bath heatings, after under 117 DEG C of oil bath heatings dry powder, obtain with nanometer CaF2For core, SiO2For shell
CaF2@SiO2Composite granule.
Embodiment 3
(1) the nanometer CaF of 1g is weighed2The dehydrated alcohol that powder is added to pyrrolidones containing polyethylene of dispersing agent (PVP) is molten
In liquid (PVP0.4g, ethyl alcohol 100mL), ultrasonic disperse 40min is placed on heating water bath in magnetic stirring apparatus and quickly stirs, temperature
Degree is maintained at 40 DEG C.
(2) 2.5mL distilled water is added in Xiang Shangshu solution, adjusts pH to 8.5 appropriate ammonium hydroxide is added.
(3) ethyl orthosilicate (TEOS) of 3mL, rate of addition 0.2mL/min is slowly added dropwise in Xiang Shangshu mixed solution.Drop
Continuous heating and 5h is quickly stirred after the completion of adding.
(4) obtained suspension is centrifuged under the conditions of 6000r/min 25min, washes of absolute alcohol is used after centrifugation, continued
3 times.
(5) cleaning is completed to be added to wet gel in the solution of n-butanol and distilled water 6:4, after 30min is stirred by ultrasonic, first
Under 93 DEG C of oil bath heatings, after under 117 DEG C of oil bath heatings dry powder, obtain with nanometer CaF2For core, SiO2For shell
CaF2@SiO2Composite granule.If Fig. 2,5 are it is found that nanometer CaF2Surface uniformly coated one layer of amorphous SiO2, observation
Lattice fringe, it can be found that the crystal of the inside is nanometer CaF2Crystal, amorphous SiO2Even compact is coated on a nanometer CaF2
Surface is tightly combined.
Embodiment 4
(1) the nanometer CaF of 1g is weighed2The dehydrated alcohol that powder is added to pyrrolidones containing polyethylene of dispersing agent (PVP) is molten
In liquid (PVP0.4g, ethyl alcohol 100mL), ultrasonic disperse 40min is placed on heating water bath in magnetic stirring apparatus and quickly stirs, temperature
Degree is maintained at 45 DEG C.
(2) 6mL distilled water is added in Xiang Shangshu solution, adjusts pH to 8.5 appropriate ammonium hydroxide is added.
(3) ethyl orthosilicate (TEOS) of 6mL, rate of addition 0.05mL/min is slowly added dropwise in Xiang Shangshu mixed solution.
It is added dropwise to complete rear continuous heating and quickly stirs 5h.
(4) obtained suspension is centrifuged under the conditions of 6000r/min 25min, washes of absolute alcohol is used after centrifugation, continued
3 times.
(5) cleaning is completed to be added to wet gel in the solution of n-butanol and distilled water 6:4, after 30min is stirred by ultrasonic, first
Under 93 DEG C of oil bath heatings, after under 117 DEG C of oil bath heatings dry powder, obtain with nanometer CaF2For core, SiO2For shell
CaF2@SiO2Composite granule.
Embodiment 5
(1) the nanometer CaF of 1g is weighed2The dehydrated alcohol that powder is added to pyrrolidones containing polyethylene of dispersing agent (PVP) is molten
In liquid (PVP0.4g, ethyl alcohol 100mL), ultrasonic disperse 40min is placed on heating water bath in magnetic stirring apparatus and quickly stirs, temperature
Degree is maintained at 35 DEG C.
(2) 2.5mL distilled water is added in Xiang Shangshu solution, adjusts pH to 8.5 appropriate ammonium hydroxide is added.
(3) ethyl orthosilicate (TEOS) of 2mL, rate of addition 0.3mL/min is slowly added dropwise in Xiang Shangshu mixed solution.Drop
Continuous heating and 5h is quickly stirred after the completion of adding.
(4) obtained suspension is centrifuged under the conditions of 5000r/min 25min, washes of absolute alcohol is used after centrifugation, continued
3 times.
(5) cleaning is completed to be added to wet gel in the solution of n-butanol and distilled water 6:4, after 30min is stirred by ultrasonic, first
Under 93 DEG C of oil bath heatings, after under 117 DEG C of oil bath heatings dry powder, obtain with nanometer CaF2For core, SiO2For shell
CaF2@SiO2Composite granule.
Embodiment 6
(1) the nanometer CaF of 1g is weighed2The dehydrated alcohol that powder is added to pyrrolidones containing polyethylene of dispersing agent (PVP) is molten
In liquid (PVP0.4g, ethyl alcohol 100mL), ultrasonic disperse 40min is placed on heating water bath in magnetic stirring apparatus and quickly stirs, temperature
Degree is maintained at 45 DEG C.
(2) 1.5mL distilled water is added in Xiang Shangshu solution, adjusts pH to 8.5 appropriate ammonium hydroxide is added.
(3) ethyl orthosilicate (TEOS) of 1mL, rate of addition 0.2mL/min is slowly added dropwise in Xiang Shangshu mixed solution.Drop
Continuous heating and 5h is quickly stirred after the completion of adding.
