CN107473659A - A kind of nanocrystalline enhancing cement paste material of modified cellulose and preparation method thereof - Google Patents
A kind of nanocrystalline enhancing cement paste material of modified cellulose and preparation method thereof Download PDFInfo
- Publication number
- CN107473659A CN107473659A CN201710773047.5A CN201710773047A CN107473659A CN 107473659 A CN107473659 A CN 107473659A CN 201710773047 A CN201710773047 A CN 201710773047A CN 107473659 A CN107473659 A CN 107473659A
- Authority
- CN
- China
- Prior art keywords
- cellulose
- cnc
- nanocrystalline
- cement
- cement paste
- 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.)
- Granted
Links
- 239000004568 cement Substances 0.000 title claims abstract description 91
- 229920002678 cellulose Polymers 0.000 title claims abstract description 60
- 239000001913 cellulose Substances 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 230000002708 enhancing effect Effects 0.000 title claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002159 nanocrystal Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000000265 homogenisation Methods 0.000 claims abstract description 5
- 239000013078 crystal Substances 0.000 claims abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 25
- 229920001223 polyethylene glycol Polymers 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000033228 biological regulation Effects 0.000 claims description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 5
- 238000000465 moulding Methods 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- 238000012805 post-processing Methods 0.000 claims description 2
- 235000010980 cellulose Nutrition 0.000 claims 19
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims 1
- 230000036571 hydration Effects 0.000 abstract description 12
- 238000006703 hydration reaction Methods 0.000 abstract description 12
- 238000002604 ultrasonography Methods 0.000 abstract description 6
- 238000007385 chemical modification Methods 0.000 abstract description 5
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 239000002002 slurry Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 21
- 230000000694 effects Effects 0.000 description 9
- 239000008187 granular material Substances 0.000 description 7
- 239000003638 chemical reducing agent Substances 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 229920005646 polycarboxylate Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- PXFBZOLANLWPMH-UHFFFAOYSA-N 16-Epiaffinine Natural products C1C(C2=CC=CC=C2N2)=C2C(=O)CC2C(=CC)CN(C)C1C2CO PXFBZOLANLWPMH-UHFFFAOYSA-N 0.000 description 2
- 239000004484 Briquette Substances 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- 239000011398 Portland cement Substances 0.000 description 2
- 230000002742 anti-folding effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000010148 water-pollination Effects 0.000 description 2
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 206010027336 Menstruation delayed Diseases 0.000 description 1
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 1
- 241001597008 Nomeidae Species 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001418 larval effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005543 nano-size silicon particle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229960003753 nitric oxide Drugs 0.000 description 1
- 235000019391 nitrogen oxide Nutrition 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/04—Portland cements
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/38—Polysaccharides or derivatives thereof
- C04B24/383—Cellulose or derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present invention relates to nanocrystalline enhancing cement paste material of a kind of modified cellulose and preparation method thereof, the modified cellulose nanometer crystal class enhancing cement paste material contains Cellulose nanocrystal derivative.Its preparation method is：Cellulose nanocrystal derivative is mixed with water, is mixed and stirred after homogenization, supersound process with cement, is subsequently placed in mould and conserves, obtains the nanocrystalline enhancing cement paste material of modified cellulose.The present invention further improves dispersiveness of the cellulose nano material in cement, improves the degree of hydration of cement, lift the mechanical property of cement slurry by surface chemical modification and appropriate homogeneous, the method for ultrasound.Cellulose nanocrystal derivative is added with the raising beneficial to cement paste material degree of hydration so as to improve rupture strength, when CNC COOH or CNC g PEG volumes are 0.20%, 3 days intensity of cement improve 30% and 40% respectively, and intensity also has 15% and 20% lifting within 28 days.
Description
Technical field
The invention belongs to building material technical field, and in particular to a kind of nanocrystalline enhancing cement paste material of modified cellulose
Material and preparation method thereof.
