CN104496189A - Boron-free high-performance glass fiber taking pulverized fuel ash and desalted river sand as raw materials, as well as preparation method thereof - Google Patents

Abstract

The invention discloses a boron-free high-performance glass fiber using fly ash and desalinated river sand as raw materials and a preparation method thereof, belonging to the field of material technology. It is made of the following raw materials in weight percentage: 30-55% of fly ash, 0-15% of blast furnace slag, 40-50% of desalinated river sand, 0-12% of magnesium oxide and 0-6% of calcium oxide. The present invention uses fly ash and desalinated river sand as raw materials, adds a small amount of blast furnace slag, magnesium oxide and calcium oxide through the pretreatment of fly ash raw materials, and can prepare high-performance glass fiber in commonly used refractory lining furnaces. The strength and modulus of elasticity are significantly higher than the commonly used E glass and ECR, Advantex boron-free glass, etc., the preparation process is simple, the melting temperature is 1400-1420 ℃, and the difference between the fiber forming temperature and the liquidus temperature is above 70 ℃, which is much higher The minimum standard for glass fiber industrial production is 50°C, and the production cost is low, which meets the glass fiber industrial production standard. And this component glass has higher chemical corrosion resistance and high temperature resistance than traditional E glass.

Description

A boron-free high-performance glass fiber using fly ash and desalinated river sand as raw materials and its preparation method

technical field

The invention relates to a boron-free high-performance glass fiber made of fly ash and desalinated river sand and its preparation method. The application in the field of materials belongs to the field of special glass fiber components.

Background technique

Glass fiber has the characteristics of large specific surface area, high specific strength, heat resistance, non-combustibility, stable physical and chemical properties, etc., and has certain functional designability. Since its birth in the 1930s, with the development of glass fiber production technology, products have been widely used and Aerospace, aviation, automobile, shipbuilding, petrochemical, electrical, electronics, construction, environmental protection, energy, sports and leisure equipment, medical and health care and other fields.

At present, the most commonly used glass fiber at home and abroad is alkali-free glass fiber (E-glass). The new ecological tensile strength of single filament is about 3038-3430MPa, and the elastic modulus is about 72GPa. The glass fiber composition is: SiO2: 52～66wt%; CaO: 16～26wt%; Al ₂ O ₃ : 12～16wt%; B ₂ O ₃ : 5～10wt%; MgO: 0～5wt%; Na ₂ O+K ₂ O: 0～2wt% %; TiO ₂ : 0-0.8 wt %; Fe ₂ O ₃ : 0-5 wt %; Fluorine: 0-1.0 wt %. E-glass is characterized by a low liquidus temperature, about 1149°C, and a wide operating temperature for the production of glass fibers, about 1038°C to 1316°C. It has good melting and fiber forming technology, and high specific strength. It has large specific surface area, heat resistance, and corrosion resistance. Therefore, it is widely used as a reinforcement of composite materials in many fields such as automobiles, electronics, ships, electrical appliances, environmental protection, sports and leisure equipment, and medical and health care. However, because the structure of the glass component contains B2O3 and F2, the acid resistance of this type of glass is poor, and at the same time, the price of raw materials containing B2O3 is high, and the volatile matter is harmful to the environment. For this reason, American Owens-Korning introduced Advantex ^TM glass fiber, which has excellent acid resistance and higher mechanical properties compared with alkali-free glass fiber. Its glass composition (US 5789329): SiO ₂ : 59-62wt%; CaO: 20-24wt%; Al ₂ O ₃ : 12-15wt%; MgO: 1.0-4.0wt%; Na ₂ O: 0-2wt% ; K ₂ O: 0-2 wt %; TiO ₂ : 0-0.9 wt %; Fe ₂ O ₃ : 0-0.5 wt %; Fluorine: 0-0.5 wt %; SO ₃ : 0-0.5 wt %. However, the melting and drawing temperature of Advantex ^TM glass is higher than that of E-glass, which puts forward higher requirements for furnace design, melting technology, fiber forming technology and other aspects.

