CN113620633B

CN113620633B - Treatment process method of anti-crack cement mortar reinforced chopped glass fibers

Info

Publication number: CN113620633B
Application number: CN202111058832.5A
Authority: CN
Inventors: 范秀娟; 张杨; 张道盘; 范兴伟
Original assignee: Wuhe Weijia Composite Material Co ltd
Current assignee: Wuhe Weijia Composite Material Co ltd
Priority date: 2021-09-10
Filing date: 2021-09-10
Publication date: 2022-10-25
Anticipated expiration: 2041-09-10
Also published as: CN113620633A

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, in the past, with increasing numbers and applications. 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 fibers, low mechanical property of products and reduced appearance performance, the geometric dimension of the chopped glass fibers is the same as that of the traditional chopped strands. 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 use in more and more fields, but high brittleness is a fundamental drawback. Chinese patent CN110818340A discloses an anti-crack cement mixture with good anti-crack performance by adjusting the components of the anti-crack cement mixture, and in order to solve the brittleness problem, people add 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 have been used in infrastructure construction and national key engineering construction every year in our country. 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 keenly required to develop a treatment process for the anti-crack 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 to 0.2mol/L sodium hydroxide solution, etching for 0.1 to 0.2h at 20 ℃, taking out the chopped glass fibers, washing the chopped glass fibers to be neutral by using pure water, then putting the chopped glass fibers into an 80 ℃ oven, drying for 2 to 4h, 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 fiber 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 5-10min, and filtering; the chopped glass fibers and the accelerator are uniformly mixed by 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 Na ₂ SiF _6， And the aqueous solution of sodium fluosilicate is acidic, and the hydrolysate of sodium fluosilicate contains hydrofluoric acid: na (Na) ₂ SiF ₆₊ 4H ₂ O→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 of 1.2-1.5 times, pouring the organic sodium silicate into a mixing kettle, stirring, weighing a lubricant, dissolving the lubricant in hot water with the weight of 10-12 times of the lubricant at 70-80 ℃, adding cold water with the weight of 7-8 times of the lubricant after dissolving, pouring the lubricant into the mixing kettle when the temperature of the solution is reduced to 30-45 ℃, continuously stirring, weighing an emulsifier, dissolving the emulsifier in water with the weight of 15-16 times of the emulsifier, pouring the mixture into the mixing kettle, continuously stirring, accurately weighing an active agent, diluting with water with the weight of 8-10 times of the emulsifier, pouring the mixture into the mixing kettle, adding the rest of water, and continuously stirring for 5-10 minutes to obtain a wetting solution for later use; and fourthly, after the chopped glass fiber obtained in the fourth step and the second step is subjected to heat treatment for 50 to 60 seconds, soaking according to a technological soaking process, baking for 10 to 12min, and cooling to 25 to 30 ℃ to obtain the glass fiber.

The organic sodium silicate is mainly used for establishing and promoting the interfacial bonding between inorganic matters and polymers, and can change the hydrophilicity of the surface of the glass fiber into 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 zirconium is highly reactive, does not exist in a metal ion state, 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 substance, thereby exhibiting 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 the addition of the emulsifier.

Further, the fourth impregnation process comprises the steps of heat treatment at a speed of 4-6 m/min at 200-220 ℃, impregnation at 25-30 ℃ for 25-30min at a bath ratio of 1: 6, and baking at 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 to 4.5 percent of organic sodium silicate, 0.2 to 0.5 percent of active agent, 0.3 to 0.5 percent of lubricant, 0.05 to 0.1 percent of emulsifier and the balance of water.

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

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

[CH ₃ Si(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 function: the film forming agent has the functions of protecting 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 zirconium is highly reactive, does not exist in a metal ion state, 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 hydrophobic 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 refine the structure of the material, so that larger gaps are filled, and the interface is smoother and denser.

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 tensile strength and the crack resistance of the concrete can be obviously improved by adding the glass fiber into the cement; 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, the dried chopped glass fiber is fluosilicic acid with the mass ratio of 0.5 percentPutting the sodium accelerator solution into a high-speed mixer, stirring at 2500r/min for 10min, and filtering; 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% of organic sodium silicate, 0.2% of active agent, 0.3% of lubricant, 0.05% 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 bis-octyl dimethyl ammonium bromide, the lubricant is magnesium lauryl sulfate, the organic sodium silicate is diluted by 1.2 times of water by weight and poured into a mixing kettle, the mixture is stirred, the lubricant is weighed, the lubricant is dissolved by 10 times of hot water at 80 ℃ by weight of the lubricant, 7 times of cold water by weight of the lubricant is added after the lubricant is dissolved, the solution is poured into the mixing kettle when the temperature is reduced to 30 ℃, the mixture is stirred continuously, the emulsifier is weighed, the emulsifier is dissolved by 16 times of water by weight of the emulsifier, the mixture is poured into the mixing kettle, the stirring is continued, the active agent is weighed accurately, the mixture is diluted by 10 times of water and poured into the mixing kettle, the rest of water is added, and the stirring is continued for 10 minutes to obtain a wetting solution for later use; and fourthly, after the chopped glass fibers obtained in the second step are subjected to heat treatment for 60 seconds, soaking for 30min at the heat treatment temperature of 520 m/min of the vehicle speed and the bath ratio of 1: 6 at the baking temperature of 150 ℃ at 30 ℃, baking for 112min after soaking according to the process soaking process, and cooling to 230 ℃ to obtain the chopped glass fibers. Water reducing agent ART-MPC of Ton science and technology Limited company, chopped glass fiber WJ101-3 of Weijia composite of Wuhe county, nominal diameter 10 μm, chopped length 3.0mm, wherein 62% is Si0 ₂ 、7%Zr0 ₂ 、0.1%TiO ₂ 、5.6CaO、0.8Al ₂ 0 ₃ 、2.0%K ₂ 0、14%Na ₂ O。