Background technology
As modern architecture is towards large span, the development in high stratification direction, the concrete performance requirement to load-carrying members is got over
Come higher.It can not meet to construct due to the anti-folding and load-bearing property of cement or concrete in itself or be wanted as structural material
Ask, it is necessary to which addition reinforcing fiber materials improve its intensity etc. wherein.Traditional reinforcing material such as nano silicon, steel are fine
Dimension, glass fibre or carbon fiber etc., all there is easily by environmental attack, environment is unfriendly, the disadvantage such as expensive.
Cellulose nanocrystal (CNC) is the bar-shaped fibre for the nanoscale that cellulose obtains after certain sour hydrolysis process
Plain crystal is tieed up, there is high intensity, high-modulus and high specific surface area, at the same it is again environmentally friendly renewable, have huge
Application prospect.CNC is added in cement paste, can effectively lift the degree of hydration of cement so as to lift the strong of concrete
Degree.It is extremely difficult scattered in cement material but CNC easily reunites when adding, have a strong impact on the enhancing effect to cement material.
CNC surfaces are modified as the present invention into carboxylated cellulose element nanocrystalline (CNC-COOH) and Cellulose nanocrystal is grafted and gathered
Ethylene glycol (CNC-g-PEG), and added in cement paste, compared to unmodified CNC, CNC surface modification derivant
Dispersiveness in water is more preferable, therefore scattered in cement matrix also can be more preferable；Simultaneously CNC derivatives to water it is affine
Lifting, contribute to diffusion lifting degree of hydration of the moisture to unhydrated region, therefore can effectively lift the aquation journey of cement
Spend so as to lift the mechanical property of cement.
The content of the invention
The technical problems to be solved by the invention are for above shortcomings in the prior art, there is provided one kind has height
Nanocrystalline enhancing cement paste material of modified cellulose of intensity and preparation method thereof.
In order to solve the above technical problems, technical scheme provided by the invention is：
There is provided a kind of modified cellulose nanocrystalline enhancing cement paste material, the modified cellulose nanometer crystal class strengthens water
Cement paste material contains Cellulose nanocrystal derivative.
By such scheme, the Cellulose nanocrystal derivative is carboxylated cellulose element nanocrystalline (CNC-COOH) or fiber
The nano-crystalline grafted polyethylene glycol (CNC-g-PEG) of element.
By such scheme, the preparation method of the CNC-COOH is：CNC ultrasonic disperses are obtained into CNC dispersion liquids in water,
Then TEMPO and the NaBr obtained aqueous solution soluble in water are added dropwise in CNC dispersion liquids, then that NaClO is slowly added dropwise is molten
Liquid, 3h is reacted at room temperature, it is 10.0 to adjust reacting liquid pH value with NaOH solution during reaction, adds ethanol and stops reaction, then
It is 5.0-6.0, stirring reaction 30min to add HCl solution regulation reacting liquid pH value, then through centrifuge washing, be dried to obtain CNC-
COOH。
By such scheme, the preparation method of the CNC-g-PEG is：CNC-COOH is scattered in amino polyethylene glycol water
CNC-COOH dispersion liquids are obtained in solution, regulation dispersion liquid pH value is 7.5-8.0, adds NHS and EDC, stirring reaction 24h, with
Post processing obtains CNC-g-PEG afterwards.
The present invention also provides the preparation method of above-mentioned modified cellulose nano-crystal enhancing cement paste material, and its step is as follows：
Cellulose nanocrystal derivative is mixed with water, is mixed and stirred after homogenization, supersound process with cement, is subsequently placed in mould and supports
Shield, obtain the nanocrystalline enhancing cement paste material of modified cellulose.
By such scheme, the Cellulose nanocrystal derivative and cement quality ratio are 0.01-2:100.
Preferably, the Cellulose nanocrystal derivative and cement quality ratio are 0.10-0.50:100.
It is particularly preferred that the Cellulose nanocrystal derivative is 0.20 with cement quality ratio:100.
By such scheme, the homogenization condition is to stir 5-10min under 4000-15000rpm rotating speeds.