(4) obtained suspension is centrifuged under the conditions of 4000r/min 25min, washes of absolute alcohol is used after centrifugation, continued
3 times.
(5) cleaning is completed to be added to wet gel in the solution of n-butanol and distilled water 6:4, after 30min is stirred by ultrasonic, first
Under 93 DEG C of oil bath heatings, after under 117 DEG C of oil bath heatings dry powder, obtain with nanometer CaF2For core, SiO2For shell
CaF2@SiO2Composite granule.As shown in Figure 3.
Embodiment 7
According toDeng JianxinPaper " Al2O3/TiC/CaF2Mechanism of Friction Reduction in self-lubrication ceramic tool cutting process " in
Method, respectively with Al2O3/TiC/CaF2With Al2O3/TiC/CaF2@SiO2Self-lubrication ceramic cutter is prepared for raw material, and is surveyed
Examination.Wherein, Al2O3/TiC/CaF2With Al2O3/TiC/CaF2@SiO2Difference is, using etc. quality CaF2@SiO2Substitution
CaF2, test result is as follows table 1.
Table 1
It follows that addition coated powder CaF2@SiO2Cutter and addition nanometer CaF2Cutter compare, hardness promoted
4.8%, bending resistance improves 21.7%, fracture toughness improves 12.6%, and performance has obtained biggish promotion.
Comparative example 1
CaF2@SiO2The preparation method of composite granule is identical with embodiment 3, the difference is that, it, will be wet solidifying in step (5)
Glue is handled with boulton process, forms coated powder.
By Fig. 2,4 comparisons it is found that agglomeration is extremely serious, it can be seen that the coated powder handled by azeotropic method
Agglomeration is significantly improved, and good improvement has also been arrived on pattern.
Finally it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not limited to this hair
It is bright, although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still
It can modify to technical solution documented by previous embodiment, or part is equivalently replaced.It is all in this hair
Within bright spirit and principle, any modification, equivalent replacement, improvement and so on should be included in protection scope of the present invention
Within.Above-mentioned, although specific embodiments of the present invention have been described, and it is not intended to limit the protection scope of the present invention, institute
Category field technical staff should be understood that based on the technical solutions of the present invention those skilled in the art do not need to pay wound
The various modifications or changes that the property made labour can be made are still within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of silicon dioxide coated nano calcirm-fluoride composite granule characterized by comprising
Nano calcium fluoride powder is dispersed in alcoholic solution, sequentially adds water, ammonium hydroxide, ethyl orthosilicate to it, makes positive silicic acid second
Suspension centrifugation, washing after reaction is obtained wet gel by ester hydrolytie polycondensation under ammonia-catalyzed；
Wet gel is added in n-butanol and distillation water mixed solution, is uniformly mixed, moisture is then first removed at low temperature, exists again
Dry powder is under high temperature to get with nanometer CaF2For core, SiO2For the CaF of shell2@SiO2Composite granule.
2. the preparation method of silicon dioxide coated nano calcirm-fluoride composite granule as described in claim 1, which is characterized in that institute
State the specific steps that nano calcium fluoride powder is dispersed in alcoholic solution are as follows: disperse ethanol solution for suitable dispersing agent
In, then nano calcium fluoride powder is added in the ethanol solution containing dispersing agent, ultrasonic disperse simultaneously quickly stirs, i.e.,
.
3. the preparation method of silicon dioxide coated nano calcirm-fluoride composite granule as claimed in claim 2, which is characterized in that institute
Stating dispersing agent is that dispersing agent has ethylene bis stearamide EBS, glyceryl tristearate HTG, polyvinylpyrrolidone PVP or poly- second
Glycol PEG.
4. the preparation method of silicon dioxide coated nano calcirm-fluoride composite granule as described in claim 1, which is characterized in that institute
State ethyl orthosilicate and nanometer CaF2The mass ratio of powder are as follows: 3~6mL:1~2g.
5. the preparation method of silicon dioxide coated nano calcirm-fluoride composite granule as described in claim 1, which is characterized in that institute
The concentration for stating ammonium hydroxide is 23~28wt%, and it is 8~10 that ammonium hydroxide control pH value, which is added dropwise,.
6. the preparation method of silicon dioxide coated nano calcirm-fluoride composite granule as described in claim 1, which is characterized in that institute
The rate of addition for stating ethyl orthosilicate is 0.05~0.3mL/min.
7. the preparation method of silicon dioxide coated nano calcirm-fluoride composite granule as described in claim 1, which is characterized in that institute
The volume ratio for stating n-butanol and distilled water is 6~6.1:4~4.5.
8. the preparation method of silicon dioxide coated nano calcirm-fluoride composite granule as described in claim 1, which is characterized in that institute
Stating low temperature is 93~95 DEG C, and the high temperature is 117~118 DEG C.
9. the silicon dioxide coated nano calcirm-fluoride composite granule of the described in any item method preparations of claim 1-8.
10. silicon dioxide coated nano calcirm-fluoride composite granule as claimed in claim 9 is in preparing self-lubricating ceramic material
Using.
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