CN115108753B - Anti-scouring agent for concrete material and application of anti-scouring agent in concrete material - Google Patents
Anti-scouring agent for concrete material and application of anti-scouring agent in concrete material Download PDFInfo
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- CN115108753B CN115108753B CN202210886487.2A CN202210886487A CN115108753B CN 115108753 B CN115108753 B CN 115108753B CN 202210886487 A CN202210886487 A CN 202210886487A CN 115108753 B CN115108753 B CN 115108753B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- 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
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- 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
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/0048—Fibrous materials
- C04B20/0068—Composite fibres, e.g. fibres with a core and sheath of different material
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- 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
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- 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
- C04B28/06—Aluminous cements
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- 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
- C04B28/06—Aluminous cements
- C04B28/065—Calcium aluminosulfate cements, e.g. cements hydrating into ettringite
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- 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
- C04B28/34—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 cold phosphate binders
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
- C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
- C08B37/009—Konjac gum or konjac mannan, i.e. beta-D-glucose and beta-D-mannose units linked by 1,4 bonds, e.g. from Amorphophallus species; Derivatives thereof
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4382—Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
- D04H1/43825—Composite fibres
- D04H1/43828—Composite fibres sheath-core
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/2038—Resistance against physical degradation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention discloses a scouring agent for a concrete material and application thereof in the concrete material, wherein the scouring agent is a natural polymer material; the natural polymer material is one or more of konjac gum, xanthan gum and guar gum; the natural polymer material is added in one or more of solution, hydrogel beads and micro-nano fibers when in use; adding the anti-scouring agent into raw materials for preparing concrete materials, and preparing any one of concrete, mortar and clean pulp civil engineering materials; the mixing amount of the scouring agent is 0.01-3% of the weight of the raw materials; the raw materials are one or more of cement, volcanic ash, hydraulic materials and active mixed materials. The anti-scouring agent has good anti-scouring effect, and can reduce the scouring quality loss rate of cement by more than 50%; the anti-scouring agent is a natural polymer material, has a simple doping mode, and is very easy to realize engineering application.
Description
Technical Field
The invention belongs to the field of chemical-building materials, and particularly relates to a scouring agent for a concrete material and application of the scouring agent in the concrete material.
Background
Along with the continuous development of hydraulic engineering such as cross-sea bridges, submarine tunnels, dams and the like, the importance of cement-based material grouting technology is gradually highlighted. Compared with the traditional cement-based grouting material which cannot form an effective seepage-proof curtain under the conditions of large seepage quantity, high-pressure large-flow water environment and the like, the underwater non-dispersed concrete improves the cohesiveness of the concrete by adding additives such as flocculating agent, thickening agent and the like, and the purpose of less separation of cementing materials during underwater construction is realized.
To meet the needs of infrastructure and concrete construction, various chemical admixtures are often used to find specific properties. The anti-scouring agent is a novel additive provided for underwater non-dispersed concrete, and has the main function of improving the anti-segregation and anti-scouring performance of the concrete by improving the viscosity, the water retention and the like of the concrete. The existing anti-scouring agent has few researches, most of the anti-scouring agent mainly uses synthetic polymer macromolecules, and meanwhile, the preparation process is complex and the anti-scouring effect is poor.
Disclosure of Invention
It is an object of the present invention to address at least the above problems and/or disadvantages and to provide at least the advantages described below.
To achieve these objects and other advantages and in accordance with the purpose of the invention, there is provided a scouring agent for concrete materials, characterized in that the scouring agent is a natural polymer material;
the natural polymer material is one or more of konjac gum, xanthan gum and guar gum;
the natural polymer material is purified before use, and the method comprises the following steps: weighing 4-6 parts by weight of natural polymer material, taking petroleum ether with the boiling range of 90-120 ℃ for complete infiltration, vibrating and stirring for 1-3 hours, pouring out the petroleum ether, and repeating degreasing for three times; adding the defatted natural polymer material into 150-250 parts of water, stirring to form uniform natural polymer material suspension, stirring at 50-70 ℃ in water bath temperature to dissolve completely, adding 100-150 parts of absolute ethyl alcohol for alcohol precipitation, and repeating dissolving and alcohol precipitation for three times to obtain crude natural polymer material; dissolving 0.5-1.5 parts of crude natural polymer material in 40-60 parts of water, sequentially adding 8-15 parts of chloroform and 8-15 parts of n-butanol, stirring for 10-30 min, centrifuging for 10-20 min under 4000-6000 r/min, separating denatured protein and impurity particles at the junction of a water layer and an organic solvent, repeating the process for 5 times, diluting the water phase with water, and filtering to remove tiny insoluble particles; precipitating natural polymer materials in the filtrate with ethanol, collecting precipitate, and freeze drying.
Preferably, the natural polymer material is added in one or more of solution, hydrogel beads and micro-nano fibers during use.
