CN107117626B - Method for preparing metal ion doped hydroxyl silicate nano-tube - Google Patents
Method for preparing metal ion doped hydroxyl silicate nano-tube Download PDFInfo
- Publication number
- CN107117626B CN107117626B CN201710256092.3A CN201710256092A CN107117626B CN 107117626 B CN107117626 B CN 107117626B CN 201710256092 A CN201710256092 A CN 201710256092A CN 107117626 B CN107117626 B CN 107117626B
- Authority
- CN
- China
- Prior art keywords
- nanotube
- metal ion
- metal
- ion mixing
- silicate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002071 nanotube Substances 0.000 title claims abstract description 109
- -1 hydroxyl silicate Chemical compound 0.000 title claims abstract description 68
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 72
- 229910052751 metal Inorganic materials 0.000 claims abstract description 64
- 239000002184 metal Substances 0.000 claims abstract description 64
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims abstract description 48
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000003756 stirring Methods 0.000 claims abstract description 27
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 229910001510 metal chloride Inorganic materials 0.000 claims abstract description 8
- 238000007789 sealing Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims description 51
- 239000011777 magnesium Substances 0.000 claims description 46
- 239000000391 magnesium silicate Substances 0.000 claims description 45
- 229910052919 magnesium silicate Inorganic materials 0.000 claims description 45
- 235000019792 magnesium silicate Nutrition 0.000 claims description 45
- UNYOJUYSNFGNDV-UHFFFAOYSA-M magnesium monohydroxide Chemical compound [Mg]O UNYOJUYSNFGNDV-UHFFFAOYSA-M 0.000 claims description 44
- 239000007822 coupling agent Substances 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000003960 organic solvent Substances 0.000 claims description 25
- 235000019441 ethanol Nutrition 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 22
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 22
- 230000004048 modification Effects 0.000 claims description 20
- 238000012986 modification Methods 0.000 claims description 20
- 150000004645 aluminates Chemical class 0.000 claims description 11
- 238000005119 centrifugation Methods 0.000 claims description 11
- 239000013049 sediment Substances 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 229910005108 Ni3Si2 Inorganic materials 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- ZDOBIJXAMNWEOE-UHFFFAOYSA-N [Mg].[Ni].OO[Si](O)(O)O Chemical compound [Mg].[Ni].OO[Si](O)(O)O ZDOBIJXAMNWEOE-UHFFFAOYSA-N 0.000 claims description 3
- QURDCGKPZJHUNO-UHFFFAOYSA-N [Ni].OO[Si](O)(O)O Chemical compound [Ni].OO[Si](O)(O)O QURDCGKPZJHUNO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 24
- 239000002244 precipitate Substances 0.000 abstract description 10
- 230000007547 defect Effects 0.000 abstract description 2
- 238000007709 nanocrystallization Methods 0.000 abstract 2
- 239000002131 composite material Substances 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 55
- 238000005299 abrasion Methods 0.000 description 49
- 238000009472 formulation Methods 0.000 description 41
- 239000000203 mixture Substances 0.000 description 41
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 238000011049 filling Methods 0.000 description 21
- 239000007791 liquid phase Substances 0.000 description 21
- 239000010687 lubricating oil Substances 0.000 description 18
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 description 16
- 239000012071 phase Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- 239000007790 solid phase Substances 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 230000007423 decrease Effects 0.000 description 9
- 238000013019 agitation Methods 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 230000005291 magnetic effect Effects 0.000 description 8
- 239000002199 base oil Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 4
- 238000005551 mechanical alloying Methods 0.000 description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000003776 cleavage reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- XQSFXFQDJCDXDT-UHFFFAOYSA-N hydroxysilicon Chemical compound [Si]O XQSFXFQDJCDXDT-UHFFFAOYSA-N 0.000 description 3
- 238000003754 machining Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000005240 physical vapour deposition Methods 0.000 description 3
- 230000007017 scission Effects 0.000 description 3
- 229910021554 Chromium(II) chloride Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910002808 Si–O–Si Inorganic materials 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 229910001567 cementite Inorganic materials 0.000 description 2
- XBWRJSSJWDOUSJ-UHFFFAOYSA-L chromium(ii) chloride Chemical compound Cl[Cr]Cl XBWRJSSJWDOUSJ-UHFFFAOYSA-L 0.000 description 2
- 229940109126 chromous chloride Drugs 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910002656 O–Si–O Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910000905 alloy phase Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 230000005307 ferromagnetism Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- SEBPBUWRSRLFQT-UHFFFAOYSA-N hydroperoxy(trihydroxy)silane Chemical compound OO[Si](O)(O)O SEBPBUWRSRLFQT-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical compound C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000005480 shot peening Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000007751 thermal spraying Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/22—Magnesium silicates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
- C10M125/26—Compounds containing silicon or boron, e.g. silica, sand
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/85—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by XPS, EDX or EDAX data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
- C10M2201/10—Compounds containing silicon
- C10M2201/102—Silicates
-
- 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
- C10N2010/00—Metal present as such or in compounds
- C10N2010/04—Groups 2 or 12
-
- 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
- C10N2030/76—Reduction of noise, shudder, or vibrations
-
- 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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/25—Internal-combustion engines
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
Abstract
The invention provides a method for manufacturing a metal ion doped hydroxyl silicate nanotube, which comprises the following steps: preparing metal chloride, magnesium nitrate, sodium silicate and sodium hydroxide according to the mass concentration of 1 (20-40): 10-30): 200-450; dissolving metal chloride and magnesium nitrate into water, and then adding sodium silicate; continuously stirring for 10-30 minutes, adding sodium hydroxide, and continuously stirring for 10-30 minutes to obtain an intermediate solution; sealing the intermediate solution and placing the intermediate solution in a reaction kettle to react for 20 to 50 hours at the temperature of between 200 and 400 ℃; and after the reaction is finished, centrifugally collecting precipitates, and centrifugally washing the precipitates by using solvents in sequence to obtain the metal ion doped hydroxyl silicate nanotube. The invention provides a method for manufacturing a metal ion doped hydroxyl silicate nanotube, which overcomes the defect that the metal ion doped hydroxyl silicate nanotube cannot be produced in the prior art, and the self-nanocrystallization efficiency of the prepared composite preparation for self-nanocrystallization of the friction and wear surface of metal is higher.
Description
Technical field
The present invention relates to a kind of manufacturing methods of metal ion mixing hydroxy silicate nanotube, belong to metal material processing
Field.
