CN107117626A - Method for preparing metal ion doped hydroxyl silicate nano-tube - Google Patents
Method for preparing metal ion doped hydroxyl silicate nano-tube Download PDFInfo
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- CN107117626A CN107117626A CN201710256092.3A CN201710256092A CN107117626A CN 107117626 A CN107117626 A CN 107117626A CN 201710256092 A CN201710256092 A CN 201710256092A CN 107117626 A CN107117626 A CN 107117626A
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- nanotube
- metal ion
- metal
- ion mixing
- silicate
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- 239000002071 nanotube Substances 0.000 title claims abstract description 110
- -1 hydroxyl silicate Chemical compound 0.000 title claims abstract description 69
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 32
- 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 65
- 239000002184 metal Substances 0.000 claims abstract description 65
- 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
- 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
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 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 52
- 239000011777 magnesium Substances 0.000 claims description 46
- UNYOJUYSNFGNDV-UHFFFAOYSA-M magnesium monohydroxide Chemical compound [Mg]O UNYOJUYSNFGNDV-UHFFFAOYSA-M 0.000 claims description 45
- 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
- 239000007822 coupling agent Substances 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- 239000003960 organic solvent Substances 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 22
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 22
- 230000004048 modification Effects 0.000 claims description 21
- 238000012986 modification Methods 0.000 claims description 21
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- XQSFXFQDJCDXDT-UHFFFAOYSA-N hydroxysilicon Chemical compound [Si]O XQSFXFQDJCDXDT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910005108 Ni3Si2 Inorganic materials 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 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
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910000077 silane 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
- 238000011049 filling Methods 0.000 description 28
- 239000007791 liquid phase Substances 0.000 description 21
- 239000010687 lubricating oil Substances 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 17
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 description 16
- 239000012071 phase Substances 0.000 description 14
- 230000009467 reduction Effects 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
- 230000007423 decrease Effects 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 238000013019 agitation Methods 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 230000000694 effects Effects 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
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 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
- 238000000227 grinding 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
- QURDCGKPZJHUNO-UHFFFAOYSA-N [Ni].OO[Si](O)(O)O Chemical compound [Ni].OO[Si](O)(O)O QURDCGKPZJHUNO-UHFFFAOYSA-N 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
- 239000013078 crystal Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000005669 field effect Effects 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 238000003754 machining Methods 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
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000001228 spectrum Methods 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- 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
- 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
- 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
- 230000003014 reinforcing effect Effects 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 manufacture method of metal ion mixing hydroxy silicate nanotube, belong to metal material processing
Field.
Background technology
Three big failure modes of element part, abrasion, fatigue and corrosion, all since surface, the surface of material
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 modification are compared, and surface is certainly
Nanosizing processing can not have the nanostructured layers of sharp interface between the formation of material its own face and matrix, wear-resisting, against corrosion,
It is greatly enhanced surface property.
Conventional 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 becomes, it is necessary to make material produce strong plasticity under the repeat function of plus load
Shape, the open grain structure on surface is gradually refined to nanometer scale.This surface self-nanocrystallinzation processing belongs to off-line technology, it is necessary to high energy
Special equipment, the activity duration is longer, costly.
The relative motion of the lower friction pair of load effect is also that the one kind on surface is machined, but not enough under normal conditions
To produce the intense plastic strain needed for surface self-nanocrystallinzation.Mechanical alloying and high temperature internal oxidition are two that developed recently gets up
The effective way of nano surface crystalline substance reinforcing is planted, can be used for metal frictional abrasion surface from nanosizing.Under general condition, friction is situated between
The thermodynamic condition in face can neither realize surface mechanical alloying, can not complete the reaction of high temperature internal oxidition.Existing simple profit
Technology of the friction surface from nanosizing is realized with solid phase components, its mechanism of action is mechanical alloying, the machinery containing surface oxidation is thrown
Light, lubrication oil-breaking carbonization and the step of mechanical alloying three.There is problems with：1st, solid phase components can not be abundant in lubricating oil
It is scattered to suspend；2nd, lubrication oil-breaking carbonization is needed to participate in reaction；Cause the efficiency from nanosizing low, 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 adds lubricating oil by metal ion mixing hydroxy silicate nanotube and formed, the hydroxyl silicic acid in liquid phase component
The surface-active key of salt nanotube has good adsorptivity to fresh metal surface, and metal ion mixing make it have it is ferromagnetic
Property, nanotube, which can be aligned, under the Surface field effect that friction is produced is enriched in metal surface.The hydroxyl silicon of liquid phase component
Contain various active chemical bond in stratiform hydroxy silicate natural ore powder particulate 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 active greatly free oxygen, O2-, O, to
Metal inside spreads by force.It is the synthesis nanotube of friction surface enrichment first, the free oxygen that subsequent natural ore powder particulate is produced is equal
This strong diffusion effect occurs.In addition, the active Free water H that deshydroxy reaction is produced2O can also spread to metal inside therewith；
And existing technology lacks the method for manufacturing metal ion mixing hydroxy silicate nanotube.