Preferably, when the natural polymer material is used as hydrogel, the preparation method comprises the following steps: according to the weight portion, 1 to 3 portions of natural polymer material are taken and added into 15 to 25 portions of water, and are stirred, 0.1 to 0.3 portion of 1mol/L NaOH solution is added, and the mixture is heated for 30 minutes at 60 ℃ and then is frozen and dried.
Preferably, when the natural polymer material is used as hydrogel beads, the preparation method comprises the following steps: preparing 1-3wt% of konjak gum solution, preparing a mixed solution of water and ethanol with the volume ratio of 1:3-5, adjusting the pH value to 12 to be used as a curing solution, and injecting and dripping the konjak gum solution into the curing solution at the speed of 0.3ml/h by using an injection pump to obtain the hydrogel beads.
Preferably, when the natural polymer material is used as micro-nano fiber, the preparation method comprises the following steps: dissolving natural polymer materials in a mixed solvent to obtain a natural polymer material shell spinning solution with the concentration of 5-10wt%; dissolving polyacrylonitrile in N, N-dimethylformamide and acetone in a volume ratio of 3:1 to obtain a polyacrylonitrile nuclear layer spinning solution with a concentration of 4-6wt%; and (3) respectively inputting the natural polymer material shell spinning solution and the polyacrylonitrile core spinning solution into the outer layer and the inner layer of the stainless steel coaxial needle by adopting high-voltage electrostatic spinning equipment, setting high-voltage electrostatic spraying conditions, and spraying the natural polymer material shell solution and the polyacrylonitrile core solution onto a tin foil receiving device in a high-voltage electrostatic manner to obtain the natural polymer material micro-nano fiber membrane.
Preferably, the mixed solvent is deionized water, ethylene glycol and formic acid with the volume ratio of 3-5:1:1;
the high-voltage electrostatic spraying conditions are as follows: the environment temperature is 50-60 ℃, the output voltage of the high-voltage power supply is 15-20 kV, the distance between the receiving device and the stainless steel coaxial needle spinneret orifice is 10-15 cm, the input speed of the polyacrylonitrile core spinning solution is 0.5-1 mL/h, and the input speed of the natural polymer material shell spinning solution is 3-5 mL/h; the inner diameter of the outer layer of the stainless steel coaxial needle is 1.2-1.6 mm, and the inner diameter of the inner layer is 0.5-0.8 mm.
Preferably, the modified solution is ultrasonically atomized into an atomized substance through an ultrasonic atomizer while high-voltage electrostatic spraying is performed, and the atomized substance is led to the continuously formed natural polymer material micro-nano fiber membrane; placing the obtained natural polymer material micro-nano fiber membrane into a baking oven, and preserving the temperature for 1-3 hours at 70-80 ℃;
the ultrasonic atomization frequency is 1.7MHz or 2.4MHz, and the atomization rate is 10-15 mL/min; the preparation method of the modified solution comprises the following steps: according to the weight portions, 3 to 5 portions of sodium hydroxide and 1 to 2 portions of sodium hyaluronate are added into 100 to 120 portions of water and stirred for 1 to 2 hours, thus obtaining the modified solution.
Preferably, the natural polymer material is used in combination with any one of water glass and water-based epoxy.
The invention also provides an application of the anti-scouring agent in concrete materials, wherein the anti-scouring agent is added into raw materials for preparing the concrete materials and is used for preparing any one of concrete, mortar and net-slurry civil engineering materials; the mixing amount of the scouring agent is 0.01-3% of the weight of the raw materials; the raw materials are one or more of cement, volcanic ash, hydraulic materials and active mixed materials.
Preferably, the cement is any one of silicate cement, aluminate cement, sulphoaluminate cement, iron aluminate cement, fluoroaluminate cement and phosphate cement.
The invention at least comprises the following beneficial effects:
the anti-scouring agent has good anti-scouring effect, and can reduce the scouring quality loss rate of cement by more than 50%; the anti-scouring agent is a natural polymer material, has a simple doping mode, and is very easy to realize engineering application.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 is an SEM image of konjac glucomannan used in the present invention;
FIG. 2 is an SEM image of konjak hydrogel prepared by the invention;
FIG. 3 is an SEM image of the konjac gel beads prepared according to the present invention;
fig. 4 is an SEM image of konjak micro-nano fiber prepared by the invention.
The specific embodiment is as follows:
the present invention is described in further detail below with reference to the drawings to enable those skilled in the art to practice the invention by referring to the description.
