CN113620633A

CN113620633A - Treatment process method of anti-crack cement mortar reinforced chopped glass fibers

Info

Publication number: CN113620633A
Application number: CN202111058832.5A
Authority: CN
Inventors: 范秀娟; 张杨; 张道盘; 范兴伟
Original assignee: Anhui Zhongxian New Material Co ltd
Current assignee: Wuhe Weijia Composite Material Co ltd
Priority date: 2021-09-10
Filing date: 2021-09-10
Publication date: 2021-11-09
Anticipated expiration: 2041-09-10
Also published as: CN113620633B

Abstract

The invention discloses a processing method of crack-resistant cement mortar reinforced chopped glass fibers, which belongs to the technical field of inorganic materials, does not adopt a silane coupling agent, and can be used for preparing a cement composite material with higher strength, better toughness and better crack resistance by changing the contact state of the glass fibers and cement after being processed by the processing method. The fiber and the polymer matrix can generate good bonding, the glass fiber can effectively improve the crack resistance of the plain cement, compared with the plain cement mortar and untreated glass fiber reinforced cement, the breaking strength and the compressive strength are obviously improved, the fiber and the polymer matrix can be widely applied to the fields of civil construction, agriculture, animal husbandry, fishery and the like, the cost is lower, the operation is simple and convenient, and the fiber and the polymer matrix have good market practical prospect.

Description

Treatment process method of anti-crack cement mortar reinforced chopped glass fibers

Technical Field

The invention belongs to the technical field of inorganic materials, and particularly relates to a treatment process method of anti-cracking cement mortar reinforced chopped glass fibers.

Background

Chopped glass fibers are a large class of glass fiber products that have been used primarily as reinforcing materials such as reinforced thermosets and reinforced thermoplastics, and are increasing in number with the ever-expanding application fields. The chopped glass fiber is made by processing continuous glass fiber through a chopping machine, can be used as various base materials such as reinforced plastics, asphalt and the like, and is widely applied to the fields of automobiles, buildings, aviation, daily necessities and the like. In order to solve the problems of poor dispersibility of the chopped glass fiber, low mechanical property of the product and reduced appearance performance, the geometric dimension of the chopped glass fiber is the same as that of the traditional chopped strand. The chopped glass fiber is a chopped strand having superior dispersibility, and therefore, is particularly suitable for FRP products having special requirements for dispersibility, and can be directly used for injection molding FRP products. Concrete has found application in more and more fields, but high brittleness is a fundamental defect. Chinese patent CN110818340A discloses that the prepared anti-cracking cement mixture has good anti-cracking performance by adjusting the components of the anti-cracking cement mixture, and in order to solve the brittleness problem, people mix different short-cut fibers, such as steel fibers, polypropylene fibers, glass fibers, etc., into the concrete. The flexible polymer composite anti-seepage anti-crack cement mortar disclosed in the Chinese patent CN107382157A uses polypropylene fibers, and the chopped fibers are randomly distributed in the concrete, and mainly play a role in improving the toughness of the concrete after cracking. Compared with other fibers, the glass fiber and the cement-based material both belong to inorganic non-metallic materials, the performance is relatively close, the uniform mixing is easy, and the glass fiber concrete has the application advantages of light weight, high strength, low cost and the like. In recent years, nearly 30 billionths of cubic meters of concrete is used in infrastructure construction and national key engineering construction every year in China. But the rapid development of the concrete is also limited by the defects of heavy weight, unstable volume, low tensile strength, poor impermeability and toughness and the like. The brittleness of the common concrete is obviously increased along with the increase of the compressive strength, and the common concrete is usually subjected to no-sign collapse and fragmentation damage under the action of load, so that the application of the concrete in actual engineering is greatly influenced. Those skilled in the art are in need of developing a treatment process for anti-cracking cement mortar reinforced chopped glass fibers to meet the existing application market and performance requirements.

Disclosure of Invention

In view of the above, the invention provides a treatment process method of anti-cracking cement mortar reinforced chopped glass fibers.

