CN112210119B - Underwater high-strength epoxy mortar treated by filler super-hydrophobicity and preparation method thereof - Google Patents

Underwater high-strength epoxy mortar treated by filler super-hydrophobicity and preparation method thereof Download PDF

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CN112210119B
CN112210119B CN202011051510.3A CN202011051510A CN112210119B CN 112210119 B CN112210119 B CN 112210119B CN 202011051510 A CN202011051510 A CN 202011051510A CN 112210119 B CN112210119 B CN 112210119B
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CN112210119A (en
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杜祥建
李光辉
戚佳飞
黄正强
张营
辛保种
徐静
冯伟利
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Henan Juyan Material Technology Co ltd
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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Abstract

The invention belongs to the technical field of underwater epoxy repair mortar, and particularly relates to underwater high-strength epoxy mortar subjected to filler super-hydrophobic treatment and a preparation method thereof. The super-hydrophobic inorganic filler is prepared from 10-30 parts of water, 10-30 parts of a shell forming material, 1-5 parts of an emulsifier, 10-30 parts of alkyl silane and 60-100 parts of an inorganic filler; the underwater high-strength epoxy mortar is prepared from super-hydrophobic inorganic filler and other raw and auxiliary materials; the specific surface area of the filler is increased by carrying out alkali etching treatment on the filler, so that the interface bonding force between the alkyl silane with long carbon chains and the filler is improved, and the hydrophobic property of the surface of the filler is further enhanced; the super-hydrophobic inorganic filler prepared by the long-carbon-chain alkyl silane has excellent hydrophobic property; the underwater high-strength epoxy mortar prepared by the super-hydrophobic inorganic filler has good bonding strength and stability.

Description

Underwater high-strength epoxy mortar treated by filler super-hydrophobicity and preparation method thereof
Technical Field
The invention belongs to the technical field of underwater epoxy repair mortar, and particularly relates to underwater high-strength epoxy mortar subjected to filler super-hydrophobic treatment and a preparation method thereof.
Background
Various epoxy bonding materials taking epoxy resin as a basic raw material are widely applied to the repair treatment of concrete defects or cracks of hydraulic engineering, and a good effect is achieved. However, the curing agent and the filler system of the common epoxy repair material both contain more hydrophilic groups, so that the adhesive property on a dry surface is good, the epoxy repair material is difficult to be well cured in low-temperature, high-humidity and underwater environments due to the intervention of more water, and the filler is mostly hydrophilic, so that the epoxy repair material can be quickly wetted and wrapped by water when meeting water and can be quickly dispersed in water, and the epoxy repair material is difficult to form good combination and compatibility with a resin system. Even if the curing is possible, the resin and the base surface have a water film, and the filler is dispersed in water, so that the resin hardly has any adhesion, strength and durability, and the resin may be peeled off or cracked by slight water washing.
In recent years, many studies have been made on underwater curable epoxy curing agents. At the earliest, a scholars utilizes a Mannich reaction to modify amines by introducing a phenolic aldehyde skeleton, the effect is very obvious, the problem of water resistance of the traditional amine curing agent is solved, the underwater curing is fast, but the curing shrinkage of the curing agent is large, and the bonding strength is influenced. Then, scholars improve the defect of curing shrinkage by introducing fatty amine, and have good water resistance and long-term use. In order to improve the compatibility between the resin and the filler, some scholars modify the filler by selecting the silane with short carbon chains so as to ensure that the filler is well compatible with the resin and improve the overall strength and long-term durability. However, most of hydrophobic groups of the silane coupling agent are short-carbon-chain epoxy, amino and alkyl alkenyl, and the carbon chain of the hydrophobic group is too short to form a completely hydrophobic state, so that the compatibility of the silane coupling agent with epoxy resin is improved. The method is still general in effect, the filler cannot be completely wrapped by the hydrophobic group to achieve the purpose of completely hydrophobic, and on the contrary, the hydrophilic group of the silane coupling agent in the resin is exposed, but the method is not beneficial to the removal of a water film between the resin and a base material, so that the bonding strength between the resin and the base material is reduced.
Disclosure of Invention
The invention aims to provide filler super-hydrophobic treated underwater high-strength epoxy mortar with good hydrophobicity and good bonding strength with a base material and a preparation method thereof.