By such scheme, the supersound process condition is to be ultrasonically treated 5-60min under power 400-800W.
Present invention additionally comprises according to the nanocrystalline enhancing cement paste material pouring molding of above-mentioned modified cellulose, maintenance, take off
The cement products that mould obtains.
Addition of the polycarboxylate water-reducer in cement, due to polycarboxylate water-reducer and the electric charge phase interaction of cement paste system
With so that polycarboxylic acids dehydragent is adsorbed in cement particle surface, is advantageous to the scattered of cement granules, is improved the stream of cement paste
Dynamic property is advantageous to construct.But adsorb and the lifting of degree of hydration is also resulted in while cement particle surface promotes scattered delay
Slowly, the progress of aquation is hindered or even sometimes, an important factor for degree of hydration is then cement paste strength enhancing, therefore water reducer
Addition can sometimes make strength enhancing slow.
CNC is a kind of poly- polysaccharide nano-crystalline palpus of high-crystallinity extracted from cellulose, has high strength and modulus ring
The good characteristics such as border close friend, while its surface can be used for chemical modification there is substantial amounts of hydroxyl, application prospect is extensive.By CNC
When being added in cement paste, due to its electric charge and steric hindrance, CNC can be made to be gathered spontaneously to aquation and unhydrated part
On interface, effect is similar to polycarboxylate water-reducer, contributes to the scattered of cement granules；Simultaneously as CNC has well in itself
Hydrophily, CNC can form a kind of water diffusion admittance on the interface of unhydrated particle, contribute to system reclaimed water to unhydrated portion
The diffusion divided, lift aquation intensity.However, the self aggregation characteristic due to nano material so that CNC is difficult to obtain in cement paste
To scattered, it is difficult to play due effect.
The present invention strengthens cement paste material using CNC-COOH and CNC-g-PEG, and the chemical modification to CNC surfaces can
It is scattered to effectively facilitate it：CNC carboxylated modification can make its surface be covered with identical electric charge, due to Coulomb repulsion effect
It is preferably scattered；In CNC surface graftings polyethylene glycol promoted using the significant space steric effect caused by macromolecular
Enter scattered.Two kinds of surfaces, which are modified, all combines the advantages of CNC and polycarboxylate water-reducer, promotes what CNC disperseed in cement
Lift degree of hydration simultaneously.It can be helped in the surface of cement granules, CNC hydrophily because CNC can be adsorbed in cement paste
Lift degree of hydration in diffusion of the moisture from liquid phase to cement granules, thus to CNC surface Modified lift its to the affine of water
Power can effectively facilitate hydration, lift the mechanical property of cement.But even if surface chemical modification, CNC are carried out to CNC
The degree of self aggregation is still very high in water, causes the aqueous dispersions viscosity of CNC class materials to increase, with being reduced during cement mix
CNC enhancing effect.Test result indicates that：Suitably homogeneous and supersound process then can significantly reduce CNC class materials in water
In self aggregation, the intensity of homogeneous and ultrasound is unsuitable too high, and too high physical dispersion intensity can cause the CNC class structures of matter
Destroy, play negative effect.
The beneficial effects of the present invention are：The present invention enters one by surface chemical modification and appropriate homogeneous, the method for ultrasound
Step improves dispersiveness of the cellulose nano material in cement, improves the degree of hydration of cement, lifts the mechanical property of cement slurry
Energy.CNC derivatives are added with the raising beneficial to cement paste material degree of hydration so as to improve rupture strength, CNC-COOH or
When CNC-g-PEG volumes are 0.20%, 3 days intensity of cement improve 30% and 40% respectively, and intensity also has 15% within 28 days
With 20% lifting.
Brief description of the drawings
Fig. 1 is the TEM photos of the CNC prepared by embodiment 1；
Fig. 2 is the TEM photos of the CNC-COOH prepared by embodiment 1；
Fig. 3 is the TEM photos of the CNC-g-PEG prepared by embodiment 1；
Fig. 4 is that the modified cellulose of embodiment 1 nanocrystalline (carboxylated) strengthens anti-folding of the cement paste test block in different larval instar
Intensity with CNC-COOH contents variation diagram；
Fig. 5 is that the modified cellulose of embodiment 1 nanocrystalline (surface grafting polyethylene glycol) strengthens cement paste test block in difference
The rupture strength of age with CNC-g-PEG contents variation diagram.