However, the properties of E-glass fiber or Advantex ^TM glass fiber cannot meet the requirements of some cutting-edge fields such as military industry and aerospace, so countries all over the world have introduced special glass fiber composition formulas one after another. Among them, high-strength glass fiber is used in the largest amount, and its monofilament new ecological tensile strength is about 4200-4900MPa, and its elastic modulus is about 82-86GPa. It is used in rocket engine shells, helicopter rotors, and bulletproof armor. important role in the application. For example, the S-2 ^TM high-strength glass fiber (US3402055) produced by AGY Company in the United States, the S-glass composition is SiO ₂ -Al ₂ O ₃ -MgO system, and its content is SiO ₂ : 65wt%, Al ₂ O ₃ : 25wt%, MgO: 10wt%; R-glass composed of _SiO2 - _Al2O3 -MgO-CaO system with content of _SiO2 : 58-60wt%, _Al2O3 : _23.5-25.5wt %, CaO and MgO: 14 -17wt% _, and _less than 2wt% of impurity components _; in addition, Chinese glass fiber manufacturers have developed S- Glass, such as patent 200910026759.6. However, no matter what kind of high-performance glass, there are problems such as high glass fiber forming temperature, difficult wire drawing, inability to melt in a furnace lined with ordinary oxide refractories, and high production costs, such as S-2 ^TM high-strength glass fiber, which The liquidus temperature of this kind of glass is 1471°C, and the temperature of the drawing bushing is as high as 1571°C. It needs to be melted in a furnace lined with platinum, rhodium and other precious metals; R-glass contains more alumina, and its melting temperature is high, △T Low, easily devitrified. Many glass fiber manufacturers solve production process problems by adjusting components or introducing metal oxides with a melting effect. But SiO ₂ -Al ₂ O ₃ -MgO-CaO is basically unchanged as the main system, which is closely related to the structure of glass.

Contents of the invention

The purpose of the present invention is to use fly ash and desalinated river sand as the main raw materials to propose a boron-free high-performance glass with reasonable composition design and suitable for the production process and equipment of alkali-free glass. Fiber and its preparation method, in order to expand the utilization means of fly ash and desalinated river sand, and reduce the production cost of glass fiber. It should be noted that the high performance here is not higher than that of S-glass or R-glass, but that its strength performance is as close as possible to S/R-glass and higher than that of E-glass under the conditions of general glass production process; Other properties such as acid and alkali resistance, heat resistance, etc. are significantly higher than S/R-glass, which is mainly related to the glass structure.

Technical scheme of the present invention is:

A boron-free high-performance glass fiber using fly ash and desalinated river sand as raw materials is characterized in that it is made of the following raw materials in weight percentage:

Fly ash 30-55%, blast furnace slag 0-15%, desalinated river sand 40-50%, magnesium oxide 0-12wt%, calcium oxide 0-6%.

Preferably, it is made of the following raw materials in weight percentage:

Fly ash 35-48wt%, blast furnace slag 0-10%, desalinated river sand 36-48%, magnesium oxide 0-12wt%, calcium oxide 3-6wt%.

The components such as SiO ₂ , Al ₂ O ₃ , CaO and MgO contained in it are all components of glass fiber. The existence of these components provides the raw materials for blast furnace slag, fly ash and desalinated river sand to be used as glass fiber. possible.

At the same time, industrial waste residues such as fly ash and blast furnace slag were used in the experiment. Due to the heating and cooling process of high-temperature quenching during the production of these industrial waste residues, refractory substances such as SiO ₂ and Al ₂ O ₃ have formed compounds, mainly forming glass and a small amount. Particles such as mullite, mullite is mainly attached to the surface of glass beads and acts as a network bridge. Therefore, the activity of the mineral is relatively high, which leads to a low melting temperature of the glass, thereby improving the efficiency of the furnace and reducing energy consumption and cost.

In the present invention, there is no restriction on the components of fly ash, blast furnace slag and desalinated river sand, because the components fluctuate greatly due to different production areas. However, through a lot of research, it is found that for high-performance glass fiber, the content of SiO ₂ + Al ₂ O ₃ in fly ash is ≥75wt%, and corresponding pretreatment is carried out, and SiO ₂ in desalinated river sand is ≥90wt%, adding an appropriate amount of additives , by adjusting the ratio of the two, high-performance glass fibers with excellent properties can be prepared.