Based on the purpose, the invention adopts the following technical scheme: a super-hydrophobic inorganic filler is prepared from the following raw materials in parts by mass: 10-30 parts of water, 10-30 parts of a shell forming material, 1-5 parts of an emulsifier, 10-30 parts of alkyl silane and 60-100 parts of an inorganic filler.
Preferably, the super-hydrophobic inorganic filler is prepared from the following raw materials in parts by mass: 20 parts of water, 20 parts of shell forming materials, 1 part of emulsifying agent, 20 parts of alkyl silane and 80 parts of inorganic filler.
Preferably, the alkylsilane is at least one of linear alkylsilane and branched alkylsilane; the length of a carbon chain in the straight chain alkyl silane or the branched alkyl silane is 3-14.
Preferably, the emulsifier is any one or two of tween 80, span 20 and OP-10.
Preferably, the shell-forming material is any one or two of polyvinyl alcohol, hydroxyethyl cellulose ether, hydroxypropyl methyl cellulose ether.
Preferably, the inorganic filler is any one or more of quartz stone, quartz powder, calcium carbonate, and barium sulfate.
The method for preparing the super-hydrophobic inorganic filler by using the raw material components of the super-hydrophobic inorganic filler comprises the following steps:
(1) carrying out alkali etching pretreatment on the inorganic filler;
(2) and (2) uniformly mixing water and the shell forming material, adding an emulsifier, stirring and emulsifying, then adding alkylsilane into an emulsifying system, further stirring and emulsifying, adding the inorganic filler subjected to the alkali etching treatment in the step (1) into the emulsifying system under a stirring state, uniformly mixing, drying and crushing to obtain the super-hydrophobic inorganic filler.
Preferably, the specific process of performing alkali etching pretreatment on the inorganic filler in step (1) is as follows:
adding 20-50 g/L of alkali liquor into the inorganic filler until the alkali liquor completely submerges the inorganic filler, stirring for 30min at 60 ℃ to perform alkali etching treatment on the inorganic filler, filtering out the alkali liquor, washing and drying the etched inorganic filler to obtain the inorganic filler subjected to alkali etching treatment.
The super-hydrophobic inorganic filler and the application of the super-hydrophobic inorganic filler prepared by the method in preparing underwater high-strength epoxy mortar.
An underwater high-strength epoxy mortar subjected to filler super-hydrophobic treatment is prepared by mixing a component A, a component B and a component C according to the weight ratio of 3:1 (8-12); wherein the component A consists of 100 parts by mass of epoxy resin, 20 parts by mass of reactive diluent, 25 parts by mass of talcum powder, 0.5 part by mass of flatting agent and 0.5 part by mass of defoaming agent; the component B consists of 25 parts by mass of modified phenolic aldehyde amine and 15 parts by mass of modified fatty amine; the component C is 400 parts by mass of super-hydrophobic inorganic filler, and the super-hydrophobic inorganic filler is the super-hydrophobic inorganic filler or the super-hydrophobic inorganic filler prepared by the method.
Preferably, the epoxy resin is any one of bisphenol a type resin and bisphenol F type resin.
Preferably, the reactive diluent is one or two of diglycidyl ether, propylene oxide butyl ether and propylene oxide propyl ether.
Preferably, the leveling agent is a modified polysiloxane leveling agent of shizhong 2420.
Preferably, the defoamer is a silicone-based defoamer of spanish 2650.
A preparation method of underwater high-strength epoxy mortar subjected to filler superhydrophobic treatment comprises the following steps: and respectively mixing the substances in the component A and the substances in the component B uniformly, and then mixing the uniformly mixed component A, component B and component C uniformly according to the ratio of 3:1 (8-12) to prepare the underwater high-strength epoxy mortar, wherein the activation period of the prepared underwater high-strength epoxy mortar is 20-30 min, and the curing time requirement of the conventional epoxy mortar is met.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method comprises the steps of firstly carrying out alkali etching pretreatment on an inorganic filler, and then carrying out hydrophobization treatment on the inorganic filler by adopting alkyl silane with a carbon chain length of 3-14 to obtain the super-hydrophobic inorganic filler, wherein the prepared super-hydrophobic inorganic filler forms a core-shell structure with an exposed hydrophobic group, has good hydrophobicity, and reduces the water absorption of the hydrophobized inorganic filler by 41-98% compared with the inorganic filler without hydrophobization treatment.