Background technique
The big failure mode of the three of element part, abrasion, fatigue and corrosion, are all the surfaces of material since surface
Intensive treatment is extremely important.
Metal-surface nano is a kind of new surface strengthening treatment technology that developed recently gets up, therein from nanosizing
Technology is by more extensive concern.With thermal spraying, Brush Plating, laser melting coating, physical vapour deposition (PVD) (PVD), chemical vapor deposition
Traditional surface strengthening technologies such as product (CVD) and three beams (laser beam, ion beam, electron beam) surface are modified are compared, and surface is certainly
Nanosizing processing can be formed in material own face does not have the nanostructured layers of sharp interface between matrix, wear-resisting, against corrosion,
Greatly improve surface property.
Previous research focuses mostly on and is realizing surface self-nanocrystallinzation, such as machine using the method for surface machining processes
Tool grinding, ultrasonic shot peening, high-energy shot and supersonic microparticle bombardment etc..
This variety of surface machining processes, need makes material generate strong plasticity under the repeat function of plus load becomes
The open grain structure of shape, surface is gradually refined to nanometer scale.This surface self-nanocrystallinzation processing belongs to off-line technology, needs high energy
Special equipment, activity duration are longer, costly.
The secondary relative motion of the lower friction of load effect is also a kind of machining to surface, but insufficient under normal conditions
With intense plastic strain needed for generating surface self-nanocrystallinzation.Mechanical alloying and high temperature internal oxidition are two that developed recently gets up
The effective way that kind nano surface crystalline substance is strengthened, can be used for metal frictional abrasion surface from nanosizing.Under general condition, friction is situated between
The thermodynamic condition in face is neither able to achieve surface mechanical alloying, can not complete the reaction of high temperature internal oxidition.Existing simple benefit
Realize that technology of the friction surface from nanosizing, the mechanism of action are mechanical alloyings with solid phase components, machinery containing surface oxidation is thrown
Light, lubrication oil-breaking carbonization and three step of mechanical alloying.Have the following problems: 1, solid phase components cannot be abundant in lubricating oil
Dispersion suspends；2, it needs to lubricate oil-breaking carbonization and participates in reaction；Lead to the low efficiency from nanosizing, nano surface crystalline substance enhanced protection
The formation speed of layer is slower.Using metal frictional abrasion surface from the compound formulation of nanosizing, including solid phase components and liquid phase group
Point；Liquid phase component is added lubricating oil by metal ion mixing hydroxy silicate nanotube and is formed, the hydroxyl silicic acid in liquid phase component
The surface-active key of salt nanotube has a good adsorptivity to fresh metal surface, and metal ion mixing make it have it is ferromagnetic
Property, nanotube, which can align, under the Surface field effect that friction generates is enriched in metal surface.The hydroxyl silicon of liquid phase component
Contain various active chemical bond in stratiform hydroxy silicate natural ore powder particle in silicate nanometer pipe and solid phase components, wherein
Silicon oxygen bond, Si-O-Si, O-Si-O, when cleavage is destroyed, easy fracture produces the great free oxygen of activity, O2-, O, Xiang Jin
Belong to internal strong diffusion.It is the synthesis nanotube of friction surface enrichment first, the free oxygen that subsequent natural ore powder particle generates can
There is this strong diffusion effect.In addition, the active Free water H that deshydroxy reaction generates2O can also be spread to metal inside therewith；And
Existing technology lacks the method for manufacturing metal ion mixing hydroxy silicate nanotube.
Summary of the invention
(1) technical problems to be solved
The object of the present invention is to provide a kind of manufacturing method of metal ion mixing hydroxy silicate nanotube, provide with
The mutually matched metal ion mixing hydroxy silicate nanotube of stratiform hydroxy silicate natural ore powder particle, solves existing
Technology can not produce the defect of metal ion mixing hydroxy silicate nanotube.
(2) technical solution
In order to solve the above-mentioned technical problem, the invention discloses a kind of systems of metal ion mixing hydroxy silicate nanotube
Make method, comprising the following steps:
1) by metal chloride, magnesium nitrate, sodium metasilicate and sodium hydroxide, according to mass concentration are as follows: 1:(20-40): (10-
30): (200-450) is prepared；
2) metal chloride and magnesium nitrate are dissolved into water, sodium metasilicate is then added；After persistently stirring 10-30 minutes,
Sodium hydroxide is added, obtains midbody solution after continuing stirring 10-30 minutes；
3) midbody solution sealing is placed in reaction kettle reacts 20-50 hours at 200-400 DEG C；
4) sediment after reaction, is collected by centrifugation, successively uses solvent centrifuge washing, obtains metal ion mixing hydroxyl silicon
Silicate nanometer pipe.
Optionally, the manufacturing method of the metal ion mixing hydroxy silicate nanotube further includes following modification procedure:
1) in organic solvent by the dispersion of metal ion mixing hydroxy silicate nanotube, it is heated to 45-85 DEG C；
2) it is 1:(0.03-1) with concentration ratio by metal ion mixing hydroxy silicate nanotube and coupling agent, coupling is added
Agent persistently stirs 1-2 hours, obtains liquid to be treated；
3) it is centrifugated liquid to be treated, is then cleaned with organic solvent, obtains oil-soluble metal ion mixing
Hydroxy silicate nanotube.
Optionally, the modification procedure 1) described in hydroxy silicate nanotube be hydroxyl magnesium silicate (Mg6[Si4O10]
[OH]8) nanotube, hydroxyl silicic acid nickel (Ni3Si2O5(OH)4) nanotube or hydroxyl silicic acid nickel magnesium ((Ni, Mg)3Si2O5(OH)4) receive
Mitron.
Optionally, the modification procedure 2) described in organic solvent be monohydric alcohol, one kind of ethyl alcohol or propyl alcohol.
Optionally, the modification procedure 2) described in coupling agent be silane coupling agent, titanate coupling agent and Aluminate
One of coupling agent is a variety of.
(3) beneficial effect
The manufacturing method of a kind of metal ion mixing hydroxy silicate nanotube provided by the invention, with following excellent
Point:
1) metal frictional abrasion surface is from the compound formulation of nanosizing due to introducing liquid phase component, required solid phase components
Concentration be greatly lowered, lubricating oil is only used as the carrier of preparation to use, and is not involved in any reaction.Internal oxidition is substantially a kind of
The thermal oxidative reaction of alloy phase in metal surface, the conversion zone of non-model control contact zone are this thermal oxidative reaction layer.Therefore, it receives certainly
Riceization it is more efficient, the formation speed of nano surface crystalline substance enhanced protection layer is faster.The metal ion mixing hydroxy silicate is received
Mitron manufacturing method, production is simple, efficiency of the metal frictional abrasion surface obtained from the compound formulation of nanosizing from nanosizing
It is higher.