The content of the invention
(1) technical problem to be solved
It is an object of the invention to provide a kind of manufacture method of metal ion mixing hydroxy silicate nanotube there is provided with
The metal ion mixing hydroxy silicate nanotube that stratiform hydroxy silicate natural ore powder particulate cooperates, is solved existing
Technology can not produce the defect of metal ion mixing hydroxy silicate nanotube.
(2) technical scheme
In order to solve the above-mentioned technical problem, the invention discloses a kind of system of metal ion mixing hydroxy silicate nanotube
Method is made, is comprised the following steps：
1) by metal chloride, magnesium nitrate, sodium metasilicate and sodium hydroxide, it is according to mass concentration：1:(20-40):(10-
30):(200-450), is prepared；
2) metal chloride and magnesium nitrate are dissolved into water, then add sodium metasilicate；After persistently stirring 10-30 minutes,
Sodium hydroxide is added, continues to obtain midbody solution after stirring 10-30 minutes；
3) midbody solution sealing is placed in reactor reacts 20-50 hours at 200-400 DEG C；
4) after reaction terminates, sediment is collected by centrifugation, solvent centrifuge washing is used successively, metal ion mixing hydroxyl silicon is obtained
Silicate nanometer pipe.
Optionally, the manufacture method of the metal ion mixing hydroxy silicate nanotube also includes following modification procedure：
1) it is metal ion mixing hydroxy silicate nanotube is scattered in organic solvent, it is heated to 45-85 DEG C；
2) by metal ion mixing hydroxy silicate nanotube and coupling agent using concentration ratio as 1:(0.03-1), is added even
Join agent, persistently stir 1-2 hours, obtain liquid to be treated；
3) liquid to be treated is centrifuged, 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 ethanol or propyl alcohol.
Optionally, the modification procedure 2) described in coupling agent be silane coupler, titanate coupling agent and Aluminate
One or more in coupling agent.
(3) beneficial effect
A kind of manufacture method for metal ion mixing hydroxy silicate nanotube that the present invention is provided, it has following excellent
Point：
1) metal frictional abrasion surface 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, 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 is this thermal oxidative reaction layer.Therefore, receive certainly
Riceization it is more efficient, nano surface crystalline substance enhanced protection layer formation speed faster.The metal ion mixing hydroxy silicate is received
Mitron manufacture method, production is simple, efficiency of the obtained metal frictional abrasion surface from the compound formulation of nanosizing from nanosizing
It is higher.
Brief description of the drawings
Fig. 1 is the Fe of the present invention3+Adulterate hydroxyl magnesium silicate nanotube transmission electron microscope (TEM) image；
Fig. 2 is the Fe of the present invention3+Adulterate hydroxyl magnesium silicate nanotube x-ray photoelectron power spectrum (XPS) figure.
Embodiment
With reference to the accompanying drawings and examples, the embodiment to the present invention is described in further detail.Following instance
For illustrating the present invention, but it is not limited to the scope of the present 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) surpass
Smart surface grinding：Solid compositions particulate and the silica (SiO that they are produced by the decomposition of friction and Extrusion cleavage in component2) and
Alundum (Al2O3) (Al2O3) nanoscale (10-7-10-9M) particulate surpasses under fricting shearing effect to metal friction and wear surface
Smooth grinding, produces fresh active surface.
(2) active material surface is adsorbed：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, is received under the Surface field effect that friction is produced
Mitron can align and be enriched in metal surface.