(2) According to the invention, through analyzing the water absorption of the inorganic filler prepared by the hydrophobization treatment of the alkyl silanes with different carbon chain lengths, the water absorption of the inorganic filler subjected to the hydrophobization treatment of the alkyl silane with a long carbon chain is lower than that of the inorganic filler subjected to the hydrophobization treatment of the alkyl silane with a short carbon chain, and the fact that the long-carbon-chain alkyl silane such as tetradecyl triethoxysilane can completely wrap the filler is estimated, so that a core-shell structure with a hydrophilic group facing inwards and a hydrophobic group facing outwards can be formed on the surface of the filler, the water absorption of the super-hydrophobic inorganic filler is reduced, and the hydrophobicity of the super-hydrophobic inorganic filler is improved.
(3) Compared with the epoxy mortar prepared by the participation of the inorganic filler without hydrophobic treatment, the underwater high-strength epoxy mortar prepared by the participation of the super-hydrophobic inorganic filler as the raw material has higher underwater bonding strength and stability, and presumably because the hydrophilic groups formed by the alkyl silane on the surface of the inorganic filler are inward and the hydrophobic groups are outward, the compatibility of the hydrophobic inorganic filler and the bisphenol A type resin is enhanced, and the discharge of interfacial water is facilitated, so that the underwater high-strength epoxy mortar prepared by the super-hydrophobic inorganic filler has good bonding strength, better scouring resistance and stability and durability.
(4) The underwater epoxy mortar prepared from the hydrophobic inorganic filler has excellent underwater bonding strength, and compared with the inorganic filler which is not subjected to hydrophobic treatment, the initial bonding strength is improved by 57.1%.
(5) The inorganic filler is subjected to alkali etching treatment in advance, so that the specific surface area of the inorganic filler is increased, the wrapping efficiency of the long-carbon chain alkyl silane on the inorganic filler is improved, meanwhile, the compatibility of the inorganic filler and epoxy resin is further improved by utilizing the characteristic of the double-end silane, the invasion of moisture is effectively prevented, the surface hydrophobic property of the inorganic filler is further improved, and compared with the hydrophobic filler prepared without alkali treatment, the water absorption of the hydrophobic filler prepared after alkali treatment is reduced by 94%; compared with the underwater high-strength epoxy mortar prepared from the super-hydrophobic inorganic filler which is not subjected to alkali etching treatment, the initial bonding strength of the underwater high-strength epoxy mortar prepared from the super-hydrophobic inorganic filler which is subjected to alkali treatment is further improved by 7.3%.
In conclusion, the inorganic aggregate filler is subjected to alkali etching pretreatment and hydrophobization treatment by selecting the alkyl silane with the carbon chain length of 3-14, a core-shell structure with inward hydrophilic groups and outward hydrophobic groups is formed, the filler is changed into a super-hydrophobic structure, and the wrapping efficiency of the alkyl silane on the inorganic filler is improved; the underwater epoxy mortar prepared from the inorganic filler after hydrophobic treatment improves the compatibility with resin, does not hinder the epoxy mortar from spreading on a base material, and simultaneously avoids forming a water film between the epoxy mortar and the base material, thereby improving the durability of the epoxy mortar and improving the interface bonding force between the epoxy mortar and the base material.
Drawings
FIG. 1 is a plot of a sample of the saturation surface of a packing.