It will be understood that terms, such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
a scouring agent for concrete materials, wherein the scouring agent is konjak gum;
preparing cement slurry according to the following conditions: cement P42.5R, cement to cement ratio 0.5, laboratory temperature 18 ℃, humidity 70%; the addition amount of the konjak gum is 0.01% of the mass of the cement; when in use, the konjak gum is dissolved in water to prepare stable and uniform solution, and then cement is added to form cement paste;
the konjak gum is purified before use, and the method comprises the following steps: weighing 4g of konjak gum, fully soaking in petroleum ether with the boiling range of 90-120 ℃, vibrating and stirring for 2 hours, pouring out the petroleum ether, and repeating degreasing for three times; adding the defatted konjac glucomannan into 200mL of water, stirring to form uniform konjac glucomannan suspension, stirring at 60 ℃ in water bath temperature to completely dissolve, adding 135mL of absolute ethyl alcohol for alcohol precipitation, and repeating dissolving and alcohol precipitation for three times to obtain crude konjac glucomannan; dissolving 1g of crude konjak gum in 50mL of water, sequentially adding 10mL of chloroform and 10mL of n-butanol, stirring for 20min, centrifuging for 15 min at 5000r/min, separating denatured protein and impurity particles at the junction of a water layer and an organic solvent, repeating the process for 5 times, diluting the water phase with water, and filtering to remove tiny insoluble particles; precipitating konjac glucomannan in the filtrate with ethanol, collecting precipitate, and freeze drying.
Example 2:
a scouring agent for concrete materials, wherein the scouring agent is konjak gum;
preparing cement slurry according to the following conditions: cement P42.5R, cement to cement ratio 0.5, laboratory temperature 18 ℃, humidity 70%; the addition amount of the konjak gum is 0.02% of the mass of the cement; when in use, the konjak gum is dissolved in water to prepare stable and uniform solution, and then cement is added to form cement paste;
the konjak gum is purified before use, and the method comprises the following steps: weighing 4g of konjak gum, fully soaking in petroleum ether with the boiling range of 90-120 ℃, vibrating and stirring for 2 hours, pouring out the petroleum ether, and repeating degreasing for three times; adding the defatted konjac glucomannan into 200mL of water, stirring to form uniform konjac glucomannan suspension, stirring at 60 ℃ in water bath temperature to completely dissolve, adding 135mL of absolute ethyl alcohol for alcohol precipitation, and repeating dissolving and alcohol precipitation for three times to obtain crude konjac glucomannan; dissolving 1g of crude konjak gum in 50mL of water, sequentially adding 10mL of chloroform and 10mL of n-butanol, stirring for 20min, centrifuging for 15 min at 5000r/min, separating denatured protein and impurity particles at the junction of a water layer and an organic solvent, repeating the process for 5 times, diluting the water phase with water, and filtering to remove tiny insoluble particles; precipitating konjac glucomannan in the filtrate with ethanol, collecting precipitate, and freeze drying.
Example 3:
a scouring agent for concrete materials, wherein the scouring agent is konjak gum;
preparing cement slurry according to the following conditions: cement P42.5R, cement to cement ratio 0.5, laboratory temperature 18 ℃, humidity 70%; the addition amount of the konjak gum is 0.05% of the mass of the cement; when in use, the konjak gum is dissolved in water to prepare stable and uniform solution, and then cement is added to form cement paste;
the konjak gum is purified before use, and the method comprises the following steps: weighing 4g of konjak gum, fully soaking in petroleum ether with the boiling range of 90-120 ℃, vibrating and stirring for 2 hours, pouring out the petroleum ether, and repeating degreasing for three times; adding the defatted konjac glucomannan into 200mL of water, stirring to form uniform konjac glucomannan suspension, stirring at 60 ℃ in water bath temperature to completely dissolve, adding 135mL of absolute ethyl alcohol for alcohol precipitation, and repeating dissolving and alcohol precipitation for three times to obtain crude konjac glucomannan; dissolving 1g of crude konjak gum in 50mL of water, sequentially adding 10mL of chloroform and 10mL of n-butanol, stirring for 20min, centrifuging for 15 min at 5000r/min, separating denatured protein and impurity particles at the junction of a water layer and an organic solvent, repeating the process for 5 times, diluting the water phase with water, and filtering to remove tiny insoluble particles; precipitating konjac glucomannan in the filtrate with ethanol, collecting precipitate, and freeze drying.
Example 4:
a scouring agent for concrete materials, wherein the scouring agent is konjak gum;
preparing cement slurry according to the following conditions: cement P42.5R, cement to cement ratio 0.5, laboratory temperature 18 ℃, humidity 70%; the addition amount of the konjak gum is 0.1% of the mass of the cement; when in use, the konjak gum is dissolved in water to prepare stable and uniform solution, and then cement is added to form cement paste;
the konjak gum is purified before use, and the method comprises the following steps: weighing 4g of konjak gum, fully soaking in petroleum ether with the boiling range of 90-120 ℃, vibrating and stirring for 2 hours, pouring out the petroleum ether, and repeating degreasing for three times; adding the defatted konjac glucomannan into 200mL of water, stirring to form uniform konjac glucomannan suspension, stirring at 60 ℃ in water bath temperature to completely dissolve, adding 135mL of absolute ethyl alcohol for alcohol precipitation, and repeating dissolving and alcohol precipitation for three times to obtain crude konjac glucomannan; dissolving 1g of crude konjak gum in 50mL of water, sequentially adding 10mL of chloroform and 10mL of n-butanol, stirring for 20min, centrifuging for 15 min at 5000r/min, separating denatured protein and impurity particles at the junction of a water layer and an organic solvent, repeating the process for 5 times, diluting the water phase with water, and filtering to remove tiny insoluble particles; precipitating konjac glucomannan in the filtrate with ethanol, collecting precipitate, and freeze drying.