(3) active oxygen spreads by force to metal inside：In hydroxy silicate nanotube and solid phase components in liquid phase component
Contain various active chemical bond in stratiform hydroxy silicate natural ore powder particulate, wherein silicon oxygen bond, Si-O-Si, O-Si-
O, when cleavage is destroyed, easy fracture produces active greatly free oxygen, O2-, O, spread by force to metal inside.It is friction first
This strong diffusion effect occurs in the synthesis nanotube of surface enrichment, the free oxygen that subsequent natural ore powder particulate is produced.In addition,
The active Free water H that deshydroxy reaction is produced2O can also 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 of internal oxidition formation3O4Nanocrystal, which is deposited on matrix, to be formed from nanosizing crystal layer；The gas of generation is to surface
Effusion, is formed from the nanoaperture in nanosizing crystal layer.
The invention discloses a kind of manufacture method of metal ion mixing hydroxy silicate nanotube, comprise the following steps：
1) by metal chloride, magnesium nitrate, sodium metasilicate and sodium hydroxide, it is according to mass concentration：1:(20-40):(10-
30):(200-450), is prepared；
2) metal chloride and magnesium nitrate are dissolved into water, then add sodium metasilicate；After persistently stirring 10-30 minutes,
Sodium hydroxide is added, continues to obtain midbody solution after stirring 10-30 minutes；
3) midbody solution sealing is placed in reactor reacts 20-50 hours at 200-400 DEG C；
4) after reaction terminates, sediment is collected by centrifugation, solvent centrifuge washing is used successively, metal ion mixing hydroxyl silicon is obtained
Silicate nanometer pipe.
Wherein, the manufacture method of the metal ion mixing hydroxy silicate nanotube also includes following modification procedure：
1) it is metal ion mixing hydroxy silicate nanotube is scattered in organic solvent, it is heated to 45-85 DEG C；
2) by metal ion mixing hydroxy silicate nanotube and coupling agent using concentration ratio as 1:(0.03-1), is added even
Join agent, persistently stir 1-2 hours, obtain liquid to be treated；
3) liquid to be treated is centrifuged, 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 ethanol or propyl alcohol.
Wherein, the modification procedure 2) described in coupling agent be silane coupler, titanate coupling agent and Aluminate it is even
Join the one or more in agent.
Wherein, the metal ion in the metal ion mixing hydroxy silicate nanotube is 3 long in the periodic table of elements
The ion of cycle (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 is dissolved into water with mass concentration ratio of the magnesium nitrate as described in step (1), obtains solution A；
(3) mass concentration ratio under magnetic agitation in solution A as described in step (1) adds sodium metasilicate, obtains solution B；
(4) agitating solution B is continued after 10 minutes, the mass concentration ratio as described in step (1) adds sodium hydroxide, continues
Stirring obtains solution C after 10 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 terminating in reaction, that may be present miscellaneous to remove with second alcohol and water centrifuge washing successively
Matter ion, obtains Fe3+Adulterate hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube, accompanying drawing 1 is resulting Fe3+ doping
Hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube transmission electron microscope (TEM) image；Fig. 2 is x-ray photoelectron power spectrum (XPS)
Analysis 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 and coupling agent concentrations ratio be 1:0.03 adds
Enter aluminate coupling agent, persistently stir 1 hour, obtain liquid D；
(3) liquid D is centrifuged, it is oil-soluble Fe to be carried out cleaning obtained white precipitate with organic solvent methanol3+
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 is dissolved into water with mass concentration ratio of the magnesium nitrate as described in step (1), obtains solution A；
(3) mass concentration ratio under magnetic agitation in solution A as described in step (1) adds sodium metasilicate, obtains solution B；
(4) agitating solution B is continued after 10 minutes, the mass concentration ratio as described in step (1) adds sodium hydroxide, continues
Stirring obtains solution C after 10 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 terminating in reaction, that may be present miscellaneous to remove with second alcohol and water centrifuge washing successively
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 and coupling agent concentrations ratio be 1:0.03 adds
Enter aluminate coupling agent, persistently stir 1 hour, obtain liquid D；
(3) liquid D is centrifuged, it is oil-soluble Fe to be carried out cleaning obtained white precipitate with organic solvent methanol3+
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, that is, the liquid phase component Y of liquid-solid compound phase component in the present invention is obtained, it is standby as solvent.
2) solid phase components prepared are added in foregoing liquid phase component Y into i.e. acquisition 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 groups to have travelled 80,000 kilometers；Another is B to have travelled 110,000 kilometers
Group) the influence experiment of engine performance has been carried out, travel 3000 from the compound formulation of nanosizing using metal frictional abrasion surface
After kilometer, 6000 kilometers of contrasts are travelled with adding existing lubricating oil, are as a result shown：
(1) filling metal frictional abrasion surface from the compound formulation of nanosizing travel 3000km when, cylinder pressure of engines is obvious
Rise, A groups averagely lift 4.5%, B groups and averagely lift 4.83%, and most vat pressure lifting capacity is 7.5%.