Detailed Description
Example 1 Effect of alkylsilanes of different carbon chain lengths on the hydrophobic Properties of the resulting Superhydrophobic inorganic Filler
1. Sample preparation
The super-hydrophobic inorganic filler samples 1-5 are prepared from 20 parts by mass of water, 20 parts by mass of polyvinyl alcohol, 1 part by mass of OP-10, 20 parts by mass of alkylsilane and 80 parts by mass of quartz sand which is 200-mesh in particle size and is subjected to alkali etching treatment, the specific types of the alkylsilanes in the samples 1-5 are shown in Table 1, meanwhile, the sample prepared from the non-added alkylsilane is used as a reference sample 1, and the method for preparing the super-hydrophobic inorganic filler from the raw materials comprises the following steps:
(1) the alkali etching treatment is carried out on the inorganic filler quartz sand, and the specific method comprises the following steps:
Figure 266293DEST_PATH_IMAGE001
placing inorganic filler quartz sand into a reaction kettle, adding a sodium hydroxide solution with the concentration of 40g/L into the reaction kettle until the sodium hydroxide solution completely submerges the quartz sand, and ensuring that the quartz sand is surrounded by the sodium hydroxide solution all the time in the subsequent stirring process;
Figure DEST_PATH_IMAGE002
sealing the reaction kettle, slowly starting stirring to prevent alkali liquor from splashing in the stirring process, slowly heating to 60 ℃ under normal pressure, and continuously stirring for 30min at 60 ℃ to perform surface alkali etching treatment on the quartz sand;
Figure 245750DEST_PATH_IMAGE003
after the surface alkali etching treatment is carried out on the filler quartz sand, the temperature is reduced to alkali liquor for cooling, the filler is taken out, and residual alkali liquor in the filler is drained;
Figure DEST_PATH_IMAGE004
soaking and cleaning the quartz sand subjected to alkali etching for several times by using distilled water until the cleaning solution is neutral;
Figure 166433DEST_PATH_IMAGE005
and drying the quartz sand subjected to alkali treatment in an oven at 105 ℃ to prepare the quartz sand with the surface subjected to alkali etching for later use.
(2) The preparation method of the super-hydrophobic inorganic filler by using the quartz sand subjected to alkali etching comprises the following specific steps:
Figure DEST_PATH_IMAGE006
20 mass% ofPutting the deionized water into a container and stirring at 800 rpm/min;
Figure 374691DEST_PATH_IMAGE007
slowly adding 20 parts by mass of polyvinyl alcohol into deionized water, after the addition of the polyvinyl alcohol is finished, increasing the rotating speed to 1500rpm/min, stirring for 20min at the rotating speed, then adding 1 part by mass of OP-10 into a container, reducing the rotating speed to 800rpm/min, stirring and emulsifying for 10min to obtain an emulsion;
Figure DEST_PATH_IMAGE008
slowly adding 20 parts by mass of alkyl silane liquid into the emulsion, and stirring at the rotating speed of 800rpm/min for 30min to fully emulsify the alkyl silane liquid to prepare alkyl silane emulsion;
Figure 923484DEST_PATH_IMAGE009
slowly adding 80 parts by mass of quartz sand subjected to alkali etching treatment into the alkyl silane emulsion, increasing the rotating speed to 1300rpm/min, stirring at the rotating speed to avoid the quartz sand from depositing at the bottom of the container, simultaneously, not demulsifying due to overhigh rotating speed, and stirring at the rotating speed for 30min to prepare modified sand slurry;
Figure DEST_PATH_IMAGE010
pouring the modified sand slurry on crawler-type drying equipment capable of controlling temperature in sections, wherein the thickness of the slurry is not more than 2mm, adjusting the belt speed to be 40m/min, controlling the temperature in sections from front to back to be 150 ℃, 120 ℃ and 70 ℃, drying to obtain anhydrous super-hydrophobic quartz sand, and mechanically crushing to obtain the quartz sand with super-hydrophobic surface, namely the super-hydrophobic inorganic filler.
Analysis of hydrophobic Properties
Respectively carrying out water absorption tests on samples 1-5 and a control sample 1, wherein the method for testing the saturated surface dry water absorption of the filler comprises the following steps:
(1) 500g of the fillers of the sample 1-5 and the reference sample 1 are respectively weighed in a natural state for later use.
(2) And respectively pouring the samples to be detected into an enamel tray, injecting clean water to enable the water surface to be 20mm higher than the surface of the samples, controlling the water temperature to be 18-28 ℃, continuously stirring for 5min by using a glass rod to remove bubbles, and standing for 24 h. After soaking, under the condition of clear water, the clear water at the upper part of the sample is carefully poured out, and the fine powder part cannot be poured out. Spreading the sample in a tray, slowly blowing warm air by using a blower, and continuously turning over the sample to uniformly evaporate surface moisture so as not to blow out filler particles.