A treatment process method of anti-crack cement mortar reinforced chopped glass fibers comprises the following steps: firstly, soaking chopped glass fibers into 0.15-0.2 mol/L sodium hydroxide solution, etching at 20 ℃ for 0.1-0.2 h, taking out, washing with pure water to be neutral, drying in an oven at 80 ℃ for 2-4 h, and cooling for later use; the organic sodium silicate has the film forming effect: the film forming agent has the functions of protecting the fiber from wetting and soaking in the stirring and using processes, and the organic sodium silicate has certain early strength and obvious delayed coagulation under the condition of proper amount;

secondly, putting the dried chopped glass fibers and an accelerator with the mass ratio of 0.5% into a high-speed mixer, wherein the accelerator is sodium fluosilicate or calcium chloride, stirring at 2000-2500 r/min for 5-10 min, and filtering; the chopped glass fiber and the accelerant are uniformly mixed by adopting a high-speed mixer. The wet mixing is carried out by adopting a high-speed mixer, and the wet mixing medium adopts aqueous solution and can further grind the materials to ensure that the materials are mixed more uniformly.

Sodium fluosilicate is a by-product of producing calcium superphosphate or fluoride salt in aluminium factories, and is used as a setting hardening agent for acid-proof cement. Molecular formula is Na₂SiF_6，And the aqueous solution of sodium fluosilicate is acidic, and the hydrolysate of sodium fluosilicate contains hydrofluoric acid: na (Na)₂SiF₆₊4H₂O→2NaF+HF+Si(OH)_4，When the sodium fluosilicate and the calcium chloride contact the water-soluble sodium silicate solution, the hydrolysate hydrofluoric acid of the sodium fluosilicate is continuously combined with the sodium oxide, so that the hydrolysis reaction of the sodium fluosilicate is continuously carried out.

The third step: taking organic sodium silicate, diluting with water with the weight being 1.2-1.5 times, pouring into a mixing kettle, stirring, weighing a lubricant, dissolving the lubricant in hot water with the weight being 10-12 times of that of the lubricant at 70-80 ℃, adding cold water with the weight being 7-8 times of that of the lubricant, pouring into the mixing kettle when the temperature of the solution is reduced to 30-45 ℃, continuing stirring, weighing an emulsifier, dissolving the emulsifier in water with the weight being 15-16 times of that of the emulsifier, pouring into the mixing kettle after dissolving, continuing stirring, accurately weighing an active agent, diluting with water with the weight being 8-10 times of that of the emulsifier, pouring into the mixing kettle, adding the rest water, continuing stirring for 5-10 minutes, and obtaining an infiltration solution for later use; and fourthly, after the chopped glass fibers obtained in the second step are subjected to heat treatment for 50-60 seconds, soaking according to a process soaking process, baking for 10-12 min, and cooling to 25-30 ℃ to obtain the chopped glass fibers.

The organic sodium silicate is mainly used for establishing and promoting the interface bonding between inorganic matters and polymers, and can change the surface of the glass fiber from hydrophilicity to hydrophobicity to attach the polymers, thereby improving the water resistance of the glass fiber and the wettability and the bonding property of the glass fiber. The zirconium compound is a highly combinable compound of zirconium, which is free of metal ions and can be combined with an element having a high electronegativity. Therefore, zirconium is easily combined with substances such as amine and ethylene glycol, and zirconium is bonded to calcium in cement to form an insoluble matter, thereby having a hydrophobic effect.

The active agent in the third step is sodium zirconium lactate and bis (citric acid diacetyl) dipropoxy zirconium chelate, the emulsifier is one of dioctyl dimethyl ammonium bromide, galactomannan hydroxypropyl quaternary ammonium salt and dimethyl benzyl dodecyl ammonium bromide, and the lubricant is one of melamine cyanurate, magnesium lauryl sulfate and polyethylene glycol monostearate.

The lubricant can effectively lubricate the protective fiber and reduce the abrasion of the glass fiber in the processing process. Emulsifier: the function is that the static electricity generated by the friction of the glass fiber in the stirring and mixing process is weakened or eliminated by adding the emulsifier.

Further, the fourth step of dipping process is carried out at the heat treatment temperature of 200-220 ℃ with the vehicle speed of 4-6 m/min, the dipping time of 25-30 min at the bath ratio of 1: 6 and the baking temperature of 140-150 ℃.

The selection of the baking and melting temperature is one of the key factors for leading the treating agent and the surface of the glass fiber to generate modification, the due modification effect cannot be achieved when the temperature is too low, and the adverse consequences such as the weaving, cohesion and the like of the treating agent can be caused when the temperature is too high. The baking time should be selected such that the coupling reaction of the treating agent with the surface of the glass fiber proceeds sufficiently at the baking temperature. Under the condition of ensuring the product performance, a proper baking system is adopted for improving the production efficiency.

The third step is that the organic sodium silicate is one of methyl sodium silicate, ethyl sodium silicate and phenyl sodium silicate, and the impregnating compound comprises the following raw materials in percentage by weight: 3.0-4.5% of organic sodium silicate, 0.2-0.5% of active agent, 0.3-0.5% of lubricant, 0.05-0.1% of emulsifier and the balance of water.