(2) filling metal frictional abrasion surface from the compound formulation of nanosizing travel 3000km when, engine noise is obvious
Decline, A groups, which averagely reduce by 16.93%, B groups, averagely reduces by 16.78%, maximum noise drop-out value 20.7dB (internal car noise).
(3) filling metal frictional abrasion surface from the compound formulation of nanosizing travel 3000km when, with not filling traveling
Compared during 6000km, A group cars CO reduces by 24%, HC+NOx reductions by 23%；B group cars CO reduces by 19%, HC+NOx reductions 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 is dissolved into water with mass concentration ratio of the magnesium nitrate as described in step (1), obtains solution A；
(3) mass concentration ratio under magnetic agitation in solution A as described in step (1) adds sodium metasilicate, obtains solution B；
(4) agitating solution B is continued after 30 minutes, the mass concentration ratio as described in step (1) adds sodium hydroxide, continues
Stirring obtains 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 terminating in reaction, that may be present miscellaneous to remove with second alcohol and water centrifuge washing successively
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 1:1 adds
Aluminate coupling agent, persistently stirs 2 hours, obtains liquid D；
(3) liquid D is centrifuged, it is oil-soluble Cr to be carried out cleaning obtained white precipitate with organic solvent methanol3+
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, that is, the liquid phase component Y of the liquid-solid compound phase component of invention is obtained, it is standby as solvent.
2) solid phase components prepared are added in foregoing liquid phase component Y into i.e. acquisition 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 groups to have travelled 80,000 kilometers；Another is B to have travelled 110,000 kilometers
Group) the influence experiment of engine performance has been carried out, travel 3000 from the compound formulation of nanosizing using metal frictional abrasion surface
After kilometer, 6000 kilometers of contrasts are travelled with adding existing lubricating oil, are as a result shown：
(1) filling metal frictional abrasion surface from the compound formulation of nanosizing travel 3000km when, cylinder pressure of engines is obvious
Rise, A groups averagely lift 5.5%, B groups and averagely lift 5.6%, and most vat pressure lifting capacity is 8.9%.
(2) filling metal frictional abrasion surface from the compound formulation of nanosizing travel 3000km when, engine noise is obvious
Decline, A groups, which averagely reduce by 19.73%, B groups, averagely reduces by 18.58%, maximum noise drop-out value 21.5dB (internal car noise).
(3) filling metal frictional abrasion surface from the compound formulation of nanosizing travel 3000km when, with not filling traveling
Compared during 6000km, A group cars CO reduces by 25%, HC+NOx reductions by 26%；B group cars CO reduces by 21%, HC+NOx reductions 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 is dissolved into water with mass concentration ratio of the magnesium nitrate as described in step (1), obtains solution A；
(3) mass concentration ratio under magnetic agitation in solution A as described in step (1) adds sodium metasilicate, obtains solution B；
(4) agitating solution B is continued after 20 minutes, the mass concentration ratio as described in step (1) adds sodium hydroxide, continues
Stirring obtains solution C after 20 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 terminating in reaction, that may be present miscellaneous to remove with second alcohol and water centrifuge washing successively
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 and coupling agent concentrations ratio be 1:0.06 adds
Enter aluminate coupling agent, persistently stir 1.5 hours, obtain liquid D；
(3) liquid D is centrifuged, it is oil-soluble Ni to be carried out cleaning obtained white precipitate with organic solvent methanol2+
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, that is, the liquid phase component Y of the liquid-solid compound phase component of invention is obtained, it is standby as solvent.
2) solid phase components prepared are added in foregoing liquid phase component Y into i.e. acquisition 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 groups to have travelled 80,000 kilometers；Another is B to have travelled 110,000 kilometers
Group) the influence experiment of engine performance has been carried out, travel 3000 from the compound formulation of nanosizing using metal frictional abrasion surface
After kilometer, 6000 kilometers of contrasts are travelled with adding existing lubricating oil, are as a result shown：
(1) filling metal frictional abrasion surface from the compound formulation of nanosizing travel 3000km when, cylinder pressure of engines is obvious
Rise, A groups averagely lift 5.3%, B groups and averagely lift 5.4%, and most vat pressure lifting capacity is 8.6%.