Example 5:
a scouring agent for concrete materials, wherein the scouring agent is konjak gum;
preparing cement slurry according to the following conditions: cement P42.5R, cement to cement ratio 0.5, laboratory temperature 18 ℃, humidity 70%; the addition amount of the konjak gum is 0.2% of the mass of the cement; when in use, the konjak gum is dissolved in water to prepare stable and uniform solution, and then cement is added to form cement paste;
the konjak gum is purified before use, and the method comprises the following steps: weighing 4g of konjak gum, fully soaking in petroleum ether with the boiling range of 90-120 ℃, vibrating and stirring for 2 hours, pouring out the petroleum ether, and repeating degreasing for three times; adding the defatted konjac glucomannan into 200mL of water, stirring to form uniform konjac glucomannan suspension, stirring at 60 ℃ in water bath temperature to completely dissolve, adding 135mL of absolute ethyl alcohol for alcohol precipitation, and repeating dissolving and alcohol precipitation for three times to obtain crude konjac glucomannan; dissolving 1g of crude konjak gum in 50mL of water, sequentially adding 10mL of chloroform and 10mL of n-butanol, stirring for 20min, centrifuging for 15 min at 5000r/min, separating denatured protein and impurity particles at the junction of a water layer and an organic solvent, repeating the process for 5 times, diluting the water phase with water, and filtering to remove tiny insoluble particles; precipitating konjac glucomannan in the filtrate with ethanol, collecting precipitate, and freeze drying.
Comparative example 1:
preparing cement slurry according to the following conditions: cement P42.5R, cement to cement ratio 0.5, laboratory temperature 18 ℃, humidity 70%;
the method for measuring the scouring mass loss rate comprises the following steps:
weighing 50g of cement paste, placing into a culture dish, standing for 30min, placing the culture dish into a 2L beaker, and adding simulated seawater (77.8% NaCl and 10.9% MgCl) into the beaker 2 、4.7％MgSO 4 、3.6％CaSO 4 、2.5％K 2 SO 4 、0.3％CaCO 3 、0.2％MgBr 2 ) The distance between the rotor of the stirrer and the bottom of the beaker was adjusted by 8cm, the rotation speed was set to 280r/min, the rotation was continued for 5min, and the scouring loss rate (mass) was calculatedLoss rate%) and the results were repeated three times.
The scouring agents provided in examples 1 to 5 and comparative example 1 above were applied to cement admixtures, and the scouring mass loss rate thereof was measured, and the results are shown in Table 1;
TABLE 1
| Examples | Mass loss rate/% |
| 1 | 87.8 |
| 2 | 86.5 |
| 3 | 4.3 |
| 4 | 1.0 |
| 5 | 0.3 |
| Comparative example 1 | 89 |
As can be seen from table 1: the scouring agent can effectively reduce the scouring quality loss rate of cement-based materials.
Example 6:
when the modified konjac glucomannan is used as hydrogel, the preparation method comprises the following steps: weighing 2g of konjak gum refined powder, dissolving in 40mL of water, stirring and dissolving, adding 200uL of 1mol/L NaOH solution, heating at 60 ℃ for 30min, and then freeze-drying to obtain konjak hydrogel; preparing cement slurry according to the following conditions: cement P42.5R, cement to cement ratio 0.5, laboratory temperature 18 ℃, humidity 70%; the addition amount of the konjak glue gel is 0.2 weight percent of the cement mass;
the konjak gum is purified before use, and the method comprises the following steps: weighing 4g of konjak gum, fully soaking in petroleum ether with the boiling range of 90-120 ℃, vibrating and stirring for 2 hours, pouring out the petroleum ether, and repeating degreasing for three times; adding the defatted konjac glucomannan into 200mL of water, stirring to form uniform konjac glucomannan suspension, stirring at 60 ℃ in water bath temperature to completely dissolve, adding 135mL of absolute ethyl alcohol for alcohol precipitation, and repeating dissolving and alcohol precipitation for three times to obtain crude konjac glucomannan; dissolving 1g of crude konjak gum in 50mL of water, sequentially adding 10mL of chloroform and 10mL of n-butanol, stirring for 20min, centrifuging for 15 min at 5000r/min, separating denatured protein and impurity particles at the junction of a water layer and an organic solvent, repeating the process for 5 times, diluting the water phase with water, and filtering to remove tiny insoluble particles; precipitating konjac glucomannan in the filtrate with ethanol, collecting precipitate, and freeze drying.