(3) The sample to be tested was divided into two layers and loaded into a saturated surface dry test mold, the first layer was loaded half the height of the mold and was uniformly pounded 13 times with a pestle (the pestle dropped freely about 10mm from the surface of the sample). The second layer is filled with the test mold, lightly crushed 13, scraped to the upper opening of the test mold, and then vertically and slowly lifted up as shown in fig. 1a), which indicates that the test sample still contains surface water, and then dried by warm air, and tested according to the method until the test sample is lifted up and then is in the shape shown in fig. 1 b). If the test piece is lifted, the test piece is in the shape of figure 1c), which indicates that the test piece is too dry, 50ml of water is sprayed, and after fully stirring the test piece uniformly, the test piece is placed in a capped container for 30min, and the test is carried out according to the method until the shape of figure 1b) is achieved.
(4) 500g of saturated dried sample is weighed immediately to the nearest 0.1g, and the mass of the saturated dried sample is recorded as m1Pouring the dried sample into a beaker with known mass, placing the beaker into a drying oven at 100-110 ℃ for drying until the weight is constant, cooling the beaker to room temperature, and weighing the dry sample to obtain a mass m0To the nearest 0.1 g.
(5) And (4) calculating and evaluating results:
the water absorption was calculated to the nearest 0.01%: qw=(m1-m0)/m0﹡ 100, respectively; wherein Q iswWater absorption (%) is shown; m is1Represents the saturated dry sample mass in grams (g); m is0Represents the dried sample mass in grams (g).
The results of the water absorption tests of samples 1-1 to 1-5 and control 1 are shown in Table 1, and the specific components of the alkylsilanes in samples 1-1 to 1-5 and the carbon chain lengths of the corresponding components are shown in Table 1.
As can be seen from Table 1, the water absorption of samples 1-1 to 1-5 is significantly lower than that of control sample 1, and compared with control sample 1, the water absorption of samples 1-1 to 1-5 is reduced by 41-98%; since samples 1-1 to 1-5 were all subjected to the hydrophobization treatment with the alkylsilane, and comparative sample 1 was not subjected to the hydrophobization treatment, the water absorption of the inorganic filler subjected to the hydrophobization modification treatment with the alkylsilane was significantly lower than that of the inorganic filler not subjected to the hydrophobization modification treatment with the alkylsilane.
Figure 542684DEST_PATH_IMAGE011
Furthermore, the water absorption of samples 1-1 to 1-5 is gradually increased, while the raw materials of samples 1-1 to 1-5 are different only in the kind of the added alkylsilane, and the obvious difference is that the carbon chain length of the alkylsilane is different, and it can be seen that the water absorption of the long-carbon alkylsilane treated filler is lower than that of the short-carbon alkylsilane treated filler in table 1, so that it can be seen that the hydrophobicity of the long-carbon alkylsilane treated inorganic filler is better than that of the short-carbon alkylsilane treated inorganic filler; the analysis conjectures that the alkyl silane with long carbon chain is more beneficial to winding interaction with the shell-forming substance because the carbon chain is longer, so that the inorganic filler is completely wrapped and is prevented from being invaded by water molecules.
Example 2 Effect of alkali etching treatment on the hydrophobic Properties of super-hydrophobic inorganic Filler
1. Sample preparation
In reference to the preparation method of the superhydrophobic inorganic filler sample in example 1, samples 2-1 to 2-5 in this example, and a control sample 2-1 and a control sample 2-2 were prepared, wherein tetradecyltriethoxysilane was used as the alkylsilane.
In the preparation process of the samples 2-1 to 2-5, the difference from the example 1 is only that the concentration of the sodium hydroxide solution in the alkali etching process in the step (1) is different, and the specific concentration value of the sodium hydroxide is shown in table 2.
The control 2-1 is a raw material of quartz sand, i.e., the quartz sand of the control 1 is not subjected to the alkali etching of the step (1) in the example 1 and is not subjected to the hydrophobization treatment of the step (2).
Control 2-2 is a hydrophobized quartz sand sample obtained without the alkali etching treatment in step (1) of example 1 but subjected to the hydrophobizing treatment in step (2).