Detailed description of the invention
Fig. 1 is Fe of the invention3+Adulterate hydroxyl magnesium silicate nanotube transmission electron microscope (TEM) image；
Fig. 2 is Fe of the invention3+Adulterate hydroxyl magnesium silicate nanotube x-ray photoelectron spectroscopy (XPS) figure.
Specific embodiment
With reference to the accompanying drawings and examples, specific embodiments of the present invention will be described in further detail.Following instance
For illustrating the present invention, but it is not intended to limit the scope of the invention.
The action principle of the metal frictional abrasion surface pointed out in the present invention from the compound formulation of nanosizing is as follows: (1) surpassing
Smart surface grinding: solid compositions particle and the silica (SiO that they are generated by the decomposition of friction and Extrusion cleavage in component2) and
Aluminum oxide (Al2O3) nanoscale (10-7-10-9M) particulate is super to metal friction and wear surface under fricting shearing effect
Smooth grinding generates fresh active surface.
(2) active material surface adsorbs: the surface-active key of hydroxy silicate nanotube is to fresh metal in liquid phase component
There is good adsorptivity on surface, and metal ion mixing makes it have ferromagnetism, receives under the Surface field effect that friction generates
Mitron can align and be enriched in metal surface.
(3) active oxygen is spread by force to metal inside: in the hydroxy silicate nanotube and solid phase components in liquid phase component
Contain various active chemical bond in stratiform hydroxy silicate natural ore powder particle, wherein silicon oxygen bond, Si-O-Si, O-Si-
O, when cleavage is destroyed, easy fracture produces the great free oxygen of activity, O2-, O, spread by force to metal inside.It is friction first
The synthesis nanotube of surface enrichment, the free oxygen that subsequent natural ore powder particle generates will appear this strong diffusion effect.In addition,
The active Free water H that deshydroxy reaction generates2O can also be spread to metal inside therewith；
(4) it is different from the special internal oxidition of high temperature internal oxidition: the free oxygen O internally spread from surface2-, O and activity
H2O is oxidized the alloying component of metal, for ferrous metal, mainly alloying component cementite Fe3C is oxidized, and is reacted
Journey is as follows:
[C]Fe+ O=CO；
[C]Fe+ 2O=CO2；
[C]Fe+H2O=CO+H2；
[C]Fe+2H2O=CO2+2H2
3[Fe]c+ 4O=Fe3O4；
3[Fe]c+ 4H2O=Fe3O4+4H2
The Fe that internal oxidition is formed3O4Nanocrystal is deposited on matrix and is formed from nanosizing crystal layer；The gas of generation is to surface
Evolution is formed from the nanoaperture in nanosizing crystal layer.
The invention discloses a kind of manufacturing methods of metal ion mixing hydroxy silicate nanotube, comprising the following steps:
1) by metal chloride, magnesium nitrate, sodium metasilicate and sodium hydroxide, according to mass concentration are as follows: 1:(20-40): (10-
30): (200-450) is prepared；
2) metal chloride and magnesium nitrate are dissolved into water, sodium metasilicate is then added；After persistently stirring 10-30 minutes,
Sodium hydroxide is added, obtains midbody solution after continuing stirring 10-30 minutes；
3) midbody solution sealing is placed in reaction kettle reacts 20-50 hours at 200-400 DEG C；
4) sediment after reaction, is collected by centrifugation, successively uses solvent centrifuge washing, obtains metal ion mixing hydroxyl silicon
Silicate nanometer pipe.
Wherein, the manufacturing method of the metal ion mixing hydroxy silicate nanotube further includes following modification procedure:
1) in organic solvent by the dispersion of metal ion mixing hydroxy silicate nanotube, it is heated to 45-85 DEG C；
2) it is 1:(0.03-1) with concentration ratio by metal ion mixing hydroxy silicate nanotube and coupling agent, coupling is added
Agent persistently stirs 1-2 hours, obtains liquid to be treated；
3) it is centrifugated liquid to be treated, is then cleaned with organic solvent, obtains oil-soluble metal ion mixing
Hydroxy silicate nanotube.
Wherein, the modification procedure 1) described in hydroxy silicate nanotube be hydroxyl magnesium silicate (Mg6[Si4O10]
[OH]8) nanotube, hydroxyl silicic acid nickel (Ni3Si2O5(OH)4) nanotube or hydroxyl silicic acid nickel magnesium ((Ni, Mg)3Si2O5(OH)4) receive
Mitron.
Wherein, the modification procedure 2) described in organic solvent be monohydric alcohol, one kind of ethyl alcohol or propyl alcohol.
Wherein, the modification procedure 2) described in coupling agent be that silane coupling agent, titanate coupling agent and Aluminate are even
Join one of agent or a variety of.
Wherein, the metal ion in the metal ion mixing hydroxy silicate nanotube is 3 long in the periodic table of elements
The ion of period (4,5,6) corresponding group vib and group VIII metal element；Such as Cr3+、Fe3+、Ni2+、Co+Deng.
It is specifically described below by embodiment
Embodiment 1:
The preparation of metal ion mixing hydroxy silicate nanotube:
(1) chemical reagent used in: frerrous chloride, magnesium nitrate, sodium metasilicate and sodium hydroxide, mass concentration ratio: 1:20:10:
200；
(2) frerrous chloride and magnesium nitrate are dissolved into water by mass concentration ratio described in step (1), obtain solution A；
(3) sodium metasilicate is added by mass concentration ratio described in step (1) in solution A under magnetic agitation, obtains solution B；
(4) continue agitating solution B after ten minutes, sodium hydroxide is added by mass concentration ratio described in step (1), continues
Stirring obtains solution C after ten minutes；
(5) solution C is sealed in polytetrafluoroethylene (PTFE) water heating kettle reacts 20 hours at 200 DEG C；
(6) sediment is collected by centrifugation after reaction, it is successively that may be present miscellaneous to remove with second alcohol and water centrifuge washing
Matter ion, obtains Fe3+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube, attached drawing 1 is obtained Fe3+ doping hydroxyl
Base magnesium silicate (Mg6[Si4O10][OH]8) nanotube transmission electron microscope (TEM) image；Fig. 2 is point of x-ray photoelectron spectroscopy (XPS)
Analyse result；
The modification of metal ion mixing hydroxy silicate nanotube:
(1) by Fe3+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube C is dispersed in monohydric alcohol organic solvent,
It is heated to 45 DEG C；
(2) Fe is pressed3+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube adds with coupling agent concentrations ratio for 1:0.03
Enter aluminate coupling agent, persistently stirs 1 hour, obtain liquid D；
(3) it is centrifugated liquid D, is oil-soluble Fe with the white precipitate that organic solvent methanol is cleaned3+
Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube.