Embodiment
To make those skilled in the art more fully understand technical scheme, the present invention is made below in conjunction with the accompanying drawings into
One step is described in detail.
Main raw material(s) is as follows used in the embodiment of the present invention：Portland cement (Portland cement, PC), Hua Xinshui
The P.C 32.5R cement of mud limited company production；Cotton linter, content of cellulose >=95%；2,2,6,6- tetramethyl piperidines-
Nitrogen-oxide (TEMPO), AR；Amino polyethylene glycol (PEG-NH2), AR；N-hydroxysuccinimide (NHS), AR；1-(3-
Dimethylamino-propyl) -3- ethyl-carbodiimide hydrochlorides (EDC), AR.
Embodiment 1
CNC preparation：180g cotton linter is added to after crushing in the NaOH solution that 7L mass fractions are 2%, and stirring is anti-
Filtered repeatedly to filtrate pH after answering 12h to be placed at 45 DEG C dry 24h after neutrality.Dried product is added to 3.5L mass point
Number is 65% dense H2SO4Middle stirring reaction 45min, add a large amount of ice cubes and be quickly cooled to room temperature, then washing centrifugation 4 times, put
Dialysed in bag filter in distilled water one week, during which change first water daily, the freeze-drying of gained dispersion liquid can obtain fiber
Element is nanocrystalline.
Fig. 1 is the TEM photos of the CNC obtained by embodiment 1, and as can be seen from the figure CNC is diameter about 50-300nm, directly
Footpath about 5-15nm rod-like nano particle.
The preparation of carboxylated cellulose element nanocrystalline (CNC-COOH)：0.5g CNC ultrasonic disperses are in 50g water, ultrasonic disperse
15min, obtains CNC aqueous dispersions, and 14.75mg TEMPO and 162mg NaBr are dissolved in other 50mL distilled water and gradually dripped
It is added in CNC aqueous dispersions, 25gNaClO solution (NaClO concentration is 12wt%) is slowly dropped to wherein, uses 0.5mol/L
NaOH solution regulation pH of mixed 10.0 or so, react 3h at room temperature, then add 1mL ethanol and stop reaction, in magnetic force
The HCl solution regulation pH that 1mol/L is added under stirring condition is 5.0-6.0, reacts 30min, suspension 0.01mol/L HCl
Solution and distilled water centrifuge washing at least 5 times are finally freeze-dried, it is nanocrystalline to obtain carboxylated cellulose element to neutral.
Fig. 2 is the TEM photos of the CNC-COOH obtained by embodiment 1, as can be seen from the figure compared to unmodified CNC,
Obvious change does not occur for CNC-COOH pattern and size, and carboxylated does not destroy CNC surface topography.
The preparation of Cellulose nanocrystal grafting polyethylene glycol (CNC-g-PEG)：1g CNC-COOH are dispersed in dissolved with 2g
Amino polyethylene glycol PEG-NH2100mL water in, adjust pH in 7.5- with 0.5mol/L NaOH solution and HCl solution
8.0,0.38g NHS and 0.23g EDC, stirring reaction 24h are successively added, during which keeps pH in 7.5-8.0, then centrifugal water
Wash 3 times, be freeze-dried, obtain Cellulose nanocrystal grafting polyethylene glycol.
Fig. 3 is the TEM of the CNC-g-PEG obtained by embodiment 1 photo, it can be seen that surface grafting PEG does not have
There are the pattern and size for destroying CNC, but CNC-g-PEG reunion reduces a lot, CNC dispersiveness has obtained very big change
It is kind.