Example 7:
preparing 2wt% of konjak gum solution, preparing a mixed solution of water and ethanol with the volume ratio of 1:3, adjusting the pH value to 12 to be used as a curing solution, and injecting the konjak gum solution into the curing solution at the speed of 0.3mL/h by using an injection pump; aging for 2 hours after injection, filtering, and freeze-drying to obtain konjak glue gel beads; preparing cement slurry according to the following conditions: cement P42.5R, cement to cement ratio 0.5, laboratory temperature 18 ℃, humidity 70%; the addition amount of the konjak glue gel beads is 0.2 weight percent of the mass of cement;
the konjak gum is purified before use, and the method comprises the following steps: weighing 4g of konjak gum, fully soaking in petroleum ether with the boiling range of 90-120 ℃, vibrating and stirring for 2 hours, pouring out the petroleum ether, and repeating degreasing for three times; adding the defatted konjac glucomannan into 200mL of water, stirring to form uniform konjac glucomannan suspension, stirring at 60 ℃ in water bath temperature to completely dissolve, adding 135mL of absolute ethyl alcohol for alcohol precipitation, and repeating dissolving and alcohol precipitation for three times to obtain crude konjac glucomannan; dissolving 1g of crude konjak gum in 50mL of water, sequentially adding 10mL of chloroform and 10mL of n-butanol, stirring for 20min, centrifuging for 15 min at 5000r/min, separating denatured protein and impurity particles at the junction of a water layer and an organic solvent, repeating the process for 5 times, diluting the water phase with water, and filtering to remove tiny insoluble particles; precipitating konjac glucomannan in the filtrate with ethanol, collecting precipitate, and freeze drying.
The anti-washout agents provided in the above examples 5 and examples 6 to 7 were applied to cement admixtures, and their anti-washout effects were measured, and the results are shown in Table 2;
TABLE 2
| Examples | Mass loss rate/% |
| 5 | 0.3 |
| 6 | 8.6 |
| 7 | 17.4 |
| Comparative example 1 | 89 |
As can be seen from table 2: the addition of hydrogel or hydrogel beads can also improve the anti-scouring performance of the cement paste.
Example 8:
a scouring agent for concrete materials, wherein the scouring agent is konjak gum;
preparing cement slurry according to the following conditions: cement P42.5R, cement to cement ratio 0.5, laboratory temperature 18 ℃, humidity 70%; the addition amount of the konjak micro-nano fiber is 0.05% of the mass of the cement;
the preparation method of the konjak micro-nano fiber membrane comprises the following steps: dissolving konjak glucomannan in a mixed solvent of deionized water, ethylene glycol and formic acid in a volume ratio of 4:1:1 to obtain konjak glucomannan shell spinning solution with a concentration of 6 wt%; dissolving polyacrylonitrile in N, N-dimethylformamide and acetone in a volume ratio of 3:1 to obtain a polyacrylonitrile nuclear layer spinning solution with a concentration of 4 wt%; respectively inputting a natural high-molecular material shell spinning solution and a polyacrylonitrile core spinning solution into an outer layer and an inner layer of a stainless steel coaxial needle by adopting high-voltage electrostatic spinning equipment, setting high-voltage electrostatic spraying conditions, and spraying the natural high-molecular material shell solution and the polyacrylonitrile core solution onto a tin foil receiving device to obtain a konjak micro-nano fiber membrane; pulverizing rhizoma Amorphophalli micro-nano fiber membrane in pulverizer, and adding into cement to prepare cement paste; because the polyacrylonitrile has more excellent electrospinning property and mechanical property than the konjak glucomannan, the polyacrylonitrile is adopted as the nuclear layer of the konjak micro-nano fiber film, so that the mechanical property of the konjak micro-nano fiber film can be increased, the combination of the konjak micro-nano fiber film in cement paste is further more stable, and the anti-scouring property of the konjak micro-nano fiber film is further improved.
The high-voltage electrostatic spraying conditions are as follows: the environment temperature is 55 ℃, the output voltage of the high-voltage power supply is 15kV, the distance between the receiving device and the spinning nozzle of the stainless steel coaxial needle head is 10cm, the input speed of the polyacrylonitrile core spinning solution is 0.5mL/h, and the input speed of the konjac glucomannan shell spinning solution is 4mL/h; the inner diameter of the outer layer of the stainless steel coaxial needle is 1.5mm, and the inner diameter of the inner layer is 0.5mm;
the konjak glucomannan is purified before use, and the method comprises the following steps: weighing 4g of konjak glucomannan, taking petroleum ether with the boiling range of 90-120 ℃ for complete infiltration, vibrating and stirring for 2 hours, pouring out the petroleum ether, and repeating degreasing for three times; adding the defatted konjac glucomannan into 200mL of water, stirring to form uniform konjac glucomannan suspension, stirring at 60 ℃ in water bath temperature to completely dissolve, adding 135mL of absolute ethyl alcohol for alcohol precipitation, and repeating dissolving and alcohol precipitation for three times to obtain crude konjac glucomannan; dissolving 1g of crude konjak gum in 50mL of water, sequentially adding 10mL of chloroform and 10mL of n-butanol, stirring for 20min, centrifuging for 15 min at 5000r/min, separating denatured protein and impurity particles at the junction of a water layer and an organic solvent, repeating the process for 5 times, diluting the water phase with water, and filtering to remove tiny insoluble particles; precipitating konjac glucomannan in the filtrate with ethanol, collecting precipitate, and freeze drying;