Analysis of hydrophobic Properties
The water absorption test was carried out on the samples 2-1 to 2-5 and the control 2-1 and the control 2-2 by the method described in example 1, and the test results are shown in Table 2.
Figure DEST_PATH_IMAGE012
As can be seen from Table 2, the water absorption of samples 2-1 to 2-5 is significantly lower than that of control sample 2-1 and control sample 2-2, and the water absorption of samples 2-1 to 2-5 is reduced by 75% to 98% compared with that of control sample 2-1. The comparison sample 2-1 is not treated, that is, the comparison sample 2-1 is a quartz sand raw material, the comparison sample 2-2 is only subjected to hydrophobization treatment but not to alkali etching treatment, and the samples 2-1 to 2-5 are subjected to alkali treatment with different excessive concentrations and then to alkylsilane hydrophobization treatment, so that when the inorganic filler subjected to alkali treatment is subjected to alkylsilane hydrophobization modification, the water absorption of the inorganic filler subjected to alkali etching treatment can be further reduced, compared with the comparison sample 2-2, the water absorption of the quartz sand sample subjected to alkali etching treatment can be further reduced to 94%, and the hydrophobic effect is remarkable.
In addition, the water absorption results of the samples 2-1 to 2-5 show that the water absorption of the prepared quartz sand sample gradually decreases to a steady trend along with the increase of the concentration of the alkali liquor, so that the specific surface area of the filler can be effectively increased and the adhesion of the long-carbon chain alkyl silane can be enhanced by treating the surface of the quartz sand with hot concentrated alkali with a certain concentration, but the alkali etching effect tends to be steady along with the increase of the concentration of the concentrated alkali. From the above results, it can be reasonably speculated that when the quartz sand subjected to alkali etching treatment with a certain concentration is subjected to long-carbon-chain alkylsilane modification, the adhesion and winding interaction of the alkylsilane are facilitated, the inorganic filler is completely wrapped, and the intrusion of water molecules is avoided, so that the hydrophobic property of the inorganic filler is further improved.
Example 3 Effect of different super-hydrophobic inorganic fillers on the adhesion Strength of epoxy mortars
Influence of super-hydrophobic inorganic filler prepared from alkylsilanes with different carbon chain lengths on bonding strength of epoxy mortar
1. Sample preparation
The filler super-hydrophobic treated underwater high-strength epoxy mortar is prepared by mixing a component A, a component B and a component C according to the weight ratio of 3:1: 10; wherein the component A consists of 100 parts by mass of bisphenol A type resin, 20 parts by mass of active diluent diglycidyl ether, 25 parts by mass of talcum powder, 0.5 part by mass of flatting agent Shizhong 2420 and 0.5 part by mass of defoaming agent Shizhong 2650; the component B consists of 25 parts by mass of modified phenolic aldehyde amine and 15 parts by mass of modified fatty amine; the component C is 400 parts by mass of super-hydrophobic inorganic filler.
And respectively mixing the substances in the component A uniformly, mixing the substances in the component B uniformly, and mixing the uniformly mixed component A, component B and component C uniformly according to the ratio of 3:1:10 to prepare the underwater high-strength epoxy mortar.
The super-hydrophobic inorganic filler in the component C is 1-5 of example 1 and 1 of a reference sample, and the underwater high-strength epoxy mortar prepared from the inorganic filler of 1-5 of example 1 and 1 of the reference sample is marked as samples 3-1-3-5 and 3 of the reference sample.
Namely, the super-hydrophobic inorganic filler as the raw material for preparing the sample 3-1-3-5 is subjected to surface alkali etching and surface hydrophobization, while the super-hydrophobic inorganic filler as the raw material for preparing the reference sample 3 is only subjected to alkali etching and is not subjected to surface hydrophobization.
Meanwhile, the kind of alkylsilane, which is one of the raw materials for preparing the super hydrophobic inorganic filler, and the corresponding carbon chain length are shown in Table 3.
Analysis of adhesive Strength
Samples 3-1 to 3-5 and a control sample 3 were subjected to an underwater positive tensile bond strength decay test, and the test results are shown in table 3.