Sample proportioning be the ratio of mud 0.40, preparation CNC derivatives volume (accounting for cement quality percentage) is respectively 0,
0.01%th, 0.04%, 0.05%, 0.1%, 0.2%, 0.4%, 1%, 2% cement paste test block：By CNC-COOH or CNC-
G-PEG is distributed in water, homogeneous 5min under 4000rpm rotating speeds, then uses ultrasonic cell disintegration under conditions of power is 400W
Machine ultrasound 5min, then cement, CNC derivative dispersion liquids are sequentially added in agitated kettle, 120s is mixed slowly, stalls 15s, quickly
Shut down after stirring 120s, the pouring molding in 40mm × 40mm × 160mm moulds, be placed in 20 ± 1 DEG C, 24h is stood under 95%RH
After be stripped, and conserved under the same conditions.
The measure of cement paste intensity of test block：Above-mentioned cement paste test block is conserved to 3d, 7d, 28d respectively, with reference to GB/T
17671-1999 tests its 3d, 7d, 28d rupture strength on microcomputer control pressure-proof and snap-resistent all-in-one, and test result is shown in Fig. 4 and figure
5。
The intensity of cement briquette is shown as in Fig. 4 and Fig. 5 as CNC derivative volumes first increase the trend reduced afterwards,
When CNC-COOH or CNC-g-PEG volumes are 0.20%, 3 days intensity of cement improve 30% and 40%, 28 days intensity respectively
Also have 15% and 20% lifting, but with the increase of CNC derivative volumes, to during more than 1.0wt% cement briquette it is strong
Spend the decline that tends to be steady, the substantially following several respects of reason：1st, CNC can adsorb the surface of the cement granules in cement paste,
Playing the effect of steric hindrance contributes to the scattered of cement granules；And CNC can play promotion water on the surface of cement granules
Divide the effect of diffusion, contribute to the lifting of degree of hydration, above two, which acts on, causes the component containing CNC-COOH and CNC-g-PEG
Embodiment test block is higher than light water cement paste test block.2nd, CNC surface is modified as carboxylated (CNC-COOH) and grafting are poly-
Ethylene glycol (CNC-g-PEG) can promote CNC scattered in matrix, the difference is that the former is that Coulomb repulsion the latter is space
Steric hindrance, it is evident that the effect of steric hindrance is greater than Coulomb repulsion, moreover, CNC is dispersedly better, the work that can be played in matrix
With also bigger, the mechanical property of lifting also just becomes apparent from, therefore intensity of test block outline made from above-mentioned CNC-g-PEG embodiments
Higher than CNC-COOH.3 but work as CNC too high levels, reuniting effect is significantly greater than promotion of the Cellulose nanocrystal to heat evolution velocity
Effect, can turn into fault in material in hydrated cementitious late period, decline its intensity.
Embodiment 2
CNC preparation：With embodiment 1.
The preparation of carboxylated cellulose element nanocrystalline (CNC-COOH)：With embodiment 1.
The preparation of Cellulose nanocrystal grafting polyethylene glycol (CNC-g-PEG)：With embodiment 1.
Sample proportioning be the ratio of mud 0.40, preparation CNC derivatives volume (accounting for cement quality percentage) is respectively 0,
0.01%th, 0.04%, 0.05%, 0.1%, 0.2%, 0.4%, 1%, 2% cement paste test block：By CNC-COOH or CNC-
G-PEG is distributed in water, homogeneous 8min under 10000rpm rotating speeds, then uses ultrasonic cell disintegration under conditions of power is 600W
Machine ultrasound 30min, then cement, CNC derivative dispersion liquids are sequentially added in agitated kettle, 120s is mixed slowly, stalls 15s, soon
Shut down after speed stirring 120s, the pouring molding in 40mm × 40mm × 160mm moulds, be placed in 20 ± 1 DEG C, stood under 95%RH
It is stripped after 24h, is then conserved under the same conditions.
The measure of cement paste intensity of test block：Above-mentioned cement paste test block is conserved to 3d, 7d, 28d respectively, with reference to GB/T
17671-1999 tests its 3d, 7d, 28d rupture strength, test result and embodiment 1 on microcomputer control pressure-proof and snap-resistent all-in-one
It is close.