(2) filling metal frictional abrasion surface from the compound formulation of nanosizing travel 3000km when, engine noise is obvious
Decline, A groups, which averagely reduce by 19.73%, B groups, averagely reduces by 18.52%, maximum noise drop-out value 21.2dB (internal car noise).
(3) filling metal frictional abrasion surface from the compound formulation of nanosizing travel 3000km when, with not filling traveling
Compared during 6000km, A group cars CO reduces by 22%, HC+NOx reductions by 23%；B group cars CO reduces by 20%, HC+NOx reductions 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 is dissolved into water with mass concentration ratio of the magnesium nitrate as described in step (1), obtains solution A；
(3) mass concentration ratio under magnetic agitation in solution A as described in step (1) adds sodium metasilicate, obtains solution B；
(4) agitating solution B is continued after 25 minutes, the mass concentration ratio as described in step (1) adds sodium hydroxide, continues
Stirring obtains 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 terminating in reaction, that may be present miscellaneous to remove with second alcohol and water centrifuge washing successively
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 and coupling agent concentrations ratio be 1:0.08 adds
Enter aluminate coupling agent, persistently stir 2 hours, obtain liquid D；
(3) liquid D is centrifuged, it is oil-soluble Co to be carried out cleaning obtained white precipitate with organic solvent methanol+
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, that is, the liquid phase component Y of liquid-solid compound phase component is obtained, it is standby as solvent.
2) solid phase components prepared are added in foregoing liquid phase component Y into i.e. acquisition realizes metal frictional abrasion surface certainly
The liquid-solid compound phase preparation of nanosizing, can be directly appended to use in lubricating oil.
Exemplified by automobile engine lubricating oil application, using prior art, power performance is obviously improved, vibrating noise substantially drops
The operation milimeter number that low, exhaust emissions substantially mitigates need to be more than 1000-5000 kilometers；Effect same is reached in the present embodiment
Operation milimeter number only needs 350 kilometers.
To 1.6 row, two passenger cars, (one is A groups to have travelled 80,000 kilometers；Another is B to have travelled 110,000 kilometers
Group) the influence experiment of engine performance has been carried out, travel 3000 from the compound formulation of nanosizing using metal frictional abrasion surface
After kilometer, 6000 kilometers of contrasts are travelled with adding existing lubricating oil, are as a result shown：
(1) filling metal frictional abrasion surface from the compound formulation of nanosizing travel 3000km when, cylinder pressure of engines is obvious
Rise, A groups averagely lift 5.2%, B groups and averagely lift 5.1%, and most vat pressure lifting capacity is 8.4%.
(2) filling metal frictional abrasion surface from the compound formulation of nanosizing travel 3000km when, engine noise is obvious
Decline, A groups, which averagely reduce by 19.73%, B groups, averagely reduces by 18.62%, maximum noise drop-out value 21.7dB (internal car noise).
(3) filling metal frictional abrasion surface from the compound formulation of nanosizing travel 3000km when, with not filling traveling
Compared during 6000km, A group cars CO reduces by 22%, HC+NOx reductions by 22%；B group cars CO reduces by 20%, HC+NOx reductions 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 is dissolved into water with mass concentration ratio of the magnesium nitrate as described in step (1), obtains solution A；
(3) mass concentration ratio under magnetic agitation in solution A as described in step (1) adds sodium metasilicate, obtains solution B；
(4) agitating solution B is continued after 25 minutes, the mass concentration ratio as described in step (1) adds sodium hydroxide, continues
Stirring obtains 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 terminating in reaction, that may be present miscellaneous to remove with second alcohol and water centrifuge washing successively
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 and coupling agent concentrations ratio be 1:0.04 adds
Enter aluminate coupling agent, persistently stir 2 hours, obtain liquid D；
(3) liquid D is centrifuged, it is oil-soluble Fe to be carried out cleaning obtained white precipitate with organic solvent methanol3+
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, that is, the liquid phase component Y of liquid-solid compound phase component is obtained, it is standby as solvent.
2) solid phase components prepared are added in foregoing liquid phase component Y into i.e. acquisition 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 groups to have travelled 80,000 kilometers；Another is B to have travelled 110,000 kilometers
Group) the influence experiment of engine performance has been carried out, travel 3000 from the compound formulation of nanosizing using metal frictional abrasion surface
After kilometer, 6000 kilometers of contrasts are travelled with adding existing lubricating oil, are as a result shown：
(1) filling metal frictional abrasion surface from the compound formulation of nanosizing travel 3000km when, cylinder pressure of engines is obvious
Rise, A groups averagely lift 6.2%, B groups and averagely lift 6.1%, and most vat pressure lifting capacity is 10.3%.