As can be seen from Table 3, the initial bonding strength of the samples 3-1 to 3-5 is higher than that of the control sample 3, and compared with the control sample 3, the initial bonding strength of the samples 3-1 to 3-5 is improved by 25 to 57.1 percent, so that the epoxy mortar prepared from the hydrophobized inorganic filler has better initial bonding strength; and the initial bonding strength of the sample 3-1 is higher than that of the other samples, and the result in the example 1 shows that the hydrophobic property of the inorganic filler in the raw material for preparing the sample 3-1 is better than that of the other samples, which shows that the underwater bonding strength of the epoxy mortar prepared from the inorganic filler with more excellent hydrophobic property is higher.
Figure 150996DEST_PATH_IMAGE013
In addition, after 12 months, the underwater bonding strength of the sample 3-1 is only reduced by 0.5%, after 12 months, the underwater bonding strength of the samples 3-2, 3-3, 3-4 and 3-5 is respectively reduced by 7.7%, 10.3%, 13.9% and 17.1%, and after 12 months, the underwater bonding strength of the reference sample 3 is reduced by 28.6%; therefore, the underwater high-strength epoxy mortar prepared from the hydrophobized inorganic filler has low forward-pulling adhesion decay, good stability and long-term water resistance.
(II) influence of super-hydrophobic inorganic filler prepared by alkali etching treatment with different concentrations on bonding strength of high-strength epoxy mortar
1. Sample preparation
The filler super-hydrophobic treated underwater high-strength epoxy mortar is prepared by mixing a component A, a component B and a component C according to the weight ratio of 3:1: 10; wherein the component A consists of 100 parts by mass of bisphenol A type resin, 20 parts by mass of active diluent diglycidyl ether, 25 parts by mass of talcum powder, 0.5 part by mass of flatting agent Shizhong 2420 and 0.5 part by mass of defoaming agent Shizhong 2650; the component B consists of 25 parts by mass of modified phenolic aldehyde amine and 15 parts by mass of modified fatty amine; the component C is 400 parts by mass of super-hydrophobic inorganic filler.
And respectively mixing the substances in the component A uniformly, mixing the substances in the component B uniformly, and mixing the uniformly mixed component A, component B and component C uniformly according to the ratio of 3:1:10 to prepare the underwater high-strength epoxy mortar.
The super-hydrophobic inorganic fillers in the component C are respectively 2-1-2-5 of the comparative sample 2-1 and 2-2 of the comparative sample in the embodiment 2, and the underwater high-strength epoxy mortar prepared from the inorganic fillers of 2-1-2-5 of the embodiment 2 and 2-1 and 2-2 of the comparative sample 2 is respectively marked as samples 4-1-4-5, 4-1 of the comparative sample and 4-2 of the comparative sample.
Namely, the inorganic filler in the preparation raw material of the comparison sample 4-1 is a quartz sand raw material, and is not subjected to alkali etching treatment or surface hydrophobization treatment of alkyl silane; the super-hydrophobic inorganic filler in the preparation raw material of the comparative sample 4-2 is only subjected to surface hydrophobization treatment and is not subjected to surface alkali etching treatment in the preparation process.
Meanwhile, the concentrations of the sodium hydroxide solutions used in the preparation of the superhydrophobic inorganic fillers in the preparation raw materials of the samples 4-1 to 4-5 and the reference samples 4-1 and 4-2 are shown in Table 4.
Analysis of adhesive Strength
Samples 4-1 to 4-5, a control sample 4-1 and a control sample 4-2 were subjected to an underwater positive tensile bond strength decay test, and the test results are shown in table 4.
Figure DEST_PATH_IMAGE014
As can be seen from the comparison of the data in Table 4, after the samples 4-1 to 4-5 are subjected to the alkali etching treatment, the initial bonding strength is improved by 2.4 to 7.3 percent compared with that of a control sample 4-2 which is not subjected to the alkali etching treatment, and is far higher than that of the control sample 4-1 which is not subjected to any treatment, so that the inorganic filler subjected to the alkali etching advanced treatment can be used for obtaining the super-hydrophobic filler with more excellent hydrophobic property when the alkyl silane is used for carrying out the super-hydrophobic treatment, and further the underwater cured epoxy mortar with higher underwater bonding strength can be obtained.