Embodiment 3
CNC preparation：With embodiment 1.
The preparation of carboxylated cellulose element nanocrystalline (CNC-COOH)：With embodiment 1.
The preparation of Cellulose nanocrystal grafting polyethylene glycol (CNC-g-PEG)：With embodiment 1.
Sample proportioning be the ratio of mud 0.40, preparation CNC derivatives volume (accounting for cement quality percentage) is respectively 0,
0.01%th, 0.04%, 0.05%, 0.1%, 0.2%, 0.4%, 1%, 2% cement paste test block：By CNC-COOH or CNC-
G-PEG is distributed in water, homogeneous 10min under 15000rpm rotating speeds, is then broken under conditions of power is 800W with ultrasonic cell
Broken machine ultrasound 60min, then cement, CNC derivative dispersion liquids are sequentially added in agitated kettle, 120s is mixed slowly, stalls 15s,
Shut down after quick stirring 120s, the pouring molding in 40mm × 40mm × 160mm moulds, be placed in 20 ± 1 DEG C, stood under 95%RH
It is stripped after 24h, is then conserved under the same conditions.
The measure of cement paste intensity of test block：Above-mentioned cement paste test block is conserved to 3d, 7d, 28d respectively, with reference to GB/T
17671-1999 tests its 3d, 7d, 28d rupture strength, test result and embodiment 1 on microcomputer control pressure-proof and snap-resistent all-in-one
It is close.
Claims (9)
- A kind of 1. nanocrystalline enhancing cement paste material of modified cellulose, it is characterised in that：The modified cellulose nanometer crystal class Enhancing cement paste material contains Cellulose nanocrystal derivative.
- 2. the nanocrystalline enhancing cement paste material of modified cellulose according to claim 1, it is characterised in that the fiber The nanocrystalline derivative of element is grafted polyethylene glycol for the plain nanocrystalline or Cellulose nanocrystal of carboxylated cellulose.
- 3. the nanocrystalline enhancing cement paste material of modified cellulose according to claim 2, it is characterised in that the carboxyl The nanocrystalline preparation method of cellulose is：Cellulose nanocrystal ultrasonic disperse is obtained into Cellulose nanocrystal in water to disperse Liquid, then TEMPO and the NaBr obtained aqueous solution soluble in water are added dropwise in CNC dispersion liquids, then NaClO is slowly added dropwise Solution, 3h is reacted at room temperature, it is 10.0 to adjust reacting liquid pH value with NaOH solution during reaction, adds ethanol and stops reaction, so It is 5.0-6.0, stirring reaction 30min to add HCl solution regulation reacting liquid pH value afterwards, then through centrifuge washing, be dried to obtain carboxyl Cellulose is nanocrystalline.
- 4. the nanocrystalline enhancing cement paste material of modified cellulose according to claim 2, it is characterised in that the fiber The preparation method of the nano-crystalline grafted polyethylene glycol of element is：By carboxylated cellulose element, nanocrystalline to be scattered in amino polyethylene glycol water-soluble CNC-COOH dispersion liquids are obtained in liquid, regulation dispersion liquid pH value is 7.5-8.0, adds NHS and EDC, stirring reaction 24h, then Post processing obtains Cellulose nanocrystal grafting polyethylene glycol.
- 5. a kind of preparation method of the nanocrystalline enhancing cement paste material of any described modified celluloses of claim 1-4, its It is characterised by that step is as follows：Cellulose nanocrystal derivative is mixed with water, mixed after homogenization, supersound process with cement With, be subsequently placed in mould and conserve, obtain modified cellulose it is nanocrystalline enhancing cement paste material.
- 6. preparation method according to claim 5, it is characterised in that the Cellulose nanocrystal derivative and cement quality Than for 0.01-2:100.
- 7. preparation method according to claim 5, it is characterised in that the homogenization condition turns for 4000-15000rpm The lower stirring 5-10min of speed.