Embodiment 1:
The preparation of metal ion mixing hydroxy silicate nanotube:
(1) chemical reagent used in: frerrous chloride, magnesium nitrate, sodium metasilicate and sodium hydroxide, mass concentration ratio: 1:20:10:
200；
(2) frerrous chloride and magnesium nitrate are dissolved into water by mass concentration ratio described in step (1), obtain solution A；
(3) sodium metasilicate is added by mass concentration ratio described in step (1) in solution A under magnetic agitation, obtains solution B；
(4) continue agitating solution B after ten minutes, sodium hydroxide is added by mass concentration ratio described in step (1), continues
Stirring obtains solution C after ten minutes；
(5) solution C is sealed in polytetrafluoroethylene (PTFE) water heating kettle reacts 20 hours at 200 DEG C；
(6) sediment is collected by centrifugation after reaction, it is successively that may be present miscellaneous to remove with second alcohol and water centrifuge washing
Matter ion, obtains Fe3+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube.
The modification of metal ion mixing hydroxy silicate nanotube:
(1) by Fe3+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube C is dispersed in monohydric alcohol organic solvent,
It is heated to 45 DEG C；
(2) Fe is pressed3+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube adds with coupling agent concentrations ratio for 1:0.03
Enter aluminate coupling agent, persistently stirs 1 hour, obtain liquid D；
(3) it is centrifugated liquid D, is oil-soluble Fe with the white precipitate that organic solvent methanol is cleaned3+
Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube.
Preparation of the metal frictional abrasion surface from the compound formulation of nanosizing:
1) by oil-soluble Fe3+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube is added to lube base oil
In to get compound phase component liquid-solid into the present invention liquid phase component Y, it is spare as solvent.
2) solid phase components prepared are added in aforementioned liquid phase component Y to obtain realizes metal frictional abrasion surface certainly
The liquid-solid compound phase preparation of nanosizing, can be directly appended to use in lubricating oil.
To 1.6 row, two passenger cars, (one is A group to have travelled 80,000 kilometers；Another is B to have travelled 110,000 kilometers
Group) the influence test that has carried out engine performance, 3000 are travelled from the compound formulation of nanosizing using metal frictional abrasion surface
After kilometer, 6000 kilometers of comparisons are travelled with existing lubricating oil is added, as the result is shown:
(1) when filling metal frictional abrasion surface travels 3000km from the compound formulation of nanosizing, cylinder pressure of engines is obvious
Rise, A group averagely promotes 4.5%, B group and averagely promotes 4.83%, and it is 7.5% that most large cylinder, which presses lifting capacity,.
(2) when filling metal frictional abrasion surface travels 3000km from the compound formulation of nanosizing, engine noise is obvious
Decline, A group, which averagely reduces by 16.93%, B group, averagely reduces by 16.78%, maximum noise drop-out value 20.7dB (internal car noise).
(3) when filling metal frictional abrasion surface travels 3000km from the compound formulation of nanosizing, and traveling is not filled
It is compared when 6000km, A group vehicle CO, which reduces by 24%, HC+NOx, reduces by 23%；B group vehicle CO, which reduces by 19%, HC+NOx, reduces by 21%.
Embodiment 2
The preparation of metal ion mixing hydroxy silicate nanotube:
(1) chemical reagent used in: chromous chloride, magnesium nitrate, sodium metasilicate and sodium hydroxide, mass concentration ratio: 1:40:30:
450；
(2) chromous chloride and magnesium nitrate are dissolved into water by mass concentration ratio described in step (1), obtain solution A；
(3) sodium metasilicate is added by mass concentration ratio described in step (1) in solution A under magnetic agitation, obtains solution B；
(4) continue agitating solution B after 30 minutes, sodium hydroxide is added by mass concentration ratio described in step (1), continues
Stirring obtained solution C after 30 minutes；
(5) solution C is sealed in polytetrafluoroethylene (PTFE) water heating kettle reacts 50 hours at 400 DEG C；
(6) sediment is collected by centrifugation after reaction, it is successively that may be present miscellaneous to remove with second alcohol and water centrifuge washing
Matter ion, obtains Cr3+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube；
The modification of metal ion mixing hydroxy silicate nanotube:
(1) by Cr3+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube C is dispersed in monohydric alcohol organic solvent,
It is heated to 85 DEG C；
(2) Cr is pressed3+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube and coupling agent concentrations ratio be that 1:1 is added
Aluminate coupling agent persistently stirs 2 hours, obtains liquid D；
(3) it is centrifugated liquid D, is oil-soluble Cr with the white precipitate that organic solvent methanol is cleaned3+
Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube.
Preparation of the metal frictional abrasion surface from the compound formulation of nanosizing:
1) by oil-soluble Cr3+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube is added to lube base oil
In to get to the liquid phase component Y of the liquid-solid compound phase component of invention, it is spare as solvent.
2) solid phase components prepared are added in aforementioned liquid phase component Y to obtain realizes metal frictional abrasion surface certainly
The liquid-solid compound phase preparation of nanosizing, can be directly appended to use in lubricating oil.
To 1.6 row, two passenger cars, (one is A group to have travelled 80,000 kilometers；Another is B to have travelled 110,000 kilometers
Group) the influence test that has carried out engine performance, 3000 are travelled from the compound formulation of nanosizing using metal frictional abrasion surface
After kilometer, 6000 kilometers of comparisons are travelled with existing lubricating oil is added, as the result is shown:
(1) when filling metal frictional abrasion surface travels 3000km from the compound formulation of nanosizing, cylinder pressure of engines is obvious
Rise, A group averagely promotes 5.5%, B group and averagely promotes 5.6%, and it is 8.9% that most large cylinder, which presses lifting capacity,.