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% of organic sodium silicate, 0.2% of active agent, 0.3% of lubricant, 0.05% of emulsifier and the balance of water, wherein the active agent is sodium lactate zirconium Aero-HX 9013-Zr-803, the emulsifier is galactomannan hydroxypropyl quaternary ammonium salt GUARC3600, the lubricant is polyethylene glycol monostearate, the organic sodium silicate is diluted by 1.2 times of water by weight and poured into a mixing kettle, the mixture is stirred, the lubricant is weighed, the lubricant is dissolved by hot water at 70 ℃ which is 10 times of the weight of the lubricant, cold water which is 7 times of the weight of the lubricant is added after the lubricant is dissolved, the solution is poured into the mixing kettle when the temperature is reduced to 30 ℃, the emulsifier is continuously stirred and weighed, the emulsifier is dissolved by water which is 15 times of the weight of the emulsifier and poured into the mixing kettle, the mixture is continuously stirred, the accurate active agent is weighed, the accurate active agent is diluted by 8 times of water and poured into the mixing kettle, the rest of water is added, and the mixture is continuously stirred for 5 minutes to obtain a wetting solution for later use; and fourthly, after the chopped glass fibers obtained in the second step are subjected to heat treatment for 50 seconds, the impregnation process is to impregnate the chopped glass fibers for 25min at the heat treatment temperature of 200 ℃ at the speed of 4 m/min and at the temperature of 25 ℃ at the bath ratio of 1: 6, bake the chopped glass fibers for 10min after the chopped glass fibers are impregnated according to the impregnation process, and cool the chopped glass fibers 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 3.0mm.

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 Guangdong Longjian building cement P.042.5 product:

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 fiber disclosed by the invention has the advantages that the glass fiber can effectively improve the anti-cracking capability 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 treatment process method 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 treatment process method has a 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 the chopped glass fiber into 0.15-0.2 mol/L sodium hydroxide solution, etching for 0.1-0.2h at 20 ℃, 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 fiber 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 5-10min, and filtering; the third step: diluting organic sodium silicate with water with the weight of 1.2-1.5 times, pouring the diluted organic sodium silicate into a mixing kettle, stirring, weighing a lubricant, dissolving the lubricant in hot water with the weight of 10-12 times and the temperature of 70-80 ℃, adding cold water with the weight of 7-8 times of the lubricant after dissolving, pouring the solution into the mixing kettle when the temperature of the solution is reduced to 30-45 ℃, continuously stirring, weighing an emulsifier, dissolving the emulsifier in water with the weight of 15-16 times of the emulsifier, pouring the solution into the mixing kettle, continuously stirring, accurately weighing an active agent, diluting the solution with water with the weight of 8-10 times, pouring the solution into the mixing kettle, adding the rest water, and continuously stirring for 5-10 minutes to obtain an impregnation solution for later use; fourthly, after the chopped glass fiber obtained in the second step is subjected to heat treatment for 50 to 60 seconds, the chopped glass fiber is soaked according to a process soaking technology and then is baked for 10 to 12min, and the chopped glass fiber is cooled to 25 to 30 ℃ to obtain the glass fiber;

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;

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 solution comprises the following raw materials in percentage by weight: 3.0 to 4.5 percent of organic sodium silicate, 0.2 to 0.5 percent of active agent, 0.3 to 0.5 percent of lubricant, 0.05 to 0.1 percent of emulsifier and the balance of water.

2. The processing method of the crack-resistant cement mortar reinforced chopped glass fiber as claimed in claim 1, wherein the fourth impregnation process is carried out at a speed of 4 to 6 m/min, a heat treatment temperature of 200 to 220 ℃, an impregnation temperature of 25 to 30 ℃ and a baking temperature of 140 to 150 ℃, wherein the bath ratio is 1: 6, and the impregnation time is 25 to 30min.