(2) filling metal frictional abrasion surface from the compound formulation of nanosizing travel 3000km when, engine noise is obvious
Decline, A groups, which averagely reduce by 20.13%, B groups, averagely reduces by 20.22%, maximum noise drop-out value 22.5dB (internal car noise).
(3) filling metal frictional abrasion surface from the compound formulation of nanosizing travel 3000km when, with not filling traveling
Compared during 6000km, A group cars CO reduces by 25%, HC+NOx reductions by 28%；B group cars CO reduces by 27%, HC+NOx reductions 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 is dissolved into water with mass concentration ratio of the magnesium nitrate as described in step (1), obtains solution A；
(3) mass concentration ratio under magnetic agitation in solution A as described in step (1) adds sodium metasilicate, obtains solution B；
(4) agitating solution B is continued after 25 minutes, the mass concentration ratio as described in step (1) adds sodium hydroxide, continues
Stirring obtains 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 terminating in reaction, that may be present miscellaneous to remove with second alcohol and water centrifuge washing successively
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 and coupling agent concentrations ratio be 1:0.08 adds
Enter aluminate coupling agent, persistently stir 2 hours, obtain liquid D；
(3) liquid D is centrifuged, it is oil-soluble Fe to be carried out cleaning obtained white precipitate with organic solvent methanol3+
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, that is, the liquid phase component Y of liquid-solid compound phase component is obtained, it is standby as solvent.
2) concentration ratio of the solid phase components prepared is added to i.e. acquisition in foregoing liquid phase component Y 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 groups to have travelled 80,000 kilometers；Another is B to have travelled 110,000 kilometers
Group) the influence experiment of engine performance has been carried out, travel 3000 from the compound formulation of nanosizing using metal frictional abrasion surface
After kilometer, 6000 kilometers of contrasts are travelled with adding existing lubricating oil, are as a result shown：
(1) filling metal frictional abrasion surface from the compound formulation of nanosizing travel 3000km when, cylinder pressure of engines is obvious
Rise, A groups averagely lift 6.5%, B groups and averagely lift 6.3%, and most vat pressure lifting capacity is 10.6%.
(2) filling metal frictional abrasion surface from the compound formulation of nanosizing travel 3000km when, engine noise is obvious
Decline, A groups, which averagely reduce by 20.54%, B groups, averagely reduces by 20.46%, maximum noise drop-out value 22.9dB (internal car noise).
(3) filling metal frictional abrasion surface from the compound formulation of nanosizing travel 3000km when, with not filling traveling
Compared during 6000km, A group cars CO reduces by 28%, HC+NOx reductions by 31%；B group cars CO reduces by 32%, HC+NOx reductions 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 is dissolved into water with mass concentration ratio of the magnesium nitrate as described in step (1), obtains solution A；
(3) mass concentration ratio under magnetic agitation in solution A as described in step (1) adds sodium metasilicate, obtains solution B；
(4) agitating solution B is continued after 25 minutes, the mass concentration ratio as described in step (1) adds sodium hydroxide, continues
Stirring obtains 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 terminating in reaction, that may be present miscellaneous to remove with second alcohol and water centrifuge washing successively
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 and coupling agent concentrations ratio be 1:0.08 adds
Enter aluminate coupling agent, persistently stir 2 hours, obtain liquid D；
(3) liquid D is centrifuged, it is oil-soluble Fe to be carried out cleaning obtained white precipitate with organic solvent methanol3+
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, that is, the liquid phase component Y of the liquid-solid compound phase component of invention is obtained, it is standby as solvent.
2) solid phase components prepared are added in foregoing liquid phase component Y into i.e. acquisition 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 groups to have travelled 80,000 kilometers；Another is B to have travelled 110,000 kilometers
Group) the influence experiment of engine performance has been carried out, travel 3000 from the compound formulation of nanosizing using metal frictional abrasion surface
After kilometer, 6000 kilometers of contrasts are travelled with adding existing lubricating oil, are as a result shown：
(1) filling metal frictional abrasion surface from the compound formulation of nanosizing travel 3000km when, cylinder pressure of engines is obvious
Rise, A groups averagely lift 2.5%, B groups and averagely lift 2.3%, and most vat pressure lifting capacity is 3.6%.