(2) when filling metal frictional abrasion surface travels 3000km from the compound formulation of nanosizing, engine noise is obvious
Decline, A group, which averagely reduces by 19.73%, B group, averagely reduces by 18.58%, maximum noise drop-out value 21.5dB (internal car noise).
(3) when filling metal frictional abrasion surface travels 3000km from the compound formulation of nanosizing, and traveling is not filled
It is compared when 6000km, A group vehicle CO, which reduces by 25%, HC+NOx, reduces by 26%；B group vehicle CO, which reduces by 21%, HC+NOx, reduces by 23%.
Embodiment 3
The preparation of metal ion mixing hydroxy silicate nanotube:
(1) chemical reagent used in: nickel chloride, magnesium nitrate, sodium metasilicate and sodium hydroxide, mass concentration ratio: 1:30:20:
325；
(2) nickel chloride and magnesium nitrate are dissolved into water by mass concentration ratio described in step (1), obtain solution A；
(3) sodium metasilicate is added by mass concentration ratio described in step (1) in solution A under magnetic agitation, obtains solution B；
(4) continue agitating solution B after twenty minutes, sodium hydroxide is added by mass concentration ratio described in step (1), continues
Stirring obtains solution C after twenty minutes；
(5) solution C is sealed in polytetrafluoroethylene (PTFE) water heating kettle reacts 35 hours at 300 DEG C；
(6) sediment is collected by centrifugation after reaction, it is successively that may be present miscellaneous to remove with second alcohol and water centrifuge washing
Matter ion, obtains Ni2+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube；
The modification of metal ion mixing hydroxy silicate nanotube:
(1) by Ni2+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube C is dispersed in monohydric alcohol organic solvent,
It is heated to 65 DEG C；
(2) Ni is pressed2+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube adds with coupling agent concentrations ratio for 1:0.06
Enter aluminate coupling agent, persistently stirs 1.5 hours, obtain liquid D；
(3) it is centrifugated liquid D, is oil-soluble Ni with the white precipitate that organic solvent methanol is cleaned2+
Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube.
Preparation of the metal frictional abrasion surface from the compound formulation of nanosizing:
1) by oil-soluble Ni2+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube is added to lube base oil
In to get to the liquid phase component Y of the liquid-solid compound phase component of invention, it is spare as solvent.
2) solid phase components prepared are added in aforementioned liquid phase component Y to obtain realizes metal frictional abrasion surface certainly
The liquid-solid compound phase preparation of nanosizing, can be directly appended to use in lubricating oil.
To 1.6 row, two passenger cars, (one is A group to have travelled 80,000 kilometers；Another is B to have travelled 110,000 kilometers
Group) the influence test that has carried out engine performance, 3000 are travelled from the compound formulation of nanosizing using metal frictional abrasion surface
After kilometer, 6000 kilometers of comparisons are travelled with existing lubricating oil is added, as the result is shown:
(1) when filling metal frictional abrasion surface travels 3000km from the compound formulation of nanosizing, cylinder pressure of engines is obvious
Rise, A group averagely promotes 5.3%, B group and averagely promotes 5.4%, and it is 8.6% that most large cylinder, which presses lifting capacity,.
(2) when filling metal frictional abrasion surface travels 3000km from the compound formulation of nanosizing, engine noise is obvious
Decline, A group, which averagely reduces by 19.73%, B group, averagely reduces by 18.52%, maximum noise drop-out value 21.2dB (internal car noise).
(3) when filling metal frictional abrasion surface travels 3000km from the compound formulation of nanosizing, and traveling is not filled
It is compared when 6000km, A group vehicle CO, which reduces by 22%, HC+NOx, reduces by 23%；B group vehicle CO, which reduces by 20%, HC+NOx, reduces by 21%.
Embodiment 4
The preparation of metal ion mixing hydroxy silicate nanotube:
(1) chemical reagent used in: cobalt chloride, magnesium nitrate, sodium metasilicate and sodium hydroxide, mass concentration ratio: 1:25:20:
300；
(2) cobalt chloride and magnesium nitrate are dissolved into water by mass concentration ratio described in step (1), obtain solution A；
(3) sodium metasilicate is added by mass concentration ratio described in step (1) in solution A under magnetic agitation, obtains solution B；
(4) continue agitating solution B after 25 minutes, sodium hydroxide is added by mass concentration ratio described in step (1), continues
Stirring obtained solution C after 25 minutes；
(5) solution C is sealed in polytetrafluoroethylene (PTFE) water heating kettle reacts 30 hours at 250 DEG C；
(6) sediment is collected by centrifugation after reaction, it is successively that may be present miscellaneous to remove with second alcohol and water centrifuge washing
Matter ion, obtains Co+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube；
The modification of metal ion mixing hydroxy silicate nanotube:
(1) by Co+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube C is dispersed in monohydric alcohol organic solvent,
It is heated to 60 DEG C；
(2) Co is pressed+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube adds with coupling agent concentrations ratio for 1:0.08
Enter aluminate coupling agent, persistently stirs 2 hours, obtain liquid D；
(3) it is centrifugated liquid D, is oil-soluble Co with the white precipitate that organic solvent methanol is cleaned+
Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube.
Preparation of the metal frictional abrasion surface from the compound formulation of nanosizing:
1) by oil-soluble Co+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube is added to lube base oil
In to get to the liquid phase component Y of liquid-solid compound phase component, it is spare as solvent.
2) solid phase components prepared are added in aforementioned liquid phase component Y to obtain realizes metal frictional abrasion surface certainly
The liquid-solid compound phase preparation of nanosizing, can be directly appended to use in lubricating oil.
For automobile engine lubricating oil application, using the prior art, power performance is obviously improved, vibrating noise obviously drops
The operation milimeter number low, exhaust emissions is substantially reduced need to be at 1000-5000 kilometers or more；Reach effect same fortune in the present embodiment
Row milimeter number only needs 350 kilometers.
To 1.6 row, two passenger cars, (one is A group to have travelled 80,000 kilometers；Another is B to have travelled 110,000 kilometers
Group) the influence test that has carried out engine performance, 3000 are travelled from the compound formulation of nanosizing using metal frictional abrasion surface
After kilometer, 6000 kilometers of comparisons are travelled with existing lubricating oil is added, as the result is shown:
(1) when filling metal frictional abrasion surface travels 3000km from the compound formulation of nanosizing, cylinder pressure of engines is obvious
Rise, A group averagely promotes 5.2%, B group and averagely promotes 5.1%, and it is 8.4% that most large cylinder, which presses lifting capacity,.