The surface of the glass fiber absorbs water to generate hydroxyl:

[CH₃Si(OH)₃]hydrogen bonds are generated with hydroxyl on the surface of the glass short glass fiber, and the glass short glass fiber is associated and bonded with the hydrogen bonds of the glass fiber:

[CH₃Si(OH)₃]bonding in association with the desired chemical bonds of the chopped glass fibers:

the invention has the beneficial effects that:

the invention adopts the impregnating solution to carry out surface treatment on the glass fiber, improves the interface bonding force and the interface hydrophobic property of the cement and the glass fiber, generates a waterproof jelly by the impregnating solution, and forms a compact film layer on the surface of the glass fiber through dehydration polymerization, thereby delaying the erosion of the cement to the glass fiber. Wherein the organic sodium silicate has the film forming effect: the film forming agent has the functions of protecting the fiber from wetting and soaking in the stirring and using processes, and the organic sodium silicate has certain early strength and obvious delayed coagulation under the condition of proper amount; the lubricant can effectively lubricate the protective fiber and reduce the abrasion of the glass fiber in the processing process. Emulsifier: the function is that the static electricity generated by the friction of the glass fiber in the stirring and mixing process is weakened or eliminated by adding the emulsifier. The organic sodium silicate is mainly used for establishing and promoting the interface bonding between inorganic matters and polymers, and can change the surface of the glass fiber from hydrophilicity to hydrophobicity to attach the polymers, thereby improving the water resistance of the glass fiber and the wettability and the bonding property of the glass fiber. The zirconium compound is a highly combinable compound of zirconium, which is free of metal ions and can be combined with an element having a high electronegativity. Therefore, zirconium is easy to combine with substances such as amine, ethylene glycol and the like, zirconium can be combined with calcium in cement to form an insoluble substance, the water repellent effect is achieved, the structure of an interface is improved, the glass fiber reinforced cement composite material is in a relatively stable environment, the durability of the glass fiber reinforced cement composite material is prolonged, the phenomenon of stress concentration is reduced, defects in the interface area are repaired, and the stress distribution is more uniform. Making the gap at the interface smaller. In addition, the active admixture can also refine the structure of the material, so that larger gaps are filled, and the interface is smoother and more compact.

Compared with the prior art, the invention has the following advantages:

in the past, alkali-resistant glass fiber materials with larger elastic modulus are uniformly distributed in cement mortar to enhance the physical and mechanical properties of a base material, glass fiber concrete is a novel light, high-strength and non-combustible building material, and has higher tensile strength and bending strength, larger toughness and good impact resistance, and the glass fiber doped in the treatment process method can obviously improve the tensile strength and the crack resistance of the concrete; however, the application of the glass fiber is limited because the glass fiber is easily corroded by strong alkali substances generated in the hydration process of cement, thereby causing the performance deterioration. In the past, the coping method for glass fiber concrete at home and abroad is to develop alkali-resistant glass fiber, and the alkali-resistant glass fiber is used in combination with portland cement, the alkali-resistant glass fiber is high in price, and silane coupling agent is adopted for treatment, so that the utilization rate of a dry coupling agent is high, but the dry coupling agent is not easily and uniformly distributed on the surface of each inorganic filler, the wet uniformity is good, the coupling agent is large in waste and high in cost, for example, the negative influence of reducing the stability is possibly generated by adding the silane coupling agent, and the reason is that a reaction group of silane and a replacement group of resin are subjected to chemical reaction or alkoxy of silane is subjected to reaction. In a general silane coupling agent, one molecule has three alkoxy groups, and stability tends to be lowered if all of them are reacted. The invention does not adopt silane coupling agent, the contact state of the glass fiber and the cement is changed after the treatment, the fiber is not easy to break in the stirring and forming processes, the reinforcing effect is enhanced, and the cement composite material with higher strength, better toughness and better crack resistance can be prepared due to the mixed reinforcing effect of the glass fiber.