(2) filling metal frictional abrasion surface from the compound formulation of nanosizing travel 3000km when, engine noise is obvious
Decline, A groups, which averagely reduce by 10.54%, B groups, averagely reduces by 10.46%, maximum noise drop-out value 11.9dB (internal car noise).
(3) filling metal frictional abrasion surface from the compound formulation of nanosizing travel 3000km when, with not filling traveling
Compared during 6000km, A group cars CO reduces by 12%, HC+NOx reductions by 15%；B group cars CO reduces by 11%, HC+NOx reductions by 12%.
Being made in above-mentioned processing range or modified metal ion mixing hydroxy silicate nanotube in summary, it is made
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 adopt
The metal frictional abrasion surface of processing range described in the embodiment 1 to 6 is taken from the compound formulation of nanosizing from nanosizing
It is less efficient, nano surface crystalline substance enhanced protection layer formation speed it is slower, cylinder pressure of engines ascending amount, engine noise decline
Amount, exhaust pollutant emission effect is not so good as embodiment.
The preferred embodiments of the present invention are the foregoing is only, the scope of patent protection of the present invention is not thereby limited, it is all
It is the equivalent structure transformation made with description of the invention and accompanying drawing content, is directly or indirectly used in other related technologies
Field, similarly includes within the scope of the present invention.
Claims (6)
1. a kind of manufacture method of metal ion mixing hydroxy silicate nanotube, it is characterised in that comprise the following steps：
1) by metal chloride, magnesium nitrate, sodium metasilicate and sodium hydroxide, it is according to mass concentration：1:(20-40):(10-30):
(200-450), is prepared；
2) metal chloride and magnesium nitrate are dissolved into water, then add sodium metasilicate；After persistently stirring 10-30 minutes, add
Sodium hydroxide, continues to obtain midbody solution after stirring 10-30 minutes；
3) midbody solution sealing is placed in reactor reacts 20-50 hours at 200-400 DEG C；
4) after reaction terminates, sediment is collected by centrifugation, solvent centrifuge washing is used successively, metal ion mixing hydroxy silicate is obtained
Nanotube.
2. the manufacture method of metal ion mixing hydroxy silicate nanotube as claimed in claim 1, it is characterised in that also wrap
Include following modification procedure：
1) it is metal ion mixing hydroxy silicate nanotube is scattered in organic solvent, it is heated to 45-85 DEG C；
2) by metal ion mixing hydroxy silicate nanotube and coupling agent using concentration ratio as 1:(0.03-1), adds coupling agent,
Persistently stir 1-2 hours, obtain liquid to be treated；
3) liquid to be treated is centrifuged, is then cleaned with organic solvent, obtains oil-soluble metal ion mixing hydroxyl
Silicate nano tube.
3. the manufacture method of metal ion mixing hydroxy silicate nanotube as claimed in claim 2, it is characterised in that described
Modification procedure 1) described in hydroxy silicate nanotube be hydroxyl magnesium silicate (Mg6[Si4O10][OH]8) nanotube, hydroxyl silicon
Sour nickel (Ni3Si2O5(OH)4) nanotube or hydroxyl silicic acid nickel magnesium ((Ni, Mg)3Si2O5(OH)4) nanotube.
4. the manufacture method of metal ion mixing hydroxy silicate nanotube as claimed in claim 2, it is characterised in that described
Modification procedure 2) described in organic solvent be monohydric alcohol, one kind of ethanol or propyl alcohol.
5. the manufacture method of metal ion mixing hydroxy silicate nanotube as claimed in claim 2, it is characterised in that described
Modification procedure 2) described in coupling agent be silane coupler, titanate coupling agent and aluminate coupling agent in one kind or many
Kind.
6. the manufacture method of metal ion mixing hydroxy silicate nanotube as claimed in claim 1, it is characterised in that described
Metal ion in metal ion mixing hydroxy silicate nanotube is corresponding for 3 long periods (4,5,6) in the periodic table of elements
The ion of group vib and group VIII metal element.
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| CN109331838A (en) * | 2018-10-09 | 2019-02-15 | 华侨大学 | A kind of preparation method of the super-hydrophobic catalytic film of noble metal@silicic acid nickel |
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| CN111436459A (en) * | 2019-12-27 | 2020-07-24 | 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 |
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