example 9:
a scouring agent for concrete materials, wherein the scouring agent is konjak gum;
preparing cement slurry according to the following conditions: cement P42.5R, cement to cement ratio 0.5, laboratory temperature 18 ℃, humidity 70%; the addition amount of the konjak micro-nano fiber is 0.2% of the mass of the cement;
the preparation method of the konjak micro-nano fiber membrane comprises the following steps: dissolving konjak glucomannan in a mixed solvent of deionized water, ethylene glycol and formic acid in a volume ratio of 4:1:1 to obtain konjak glucomannan shell spinning solution with a concentration of 6 wt%; dissolving polyacrylonitrile in N, N-dimethylformamide and acetone in a volume ratio of 3:1 to obtain a polyacrylonitrile nuclear layer spinning solution with a concentration of 4 wt%; respectively inputting a natural high-molecular material shell spinning solution and a polyacrylonitrile core spinning solution into an outer layer and an inner layer of a stainless steel coaxial needle by adopting high-voltage electrostatic spinning equipment, setting high-voltage electrostatic spraying conditions, and spraying the natural high-molecular material shell solution and the polyacrylonitrile core solution onto a tin foil receiving device to obtain a konjak micro-nano fiber membrane; pulverizing rhizoma Amorphophalli micro-nano fiber membrane in pulverizer, and adding into cement to prepare cement paste;
the high-voltage electrostatic spraying conditions are as follows: the environment temperature is 55 ℃, the output voltage of the high-voltage power supply is 15kV, the distance between the receiving device and the spinning nozzle of the stainless steel coaxial needle head is 10cm, the input speed of the polyacrylonitrile core spinning solution is 0.5mL/h, and the input speed of the konjac glucomannan shell spinning solution is 4mL/h; the inner diameter of the outer layer of the stainless steel coaxial needle is 1.5mm, and the inner diameter of the inner layer is 0.5mm;
the konjak glucomannan is purified before use, and the method comprises the following steps: weighing 4g of konjak glucomannan, taking petroleum ether with the boiling range of 90-120 ℃ for complete infiltration, vibrating and stirring for 2 hours, pouring out the petroleum ether, and repeating degreasing for three times; adding the defatted konjac glucomannan into 200mL of water, stirring to form uniform konjac glucomannan suspension, stirring at 60 ℃ in water bath temperature to completely dissolve, adding 135mL of absolute ethyl alcohol for alcohol precipitation, and repeating dissolving and alcohol precipitation for three times to obtain crude konjac glucomannan; dissolving 1g of crude konjak gum in 50mL of water, sequentially adding 10mL of chloroform and 10mL of n-butanol, stirring for 20min, centrifuging for 15 min at 5000r/min, separating denatured protein and impurity particles at the junction of a water layer and an organic solvent, repeating the process for 5 times, diluting the water phase with water, and filtering to remove tiny insoluble particles; precipitating konjac glucomannan in the filtrate with ethanol, collecting precipitate, and freeze drying;
example 10:
a scouring agent for concrete materials, wherein the scouring agent is konjak gum;
preparing cement slurry according to the following conditions: cement P42.5R, cement to cement ratio 0.5, laboratory temperature 18 ℃, humidity 70%; the addition amount of the konjak micro-nano fiber is 0.05% of the mass of the cement;
the preparation method of the konjak micro-nano fiber membrane comprises the following steps: dissolving konjak glucomannan in a mixed solvent of deionized water, ethylene glycol and formic acid in a volume ratio of 4:1:1 to obtain konjak glucomannan shell spinning solution with a concentration of 6 wt%; dissolving polyacrylonitrile in N, N-dimethylformamide and acetone in a volume ratio of 3:1 to obtain a polyacrylonitrile nuclear layer spinning solution with a concentration of 4 wt%; respectively inputting a natural high polymer material shell spinning solution and a polyacrylonitrile core spinning solution into an outer layer and an inner layer of a stainless steel coaxial needle by adopting high-voltage electrostatic spinning equipment, setting high-voltage electrostatic spraying conditions, spraying the natural high polymer material shell solution and the polyacrylonitrile core solution onto a tin foil receiving device in a high-voltage electrostatic manner to obtain a konjak micro-nanofiber membrane, simultaneously carrying out ultrasonic atomization on the modified solution through an ultrasonic atomizer to obtain an atomized matter, and leading the atomized matter to the continuously formed natural high polymer material micro-nanofiber membrane; placing the obtained konjak micro-nano fiber film in a baking oven, preserving heat for 2 hours at 75 ℃ to obtain the konjak micro-nano fiber film, and adding the konjak micro-nano fiber film into cement to prepare cement paste after being crushed by a crusher; the ultrasonic atomization frequency is 1.7MHz, and the atomization rate is 12mL/min; the preparation method of the modified solution comprises the following steps: 5g of sodium hydroxide and 1g of sodium hyaluronate were added to 120g of water and stirred for 1.5 hours to obtain a modified solution.