Detailed Description

Example 1

Firstly, soaking chopped glass fibers into 0.2mol/L sodium hydroxide solution, etching for 0.2h at 20 ℃, taking out the chopped glass fibers, washing the chopped glass fibers to be neutral by using pure water, drying the chopped glass fibers in an oven at 80 ℃ for 4h, and cooling the dried chopped glass fibers for later use; secondly, putting the dried chopped glass fiber into a high-speed mixer, stirring for 10min at 2500r/min and filtering, wherein the mass ratio of the sodium fluosilicate accelerator solution is 0.5%; the third step: the organic sodium silicate is methyl sodium silicate, and the impregnating solution comprises the following raw materials in percentage by weight: 3.0 percent of organic sodium silicate, 0.2 percent of active agent, 0.3 percent of lubricant, 0.05 percent of emulsifier and the balance of water, wherein the active agent is bis (citric acid diacetyl) dipropoxy zirconium chelate Nanjing eosin SG-Zr805, the emulsifier is dioctyl dimethyl ammonium bromide, the lubricant is magnesium lauryl sulfate, the organic sodium silicate is diluted by water with the weight of 1.2 times, the diluted organic sodium silicate is poured into a mixing kettle, stirring, weighing the lubricant, dissolving the lubricant in hot water at 80 ℃ which is 10 times of the weight of the lubricant, adding cold water which is 7 times of the weight of the lubricant after dissolving, when the temperature of the solution is reduced to 30 ℃, pouring the solution into a mixing kettle, continuously stirring, weighing the emulsifier, dissolving the emulsifier by using water with the weight 16 times that of the emulsifier, dissolving, pouring into a mixing kettle, continuously stirring, accurately weighing the active agent, diluting with 10 times of water, pouring into the mixing kettle, adding the rest water, and continuously stirring for 10 minutes to obtain an immersion liquid for later use; after the chopped glass fibers obtained in the fourth step and the second step are subjected to heat treatment for 60 seconds, the dipping process is carried out at the heat treatment temperature of 6 m/min of vehicle speed520, soaking at 30 ℃ for 30min at the bath ratio of 1: 6, baking at 150 ℃, soaking according to the technological soaking process, baking for 112min, and cooling to 230 ℃ to obtain the product. Water reducing agent ART-MPC of Tonka science and technology Limited company, chopped glass fiber WJ101-3 of Wuhe county Weijia composite material Limited company, nominal diameter 10 μm, chopped length 3.0mm, wherein 62% Si0₂、7%Zr0₂、0.1%TiO₂、5.6CaO、0.8Al₂0₃、2.0%K₂0、14%Na₂O。

2.5% of chopped glass fiber:

example 2

Firstly, soaking chopped glass fibers into 0.15mol/L sodium hydroxide solution, etching for 0.1h at 20 ℃, taking out the chopped glass fibers, washing the chopped glass fibers to be neutral by using pure water, drying the chopped glass fibers in an oven at 80 ℃ for 2h, and cooling the dried chopped glass fibers for later use; secondly, putting the dried chopped glass fiber and an accelerant with the mass ratio of 0.5 percent into a high-speed mixer, wherein the accelerant is calcium chloride, stirring at 2000r/min for 5min, and filtering; the third step: thirdly, the organic sodium silicate is ethyl sodium silicate, and the components of the impregnating solution in percentage by weight are as follows: 3.0 percent of organic sodium silicate, 0.2 percent of active agent, 0.3 percent of lubricant, 0.05 percent of emulsifier and the balance of water, wherein the active agent is sodium lactate zirconium Naoxing HX9013-Zr-803, the emulsifier is galactomannan hydroxypropyl quaternary ammonium salt GUARC3600, the lubricant is polyethylene glycol monostearate, organic sodium silicate is diluted by water with the weight of 1.2 times, the diluted organic sodium silicate is poured into a mixing kettle, stirring, weighing the lubricant, dissolving the lubricant in hot water at 70 ℃ which is 10 times of the weight of the lubricant, adding cold water which is 7 times of the weight of the lubricant after dissolving, when the temperature of the solution is reduced to 30 ℃, pouring the solution into a mixing kettle, continuously stirring, weighing the emulsifier, dissolving the emulsifier by using water with the weight 15 times that of the emulsifier, dissolving, pouring into a mixing kettle, continuously stirring, accurately weighing the active agent, diluting with 8 times of water, pouring into the mixing kettle, adding the rest water, and continuously stirring for 5 minutes to obtain an immersion liquid for later use; and fourthly, after the chopped glass fibers obtained in the second step are subjected to heat treatment for 50 seconds, dipping for 25min at the heat treatment temperature of 200 ℃ with the speed of 4 m/min and at the temperature of 25 ℃ with the bath ratio of 1: 6 at the baking temperature of 140 ℃, baking for 10min after dipping according to the process dipping process, and cooling to 25 ℃ to obtain the chopped glass fibers. Water reducing agent ART-MPC of Tonka science and technology Limited company, chopped glass fiber WJ101-3 of Weijia composite material Limited company, Wuhe county, the nominal diameter of the fiber is 10 μm, and the chopped length is 3.0 mm.