- 8. preparation method according to claim 5, it is characterised in that the supersound process condition is in power 400-800W Lower supersound process 5-60min.
- 9. modified cellulose according to claim 1 is nanocrystalline to be strengthened cement paste material pouring molding, maintenance, is stripped The cement products arrived.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710773047.5A CN107473659B (en) | 2017-08-31 | 2017-08-31 | Modified cellulose nanocrystalline reinforced cement paste material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710773047.5A CN107473659B (en) | 2017-08-31 | 2017-08-31 | Modified cellulose nanocrystalline reinforced cement paste material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107473659A true CN107473659A (en) | 2017-12-15 |
| CN107473659B CN107473659B (en) | 2020-01-14 |
Family
ID=60604267
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710773047.5A Active CN107473659B (en) | 2017-08-31 | 2017-08-31 | Modified cellulose nanocrystalline reinforced cement paste material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107473659B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922493A (en) * | 2019-11-29 | 2020-03-27 | 济南圣泉集团股份有限公司 | Modified lignin nanocellulose, preparation method and application thereof, and modified mortar containing modified lignin nanocellulose |
| CN112555563A (en) * | 2020-12-16 | 2021-03-26 | 常州敏兆建设发展有限公司 | Drain pipe lining repairing material and repairing method applying same |
| CN114195451A (en) * | 2021-12-09 | 2022-03-18 | 北京科技大学 | Preparation method of nano-cellulose reinforced filling slurry |
| CN114591018A (en) * | 2022-01-26 | 2022-06-07 | 浙江建设职业技术学院 | Nano-cellulose/cellulose ether composite reinforced cement material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448007A (en) * | 2014-11-14 | 2015-03-25 | 中国科学院青岛生物能源与过程研究所 | Method for preparing nano-cellulose |
| CN105013018A (en) * | 2015-07-01 | 2015-11-04 | 西南交通大学 | Preparation method of carboxylated nano-crystal cellulose enhanced calcium phosphate support |
| CN106699905A (en) * | 2016-12-31 | 2017-05-24 | 武汉理工大学 | Preparation method of high-carboxyl-functionality cellulose nanocrystals |
-
2017
- 2017-08-31 CN CN201710773047.5A patent/CN107473659B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104448007A (en) * | 2014-11-14 | 2015-03-25 | 中国科学院青岛生物能源与过程研究所 | Method for preparing nano-cellulose |
| CN105013018A (en) * | 2015-07-01 | 2015-11-04 | 西南交通大学 | Preparation method of carboxylated nano-crystal cellulose enhanced calcium phosphate support |
| CN106699905A (en) * | 2016-12-31 | 2017-05-24 | 武汉理工大学 | Preparation method of high-carboxyl-functionality cellulose nanocrystals |
Non-Patent Citations (2)
| Title |
|---|
| 裴继诚: "《植物纤维化学》", 31 July 2012, 北京：中国轻工业出版社 * |
| 谢炎龙: "纳米晶体纤维素对水泥基复合材料性质的影响", 《万方数据库》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922493A (en) * | 2019-11-29 | 2020-03-27 | 济南圣泉集团股份有限公司 | Modified lignin nanocellulose, preparation method and application thereof, and modified mortar containing modified lignin nanocellulose |
| CN112555563A (en) * | 2020-12-16 | 2021-03-26 | 常州敏兆建设发展有限公司 | Drain pipe lining repairing material and repairing method applying same |
| CN112555563B (en) * | 2020-12-16 | 2023-11-03 | 常州敏兆建设发展有限公司 | Drain pipe lining repairing material and repairing method using same |
| CN114195451A (en) * | 2021-12-09 | 2022-03-18 | 北京科技大学 | Preparation method of nano-cellulose reinforced filling slurry |
| CN114591018A (en) * | 2022-01-26 | 2022-06-07 | 浙江建设职业技术学院 | Nano-cellulose/cellulose ether composite reinforced cement material and preparation method thereof |
| CN114591018B (en) * | 2022-01-26 | 2022-12-20 | 浙江建设职业技术学院 | Nano-cellulose/cellulose ether composite reinforced cement material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107473659B (en) | 2020-01-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107473659A (en) | A kind of nanocrystalline enhancing cement paste material of modified cellulose and preparation method thereof | |