(2) when filling metal frictional abrasion surface travels 3000km from the compound formulation of nanosizing, engine noise is obvious
Decline, A group, which averagely reduces by 19.73%, B group, averagely reduces by 18.62%, maximum noise drop-out value 21.7dB (internal car noise).
(3) when filling metal frictional abrasion surface travels 3000km from the compound formulation of nanosizing, and traveling is not filled
It is compared when 6000km, A group vehicle CO, which reduces by 22%, HC+NOx, reduces by 22%；B group vehicle CO, which reduces by 20%, HC+NOx, reduces by 20%.
Embodiment 5
The preparation of metal ion mixing hydroxy silicate nanotube:
(1) chemical reagent used in: frerrous chloride, magnesium nitrate, sodium metasilicate and sodium hydroxide, mass concentration ratio: 1:30:20:
300；
(2) frerrous chloride and magnesium nitrate are dissolved into water by mass concentration ratio described in step (1), obtain solution A；
(3) sodium metasilicate is added by mass concentration ratio described in step (1) in solution A under magnetic agitation, obtains solution B；
(4) continue agitating solution B after 25 minutes, sodium hydroxide is added by mass concentration ratio described in step (1), continues
Stirring obtained solution C after 25 minutes；
(5) solution C is sealed in polytetrafluoroethylene (PTFE) water heating kettle reacts 30 hours at 250 DEG C；
(6) sediment is collected by centrifugation after reaction, it is successively that may be present miscellaneous to remove with second alcohol and water centrifuge washing
Matter ion, obtains Fe3+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube；
The modification of metal ion mixing hydroxy silicate nanotube:
(1) by Fe3+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube C is dispersed in monohydric alcohol organic solvent,
It is heated to 65 DEG C；
(2) Fe is pressed3+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube adds with coupling agent concentrations ratio for 1:0.04
Enter aluminate coupling agent, persistently stirs 2 hours, obtain liquid D；
(3) it is centrifugated liquid D, is oil-soluble Fe with the white precipitate that organic solvent methanol is cleaned3+
Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube.
Preparation of the metal frictional abrasion surface from the compound formulation of nanosizing:
1) by oil-soluble Fe3+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube is added to lube base oil
In to get to the liquid phase component Y of liquid-solid compound phase component, it is spare as solvent.
2) solid phase components prepared are added in aforementioned liquid phase component Y to obtain realizes metal frictional abrasion surface certainly
The liquid-solid compound phase preparation of nanosizing, can be directly appended to use in lubricating oil.
To 1.6 row, two passenger cars, (one is A group to have travelled 80,000 kilometers；Another is B to have travelled 110,000 kilometers
Group) the influence test that has carried out engine performance, 3000 are travelled from the compound formulation of nanosizing using metal frictional abrasion surface
After kilometer, 6000 kilometers of comparisons are travelled with existing lubricating oil is added, as the result is shown:
(1) when filling metal frictional abrasion surface travels 3000km from the compound formulation of nanosizing, cylinder pressure of engines is obvious
Rise, A group averagely promotes 6.2%, B group and averagely promotes 6.1%, and it is 10.3% that most large cylinder, which presses lifting capacity,.
(2) when filling metal frictional abrasion surface travels 3000km from the compound formulation of nanosizing, engine noise is obvious
Decline, A group, which averagely reduces by 20.13%, B group, averagely reduces by 20.22%, maximum noise drop-out value 22.5dB (internal car noise).
(3) when filling metal frictional abrasion surface travels 3000km from the compound formulation of nanosizing, and traveling is not filled
It is compared when 6000km, A group vehicle CO, which reduces by 25%, HC+NOx, reduces by 28%；B group vehicle CO, which reduces by 27%, HC+NOx, reduces by 29%.
Embodiment 6
The preparation of metal ion mixing hydroxy silicate nanotube:
(1) chemical reagent used in: frerrous chloride, magnesium nitrate, sodium metasilicate and sodium hydroxide, mass concentration ratio: 1:25:30:
300；
(2) frerrous chloride and magnesium nitrate are dissolved into water by mass concentration ratio described in step (1), obtain solution A；
(3) sodium metasilicate is added by mass concentration ratio described in step (1) in solution A under magnetic agitation, obtains solution B；
(4) continue agitating solution B after 25 minutes, sodium hydroxide is added by mass concentration ratio described in step (1), continues
Stirring obtained solution C after 25 minutes；
(5) solution C is sealed in polytetrafluoroethylene (PTFE) water heating kettle reacts 35 hours at 250 DEG C；
(6) sediment is collected by centrifugation after reaction, it is successively that may be present miscellaneous to remove with second alcohol and water centrifuge washing
Matter ion, obtains Fe3+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube；
The modification of metal ion mixing hydroxy silicate nanotube:
(1) by Fe3+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube C is dispersed in monohydric alcohol organic solvent,
It is heated to 60 DEG C；
(2) Fe is pressed3+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube adds with coupling agent concentrations ratio for 1:0.08
Enter aluminate coupling agent, persistently stirs 2 hours, obtain liquid D；
(3) it is centrifugated liquid D, is oil-soluble Fe with the white precipitate that organic solvent methanol is cleaned3+
Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube.
Preparation of the metal frictional abrasion surface from the compound formulation of nanosizing:
1) by oil-soluble Fe3+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube is added to lube base oil
In to get to the liquid phase component Y of liquid-solid compound phase component, it is spare as solvent.
2) concentration ratio of the solid phase components prepared is added in aforementioned liquid phase component Y to obtain and realizes metal friction
Wear surface can be directly appended to use in lubricating oil from the liquid-solid compound phase preparation of nanosizing.
To 1.6 row, two passenger cars, (one is A group to have travelled 80,000 kilometers；Another is B to have travelled 110,000 kilometers
Group) the influence test that has carried out engine performance, 3000 are travelled from the compound formulation of nanosizing using metal frictional abrasion surface
After kilometer, 6000 kilometers of comparisons are travelled with existing lubricating oil is added, as the result is shown:
(1) when filling metal frictional abrasion surface travels 3000km from the compound formulation of nanosizing, cylinder pressure of engines is obvious
Rise, A group averagely promotes 6.5%, B group and averagely promotes 6.3%, and it is 10.6% that most large cylinder, which presses lifting capacity,.