2.5% of chopped glass fiber:

control example 1 untreated chopped strand glass fibers

2.5% of chopped glass fiber:

note: reference is made to a GB/T29756-2013 dry-mixed mortar physical property test method; the strength grade is changed by changing the sand-lime ratio, which is 1: 1.5,1: 2. 1: 3.1: 4. 1: 5.1: 7. and measuring the consistency of the mortar and the 28d compression strength and the flexural strength of the mortar. Wherein the reference mortar has the following mixing proportion and performance:

wherein the shaping examination mould: the three-link mold is 40mm multiplied by 160mm, wherein the cement P. 042.5 product of Guangdong Longjian building is as follows:

wherein the sand is a gingko sand Hubei Yuanchang mineral manufactured sand product which meets the II-class requirements in GB/T14684-2001:

in conclusion, the treatment process method of the anti-cracking cement mortar reinforced chopped glass fibers disclosed by the invention has the advantages that the glass fibers can effectively improve the anti-cracking capability of the plain cement, and the plain cement mortar and untreated glass fiber reinforced waterCompared with the mud, the breaking strength and the compressive strength are obviously improved, the mud is widely applied to the fields of civil construction, agriculture, animal husbandry, fishery and the like, the cost is lower, the operation is simple and convenient, and the mud has very good market practical prospect.

Claims

1. The processing method of the crack-resistant cement mortar reinforced chopped glass fiber is characterized by comprising the following steps of: firstly, soaking chopped glass fibers into 0.15-0.2 mol/L sodium hydroxide solution, etching at 20 ℃ for 0.1-0.2 h, taking out, washing with pure water to be neutral, drying in an oven at 80 ℃ for 2-4 h, and cooling for later use; secondly, putting the dried chopped glass fibers and an accelerator with the mass ratio of 0.5% into a high-speed mixer, wherein the accelerator is sodium fluosilicate or calcium chloride, stirring at 2000-2500 r/min for 5-10 min, and filtering; the third step: taking organic sodium silicate, diluting with water with the weight being 1.2-1.5 times, pouring into a mixing kettle, stirring, weighing a lubricant, dissolving the lubricant in hot water with the weight being 10-12 times of that of the lubricant at 70-80 ℃, adding cold water with the weight being 7-8 times of that of the lubricant, pouring into the mixing kettle when the temperature of the solution is reduced to 30-45 ℃, continuing stirring, weighing an emulsifier, dissolving the emulsifier in water with the weight being 15-16 times of that of the emulsifier, pouring into the mixing kettle after dissolving, continuing stirring, accurately weighing an active agent, diluting with water with the weight being 8-10 times of that of the emulsifier, pouring into the mixing kettle, adding the rest water, continuing stirring for 5-10 minutes, and obtaining an infiltration solution for later use; and fourthly, after the chopped glass fibers obtained in the second step are subjected to heat treatment for 50-60 seconds, soaking according to a process soaking process, baking for 10-12 min, and cooling to 25-30 ℃ to obtain the chopped glass fibers.

2. The processing method of crack-resistant cement mortar reinforced chopped glass fibers as claimed in claim 1, wherein the active agent in the third step is one of sodium zirconium lactate and bis (citric acid diacetyl) dipropoxy zirconium chelate, the emulsifier is one of dioctyl dimethyl ammonium bromide, galactomannan hydroxypropyl quaternary ammonium salt and dimethyl benzyl dodecyl ammonium bromide, and the lubricant is one of melamine cyanurate, magnesium lauryl sulfate and polyethylene glycol monostearate.

3. The processing method of the anti-crack cement mortar reinforced chopped glass fibers as claimed in claim 1, wherein the fourth impregnation process comprises the steps of carrying out impregnation at a bath temperature of 25-30 ℃ for 25-30 min at a bath ratio of 1: 6 at a heat treatment temperature of 200-220 ℃ at a speed of 4-6 m/min and baking at a baking temperature of 140-150 ℃.

4. The processing method of the crack-resistant cement mortar reinforced chopped glass fiber as claimed in claim 1, wherein the third step of organic sodium silicate is one of methyl sodium silicate, ethyl sodium silicate and phenyl sodium silicate, and the impregnating solution comprises the following raw materials in percentage by weight: 3.0-4.5% of organic sodium silicate, 0.2-0.5% of active agent, 0.3-0.5% of lubricant, 0.05-0.1% of emulsifier and the balance of water.