The high-voltage electrostatic spraying conditions are as follows: the environment temperature is 55 ℃, the output voltage of the high-voltage power supply is 15kV, the distance between the receiving device and the spinning nozzle of the stainless steel coaxial needle head is 10cm, the input speed of the polyacrylonitrile core spinning solution is 0.5mL/h, and the input speed of the konjac glucomannan shell spinning solution is 4mL/h; the inner diameter of the outer layer of the stainless steel coaxial needle is 1.5mm, and the inner diameter of the inner layer is 0.5mm;
the konjak glucomannan is purified before use, and the method comprises the following steps: weighing 4g of konjak glucomannan, taking petroleum ether with the boiling range of 90-120 ℃ for complete infiltration, vibrating and stirring for 2 hours, pouring out the petroleum ether, and repeating degreasing for three times; adding the defatted konjac glucomannan into 200mL of water, stirring to form uniform konjac glucomannan suspension, stirring at 60 ℃ in water bath temperature to completely dissolve, adding 135mL of absolute ethyl alcohol for alcohol precipitation, and repeating dissolving and alcohol precipitation for three times to obtain crude konjac glucomannan; dissolving 1g of crude konjak gum in 50mL of water, sequentially adding 10mL of chloroform and 10mL of n-butanol, stirring for 20min, centrifuging for 15 min at 5000r/min, separating denatured protein and impurity particles at the junction of a water layer and an organic solvent, repeating the process for 5 times, diluting the water phase with water, and filtering to remove tiny insoluble particles; precipitating konjac glucomannan in the filtrate with ethanol, collecting precipitate, and freeze drying;
example 11:
a scouring agent for concrete materials, wherein the scouring agent is konjak gum;
preparing cement slurry according to the following conditions: cement P42.5R, cement to cement ratio 0.5, laboratory temperature 18 ℃, humidity 70%; the addition amount of the konjak micro-nano fiber is 0.2% of the mass of the cement;
the preparation method of the konjak micro-nano fiber membrane comprises the following steps: dissolving konjak glucomannan in a mixed solvent of deionized water, ethylene glycol and formic acid in a volume ratio of 4:1:1 to obtain konjak glucomannan shell spinning solution with a concentration of 6 wt%; dissolving polyacrylonitrile in N, N-dimethylformamide and acetone in a volume ratio of 3:1 to obtain a polyacrylonitrile nuclear layer spinning solution with a concentration of 4 wt%; respectively inputting a natural high polymer material shell spinning solution and a polyacrylonitrile core spinning solution into an outer layer and an inner layer of a stainless steel coaxial needle by adopting high-voltage electrostatic spinning equipment, setting high-voltage electrostatic spraying conditions, spraying the natural high polymer material shell solution and the polyacrylonitrile core solution onto a tin foil receiving device in a high-voltage electrostatic manner to obtain a konjak micro-nanofiber membrane, simultaneously carrying out ultrasonic atomization on the modified solution through an ultrasonic atomizer to obtain an atomized matter, and leading the atomized matter to the continuously formed natural high polymer material micro-nanofiber membrane; placing the obtained konjak micro-nano fiber film in a baking oven, preserving heat for 2 hours at 75 ℃ to obtain the konjak micro-nano fiber film, and adding the konjak micro-nano fiber film into cement to prepare cement paste after being crushed by a crusher; the ultrasonic atomization frequency is 1.7MHz, and the atomization rate is 12mL/min; the preparation method of the modified solution comprises the following steps: 5g of sodium hydroxide and 1g of sodium hyaluronate were added to 120g of water and stirred for 1.5 hours to obtain a modified solution.
The high-voltage electrostatic spraying conditions are as follows: the environment temperature is 55 ℃, the output voltage of the high-voltage power supply is 15kV, the distance between the receiving device and the spinning nozzle of the stainless steel coaxial needle head is 10cm, the input speed of the polyacrylonitrile core spinning solution is 0.5mL/h, and the input speed of the konjac glucomannan shell spinning solution is 4mL/h; the inner diameter of the outer layer of the stainless steel coaxial needle is 1.5mm, and the inner diameter of the inner layer is 0.5mm;
the konjak glucomannan is purified before use, and the method comprises the following steps: weighing 4g of konjak glucomannan, taking petroleum ether with the boiling range of 90-120 ℃ for complete infiltration, vibrating and stirring for 2 hours, pouring out the petroleum ether, and repeating degreasing for three times; adding the defatted konjac glucomannan into 200mL of water, stirring to form uniform konjac glucomannan suspension, stirring at 60 ℃ in water bath temperature to completely dissolve, adding 135mL of absolute ethyl alcohol for alcohol precipitation, and repeating dissolving and alcohol precipitation for three times to obtain crude konjac glucomannan; dissolving 1g of crude konjak gum in 50mL of water, sequentially adding 10mL of chloroform and 10mL of n-butanol, stirring for 20min, centrifuging for 15 min at 5000r/min, separating denatured protein and impurity particles at the junction of a water layer and an organic solvent, repeating the process for 5 times, diluting the water phase with water, and filtering to remove tiny insoluble particles; precipitating konjac glucomannan in the filtrate with ethanol, collecting precipitate, and freeze drying;
the anti-scour agents provided in examples 8 to 11 above were applied to cement admixtures, and the anti-scour effects thereof were measured, and the results are shown in Table 3;
TABLE 3 Table 3
As can be seen from table 3: the addition mode of konjak micro-nano fibers can also improve the anti-scouring performance of cement paste.