| CN110156367A (en) | By the method for Industrial Solid Waste wet-milling preparation nanometer C-S-H gel early strength agent | |
| CN105566502B (en) | The preparation method of the renewable nano-cellulose film of water resistance | |
| CN102080343B (en) | Application of anion nano microcrystalline cellulose as paper reinforcer | |
| CN107382205A (en) | A kind of super high strength high performance fiber concrete of C160 strength grades and preparation method thereof | |
| CN101994153A (en) | Method for preparing modified calcium sulfate whisker by using desulfurization gypsum | |
| CN108164208A (en) | A kind of nano silicon dioxide regeneration concrete and preparation method thereof | |
| CN107601977A (en) | A kind of Cellulose nanocrystal enhancing cement paste material and preparation method thereof | |
| CN107285709B (en) | A kind of high-performance fiber concrete of C120 strength grade and preparation method thereof | |
| CN108676099A (en) | A kind of preparation method of oxidizing bacteria cellulose solution | |
| CN108383406A (en) | The method of modified coal ash | |
| CN109678427A (en) | Nanometer carbon black cement-base composite material and preparation method thereof | |
| CN107474343A (en) | The method that one kettle way prepares ascidian nano micro crystal cellulose/rubber nano composite material | |
| CN104692741A (en) | Straw cellulose fiber/cement-based composite material and preparation method thereof | |
| CN107352915A (en) | A kind of high-performance fiber concrete of C110 strength grades and preparation method thereof | |
| CN107352913A (en) | A kind of super high strength high performance fiber concrete of C180 strength grades and preparation method thereof | |
| CN107512888A (en) | A kind of high-performance fiber concrete of C140 strength grades and preparation method thereof | |
| CN107352912A (en) | A kind of super high strength high performance fiber concrete of C170 strength grades and preparation method thereof | |
| CN107324728A (en) | A kind of high-performance fiber concrete of C80 strength grades and preparation method thereof | |
| CN109987908A (en) | A kind of Environment-friendlymortar mortar and preparation method thereof | |
| CN113024211A (en) | High-toughness high-cohesiveness C150 strength ultrahigh-strength fiber concrete and preparation method thereof | |
| CN108103839A (en) | A kind of preparation method of modified calcium sulfate crystal whisker papermaking filler | |
| CN107324729B (en) | A kind of high-performance fiber concrete of C100 strength grade and preparation method thereof | |
| CN107298563B (en) | A kind of high-performance fiber concrete of C90 strength grade and preparation method thereof | |
| CN107512889B (en) | A kind of high-performance fiber concrete of C130 strength grade and preparation method thereof |
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 | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231108 Address after: 400021 15-5, Building 18, Shimahe Shanshui Jingyuan, Jiangbei District, Chongqing Patentee after: Chongqing Beirun Electromechanical Equipment Co.,Ltd. Address before: 430070 Hubei Province, Wuhan city Hongshan District Luoshi Road No. 122 Patentee before: WUHAN University OF TECHNOLOGY |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231123 Address after: 400023 10-3, Building 4, No. 36, Wulidian, Jiangbei District, Chongqing Patentee after: Huang Yi Address before: 400021 15-5, Building 18, Shimahe Shanshui Jingyuan, Jiangbei District, Chongqing Patentee before: Chongqing Beirun Electromechanical Equipment Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240221 Address after: 402760 No.92 Donglin Avenue, Biquan street, Bishan District, Chongqing Patentee after: Carbon Heng (Chongqing) Biomass New Materials Co.,Ltd. Country or region after: China Address before: 400023 10-3, Building 4, No. 36, Wulidian, Jiangbei District, Chongqing Patentee before: Huang Yi Country or region before: China |
|
| TR01 | Transfer of patent right |