In addition, after 12 months, the adhesive strength of the samples 4-1 to 4-5 subjected to the alkali etching treatment is respectively reduced by 4.8%, 2.3%, 0.5% and 0.5%, and after 12 months, the adhesive strength of the comparison sample 4-1 and the comparison sample 4-2 is respectively reduced by 28.6% and 4.9%. The data comparison shows that the inorganic filler after alkali treatment enables the retention rate of the bonding strength of the epoxy mortar under water to be higher, the alkali treatment effect tends to be stable along with the increase of the alkali liquor concentration, and the inorganic filler is the optimal alkali treatment condition when the alkali liquor concentration is 40 g/L.

Claims (8)

1. The super-hydrophobic inorganic filler is characterized by being prepared from the following raw materials in parts by mass: 10-30 parts of water, 10-30 parts of a shell forming material, 1-5 parts of an emulsifier, 10-30 parts of alkyl silane and 60-100 parts of an inorganic filler;
the shell forming material is one or two of polyvinyl alcohol, hydroxyethyl cellulose ether and hydroxypropyl methyl cellulose ether;
the alkyl silane is at least one of straight chain alkyl silane and branched chain alkyl silane, and the length of a carbon chain in the straight chain alkyl silane or the branched chain alkyl silane is 8-14;
and adding an inorganic filler into the emulsifying system under the stirring state, uniformly mixing, drying and crushing to obtain the super-hydrophobic inorganic filler.
2. The super-hydrophobic inorganic filler according to claim 1, wherein the super-hydrophobic inorganic filler is prepared from the following raw materials in parts by mass: 20 parts of water, 20 parts of shell forming materials, 1 part of emulsifying agent, 20 parts of alkyl silane and 80 parts of inorganic filler.
3. The superhydrophobic inorganic filler of claim 1 or 2, wherein the alkylsilane is at least one of tetradecyltriethoxysilane, n-dodecylsilane, n-decyltrimethoxysilane, and n-octyltrimethoxysilane.
4. A method for preparing the superhydrophobic inorganic filler of claim 3, comprising the steps of:
(1) carrying out alkali etching pretreatment on the inorganic filler;
(2) and (2) uniformly mixing water and the shell forming material, adding an emulsifier, stirring and emulsifying, then adding alkylsilane into an emulsifying system, further stirring and emulsifying, adding the inorganic filler subjected to the alkali etching treatment in the step (1) into the emulsifying system under a stirring state, uniformly mixing, drying and crushing to obtain the super-hydrophobic inorganic filler.
5. The preparation method of the super-hydrophobic inorganic filler according to claim 4, wherein the specific process of performing the alkali etching pretreatment on the inorganic filler in the step (1) is as follows:
adding 20-50 g/L of alkali liquor into the inorganic filler until the alkali liquor completely submerges the inorganic filler, stirring for 30min at 60 ℃ to perform alkali etching treatment on the inorganic filler, filtering out the alkali liquor, washing and drying the etched inorganic filler to obtain the inorganic filler subjected to alkali etching treatment.
6. Use of the superhydrophobic inorganic filler of claim 3 or the superhydrophobic inorganic filler made from claim 5 in the preparation of an underwater high-strength epoxy mortar.
7. The underwater high-strength epoxy mortar subjected to filler super-hydrophobic treatment is characterized by being prepared by mixing a component A, a component B and a component C according to the weight ratio of 3:1 (8-12); the component A consists of 100 parts by mass of epoxy resin, 20 parts by mass of reactive diluent, 25 parts by mass of talcum powder, 0.5 part by mass of flatting agent and 0.5 part by mass of defoaming agent; the component B consists of 25 parts by mass of modified phenolic aldehyde amine and 15 parts by mass of modified fatty amine; the component C is 400 parts by mass of super-hydrophobic inorganic filler; the super-hydrophobic inorganic filler is the super-hydrophobic inorganic filler described in claim 3 or the super-hydrophobic inorganic filler prepared by the method described in claim 5.
8. The preparation method of the underwater high-strength epoxy mortar treated by the filler of claim 7 in a super-hydrophobic manner is characterized by comprising the following steps: and respectively mixing the substances in the component A uniformly, mixing the substances in the component B uniformly, and mixing the uniformly mixed component A, component B and component C uniformly according to the ratio of 3:1 (8-12) to prepare the underwater high-strength epoxy mortar.
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