(2) when filling metal frictional abrasion surface travels 3000km from the compound formulation of nanosizing, engine noise is obvious
Decline, A group, which averagely reduces by 20.54%, B group, averagely reduces by 20.46%, maximum noise drop-out value 22.9dB (internal car noise).
(3) when filling metal frictional abrasion surface travels 3000km from the compound formulation of nanosizing, and traveling is not filled
It is compared when 6000km, A group vehicle CO, which reduces by 28%, HC+NOx, reduces by 31%；B group vehicle CO, which reduces by 32%, HC+NOx, reduces by 31%.
Comparative example 1:
The preparation of metal ion mixing hydroxy silicate nanotube:
(1) chemical reagent used in: frerrous chloride, magnesium nitrate, sodium metasilicate and sodium hydroxide, mass concentration ratio: 1:10:5:
100；
(2) frerrous chloride and magnesium nitrate are dissolved into water by mass concentration ratio described in step (1), obtain solution A；
(3) sodium metasilicate is added by mass concentration ratio described in step (1) in solution A under magnetic agitation, obtains solution B；
(4) continue agitating solution B after 25 minutes, sodium hydroxide is added by mass concentration ratio described in step (1), continues
Stirring obtained solution C after 25 minutes；
(5) solution C is sealed in polytetrafluoroethylene (PTFE) water heating kettle reacts 55 hours at 500 DEG C；
(6) sediment is collected by centrifugation after reaction, it is successively that may be present miscellaneous to remove with second alcohol and water centrifuge washing
Matter ion, obtains Fe3+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube；
The modification of metal ion mixing hydroxy silicate nanotube:
(1) by Fe3+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube C is dispersed in monohydric alcohol organic solvent,
It is heated to 60 DEG C；
(2) Fe is pressed3+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube adds with coupling agent concentrations ratio for 1:0.08
Enter aluminate coupling agent, persistently stirs 2 hours, obtain liquid D；
(3) it is centrifugated liquid D, is oil-soluble Fe with the white precipitate that organic solvent methanol is cleaned3+
Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube.
Preparation of the metal frictional abrasion surface from the compound formulation of nanosizing:
1) by oil-soluble Fe3+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube is added to lube base oil
In to get to the liquid phase component Y of the liquid-solid compound phase component of invention, it is spare as solvent.
2) solid phase components prepared are added in aforementioned liquid phase component Y to obtain realizes metal frictional abrasion surface certainly
The liquid-solid compound phase preparation of nanosizing, can be directly appended to use in lubricating oil.
To 1.6 row, two passenger cars, (one is A group to have travelled 80,000 kilometers；Another is B to have travelled 110,000 kilometers
Group) the influence test that has carried out engine performance, 3000 are travelled from the compound formulation of nanosizing using metal frictional abrasion surface
After kilometer, 6000 kilometers of comparisons are travelled with existing lubricating oil is added, as the result is shown:
(1) when filling metal frictional abrasion surface travels 3000km from the compound formulation of nanosizing, cylinder pressure of engines is obvious
Rise, A group averagely promotes 2.5%, B group and averagely promotes 2.3%, and it is 3.6% that most large cylinder, which presses lifting capacity,.
(2) when filling metal frictional abrasion surface travels 3000km from the compound formulation of nanosizing, engine noise is obvious
Decline, A group, which averagely reduces by 10.54%, B group, averagely reduces by 10.46%, maximum noise drop-out value 11.9dB (internal car noise).
(3) when filling metal frictional abrasion surface travels 3000km from the compound formulation of nanosizing, and traveling is not filled
It is compared when 6000km, A group vehicle CO, which reduces by 12%, HC+NOx, reduces by 15%；B group vehicle CO, which reduces by 11%, HC+NOx, reduces by 12%.
The metal ion mixing hydroxy silicate nanotube for being made or being modified in above-mentioned processing range in summary, system
Efficiency highest of the standby metal frictional abrasion surface from the compound formulation of nanosizing from nanosizing, nano surface crystalline substance enhanced protection layer
Formation speed faster；Cylinder pressure of engines rising is higher, engine noise decline is bigger, and exhaust pollutant discharge is lower.And it adopts
Take the metal frictional abrasion surface beyond processing range described in embodiment 1 to 6 from the compound formulation of nanosizing from nanosizing
Efficiency it is lower, the formation speed of nano surface crystalline substance enhanced protection layer is slower, cylinder pressure of engines ascending amount, engine noise decline
Amount, exhaust pollutant emission effect are not so good as embodiment.
The above description is only a preferred embodiment of the present invention, not thereby limits scope of patent protection of the invention, all
It is directly or indirectly to be used in other relevant technologies with equivalent structure transformation made by description of the invention and accompanying drawing content
Field similarly includes within the scope of the present invention.
Claims (5)
1. a kind of manufacturing method of metal ion mixing hydroxy silicate nanotube, which comprises the following steps:
1) by metal chloride, magnesium nitrate, sodium metasilicate and sodium hydroxide, according to mass concentration are as follows: 1:(20-40): (10-30):
(200-450), is prepared；
2) metal chloride and magnesium nitrate are dissolved into water, sodium metasilicate is then added；After persistently stirring 10-30 minutes, it is added
Sodium hydroxide obtains midbody solution after continuing stirring 10-30 minutes；
3) midbody solution sealing is placed in reaction kettle reacts 20-50 hours at 200-400 DEG C；
4) sediment after reaction, is collected by centrifugation, successively uses solvent centrifuge washing, obtains metal ion mixing hydroxy silicate
Nanotube；
Further include following modification procedure:
1) in organic solvent by the dispersion of metal ion mixing hydroxy silicate nanotube, it is heated to 45-85 DEG C；
2) it is 1:(0.03-1) with concentration ratio by metal ion mixing hydroxy silicate nanotube and coupling agent, coupling agent is added,
It persistently stirs 1-2 hours, obtains liquid to be treated；
3) it is centrifugated liquid to be treated, is then cleaned with organic solvent, obtains oil-soluble metal ion mixing hydroxyl
Silicate nano tube.
2. the manufacturing method of metal ion mixing hydroxy silicate nanotube as described in claim 1, which is characterized in that described
Modification procedure 1) described in hydroxy silicate nanotube be hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube, hydroxyl silicic acid
Nickel (Ni3Si2O5(OH)4) nanotube or hydroxyl silicic acid nickel magnesium ((Ni, Mg)3Si2O5(OH)4) nanotube.