Example 12:
a scouring agent for concrete materials, wherein the scouring agent is xanthan gum;
example 13:
a kind of anti-scouring agent for concrete material, this anti-scouring agent is guar gum.
Although embodiments of the present invention have been disclosed above, it is not limited to the details and embodiments shown and described, it is well suited to various fields of use for which the invention would be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the specific details and illustrations shown and described herein, without departing from the general concepts defined in the claims and their equivalents.
Claims (3)
1. The anti-scouring agent for the concrete material is characterized in that the anti-scouring agent is a natural polymer material;
the natural polymer material is one or more of konjac gum, xanthan gum and guar gum;
the natural polymer material is purified before use, and the method comprises the following steps: weighing 4-6 parts by weight of natural polymer material, taking petroleum ether with the boiling range of 90-120 ℃ for complete infiltration, vibrating and stirring for 1-3 hours, pouring out the petroleum ether, and repeating degreasing for three times; adding the degreased natural polymer material into 150-250 parts of water, stirring to form uniform natural polymer material suspension, stirring at 50-70 ℃ in water bath temperature to completely dissolve, adding 100-150 parts of absolute ethyl alcohol for alcohol precipitation, and repeatedly dissolving and alcohol precipitating for three times to obtain a crude natural polymer material; dissolving 0.5-1.5 parts of crude natural polymer material in 40-60 parts of water, sequentially adding 8-15 parts of chloroform and 8-15 parts of n-butanol, stirring for 10-30 min, centrifuging for 10-20 min under the condition of 4000-6000 r/min, separating denatured protein and impurity particles at the junction of a water layer and an organic solvent, repeating the process for 5 times, diluting the water phase with water, and filtering to remove tiny insoluble particles; precipitating natural polymer materials in the filtrate with ethanol, collecting precipitate, and freeze drying;
the natural polymer material is added in the mode of micro-nano fiber when in use;
when the natural polymer material is used as micro-nano fiber, the preparation method comprises the following steps: dissolving a natural polymer material in a mixed solvent to obtain a natural polymer material shell spinning solution with the concentration of 5-10wt%; dissolving polyacrylonitrile in N, N-dimethylformamide and acetone in a volume ratio of 3:1 to obtain a polyacrylonitrile nuclear layer spinning solution with a concentration of 4-6wt%; respectively inputting a natural high polymer material shell spinning solution and a polyacrylonitrile core spinning solution into an outer layer and an inner layer of a stainless steel coaxial needle by adopting high-voltage electrostatic spinning equipment, setting high-voltage electrostatic spraying conditions, and spraying the natural high polymer material shell spinning solution and the polyacrylonitrile core spinning solution onto a tin foil receiving device to obtain a natural high polymer material micro-nano fiber membrane;
the mixed solvent is deionized water, ethylene glycol and formic acid with the volume ratio of 3-5:1:1;
the high-voltage electrostatic spraying conditions are as follows: the environment temperature is 50-60 ℃, the output voltage of the high-voltage power supply is 15-20 kV, the distance between the receiving device and the stainless steel coaxial needle spinneret orifice is 10-15 cm, the input speed of the polyacrylonitrile core spinning solution is 0.5-1 mL/h, and the input speed of the natural polymer material shell spinning solution is 3-5 mL/h; the inner diameter of the outer layer of the stainless steel coaxial needle is 1.2-1.6 mm, and the inner diameter of the inner layer is 0.5-0.8 mm.
2. The anti-scouring agent for concrete materials according to claim 1, wherein the modified solution is ultrasonically atomized into an atomized substance by an ultrasonic atomizer while being sprayed under high pressure, and the atomized substance is led to the continuously formed natural polymer material micro-nanofiber membrane; placing the obtained natural polymer material micro-nano fiber membrane in an oven, and preserving heat for 1-3 hours at 70-80 ℃;
the ultrasonic atomization frequency is 1.7MHz or 2.4MHz, and the atomization rate is 10-15 mL/min; the preparation method of the modified solution comprises the following steps: and 3-5 parts of sodium hydroxide and 1-2 parts of sodium hyaluronate are added into 100-120 parts of water according to parts by weight, and the mixture is stirred for 1-2 hours to obtain a modified solution.
3. Use of an anti-scour agent according to any one of claims 1 to 2 in concrete materials, characterized in that the anti-scour agent is added to the raw materials for preparing the net-work civil engineering material; the raw materials are any one of silicate cement, aluminate cement, sulphoaluminate cement, iron aluminate cement, fluoroaluminate cement and phosphate cement; the mixing amount of the anti-scouring agent is 0.01% -3% of the weight of the raw materials.
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