3. the manufacturing method of metal ion mixing hydroxy silicate nanotube as described in claim 1, which is characterized in that described
Modification procedure 2) described in organic solvent be monohydric alcohol, the monohydric alcohol is one kind of ethyl alcohol or propyl alcohol.
4. the manufacturing method of metal ion mixing hydroxy silicate nanotube as described in claim 1, which is characterized in that described
Modification procedure 2) described in coupling agent be one of silane coupling agent, titanate coupling agent and aluminate coupling agent or more
Kind.
5. the manufacturing method of metal ion mixing hydroxy silicate nanotube as described in claim 1, which is characterized in that described
Metal ion in metal ion mixing hydroxy silicate nanotube is that 3 long periods (4,5,6) are corresponding in the periodic table of elements
The ion of group vib and group VIII metal element.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710256092.3A CN107117626B (en) | 2017-04-19 | 2017-04-19 | Method for preparing metal ion doped hydroxyl silicate nano-tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710256092.3A CN107117626B (en) | 2017-04-19 | 2017-04-19 | Method for preparing metal ion doped hydroxyl silicate nano-tube |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107117626A CN107117626A (en) | 2017-09-01 |
| CN107117626B true CN107117626B (en) | 2019-08-13 |
Family
ID=59724804
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710256092.3A Active CN107117626B (en) | 2017-04-19 | 2017-04-19 | Method for preparing metal ion doped hydroxyl silicate nano-tube |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107117626B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109331838B (en) * | 2018-10-09 | 2021-04-30 | 华侨大学 | Preparation method of noble metal @ nickel silicate super-hydrophobic catalytic film |
| CN111436459B (en) * | 2019-12-27 | 2021-12-28 | 福建格瑞诗化工科技有限公司 | Inorganic mildew-proof antibacterial material, preparation method and application thereof, and inorganic mildew-proof antibacterial liquid |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100432279C (en) * | 2006-04-20 | 2008-11-12 | 金元生 | Preparation for forming protective layer on metal friction and wear-out surface and its preparing method |
| CN103466647B (en) * | 2013-09-10 | 2015-03-11 | 合肥工业大学 | Method for preparing magnetic chrysotile nanotube |
| CN103880027A (en) * | 2014-04-10 | 2014-06-25 | 周璐 | Hydroxyl magnesium silicate nanotube wear-resistant material and preparation method thereof |
| CN105152178B (en) * | 2015-07-13 | 2017-12-22 | 北京交通大学 | The preparation method of nano hydroxyl magnesium silicate, the preparation method and application of antiwear additive |
-
2017
- 2017-04-19 CN CN201710256092.3A patent/CN107117626B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107117626A (en) | 2017-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Micro and nano sulfide solid lubrication | |
| CN100445353C (en) | Metal/ ceramic nano composite additive of self-rehabilitation and its preparation method | |
| Tang et al. | Applications of carbon quantum dots in lubricant additives: A review | |
| CN100432279C (en) | Preparation for forming protective layer on metal friction and wear-out surface and its preparing method | |
| Cui et al. | Fabrication of carbon dots intercalated MXene hybrids via laser treatment as oil-based additives for synergistic lubrication | |
| CN107384512A (en) | Micro-nano intelligent Base Metal abrasion self-repair material and its preparation and application | |
| CN107117626B (en) | Method for preparing metal ion doped hydroxyl silicate nano-tube | |
| CN108837801A (en) | Double-shell hydrophobic magnetic microsphere and preparation method thereof | |
| Meng et al. | Nickel/multi-walled carbon nanotube nanocomposite synthesized in supercritical fluid as efficient lubricant additive for mineral oil | |
| CN101979480B (en) | Molybdenum disulfide nanosphere/titanium dioxide composite material and preparation method thereof | |
| CN103880027A (en) | Hydroxyl magnesium silicate nanotube wear-resistant material and preparation method thereof | |
| Wu et al. | Controllable synthesis and friction reduction of ZnFe2O4@ C microspheres with diverse core-shell architectures | |
| CN107011967B (en) | Self-nanocrystallized composite preparation for metal friction and wear surface | |
| CN1254337C (en) | Preparation method of nanometer sized superfine ferro nickel alloy powder | |
| Chen et al. | Inhibition of cold‐welding and adhesive wear occurring on surface of the 6061 aluminum alloy by graphene oxide/polyethylene glycol composite water‐based lubricant | |
| CN106467767A (en) | A kind of preparation method of micro crystal graphite alkene lube oil additive | |
| Saka | Facile oxygen doped heterojunction structured hybrid particles with γ-aluminium oxide dispersed over graphitic carbon nitride for dehydrogenation of sodium borohydride in methanol: Catalytic properties and mechanism | |
| Guo et al. | Superhydrophobic behaviors of nanoSiO2 coating on stainless steel mesh and its application in oil/water separation | |
| KR100948361B1 (en) | Manufacturing method of engine oil additive using nanofiber and nano-particle and engine oil additive thereby | |
| Ivanov et al. | Inventions of scientists, engineers and specialists from different countries in the area of nanotechnologies. Part I | |
| Jian et al. | Severe plastic deformation for advanced electrocatalysts for electrocatalytic hydrogen production | |
| KR101409132B1 (en) | preparing method of lubricant additives for improving performance in power driving | |
| Nada et al. | Conversion of Waste Cheap Petroleum Paraffinic Wax By-Products to Expensive Valuable Multiple Carbon Nanomaterials | |
| Gurjar et al. | Applications of nanotechnology in automobile industry for efficiency enhancement and energy saving-a review | |
| Aher et al. | Insight on the Effect of Nanoparticles addition in Oil Lubrication: A Review. |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PP01 | Preservation of patent right | ||
| PP01 | Preservation of patent right |
Effective date of registration: 20191226 Granted publication date: 20190813 |
|
| PD01 | Discharge of preservation of patent | ||
| PD01 | Discharge of preservation of patent |
Date of cancellation: 20211008 Granted publication date: 20190813 |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211115 Address after: 1702, 7th floor, lanqiying, Haidian District, Beijing 100084 Patentee after: Jin Yuansheng Address before: 313000 room A201, room A203, area a, room C101, area C, building 3, No. 666, Qixing Road, Huzhou City, Zhejiang Province Patentee before: Huzhou Yongxuan New Material Technology Co., Ltd |