Further, clarifiers are also included;

The clarifying agent is a mixture of CeO ₂ and Li ₂ O, wherein, CeO ₂ <0.6wt%, Li ₂ O<0.6wt%, CeO ₂ +Li ₂ O<0.8wt%;

Alternatively, the clarifying agent is Glauber's salt, and the added amount of Glauber's salt is less than 1.6%.

The composition of the boron-free high-performance glass fiber using fly ash and desalinated river sand as raw materials is as follows: SiO ₂ 60-70wt%, Al ₂ O ₃ 13-25wt%, CaO 6-12wt%, MgO 3-16wt%, Na ₂ O 0.15-0.40wt%, K ₂ O 0.5-0.9wt%, TiO ₂ 0.4-0.9wt%, iron oxide 0.3-0.7wt%, S 0.2-0.9wt%, others 0-1.6wt%.

Further, the composition of the boron-free high-performance glass fiber using fly ash and desalinated river sand as raw materials is as follows: SiO ₂ 64-67wt%, Al ₂ O ₃ 14-20wt%, CaO 7-10wt%, MgO 4- 12wt%, Na ₂ O 0.23-0.4wt%, K ₂ O 0.5-0.8wt%, TiO ₂ 0.5-0.8wt%, iron oxide 0.45-0.62wt%, S 0.3-0.8wt%.

Further, the molding temperature of the boron-free high-performance glass fiber is about 1370°C, the crystallization upper limit temperature of the glass is about 1290°C, and the difference between the glass fiber molding temperature and the glass crystallization upper limit temperature is ≥70°C.

A method for preparing boron-free high-performance glass fibers using fly ash and desalinated river sand as raw materials is characterized in that it includes the following steps:

(1) Take the raw material according to the above weight percentage, heat the fly ash and blast furnace slag in the raw material to 650°C in the muffle furnace, and sieve it once with an electrified iron net. The iron net grid standard is 40 mesh, Then grind the sieved granules below 200 meshes, and sieve them twice with an electrified iron net, the number of times of the second sieves is 3-5 times, and finally obtain the powder as the experimental raw material;

(2) Mix the pretreated fly ash, pretreated blast furnace slag, desalinated river sand, magnesium oxide and calcium oxide according to the ratio, and melt it at 1450°C to obtain molten glass, then cool down the molten glass to the drawing temperature, and draw it. Obtain boron-free high performance glass fiber.

preferred,

The particle size of the raw material particles is 45 mesh sieve residue≤25%.

further,

The magnetic field strength of once sieving described in step (1) is 764-825KA/m;

The magnetic field intensity of secondary sieving described in step (1) is 568-647KA/m.

In the present invention, the SiO ₂ -Al ₂ O ₃ -MgO-CaO system is prepared by using fly ash and desalinated river sand, and adding a small amount of blast furnace slag and magnesium oxide. High-performance glass fiber, in which the total content of SiO ₂ , Al ₂ O ₃ , MgO and CaO is as high as 95wt%-98wt%. This is mainly determined by the relationship between the structure of the glass and its performance. As a high-performance glass fiber, its strength is determined by the structure of the glass and is affected by the diameter of the single filament. Therefore, common high-performance glass fibers are all high-silicon and high-aluminum ratios.

As the basic network skeleton in glass fiber, SiO ₂ has an important influence on the properties of glass fiber. In the classic S-system high-strength glass, the content of _SiO2 is as high as 65%. A certain content of SiO ₂ can make the glass fiber have excellent mechanical strength, chemical resistance and temperature resistance. However, if the content of _SiO2 is too high, the high-temperature viscosity of the glass fiber is high, and it is difficult to melt. If the content of SiO2 is too low, the performance of the glass fiber will be poor and cannot meet the requirements of the glass fiber, because the mechanical strength of the glass depends on the glass fiber. The density of the network structure, especially the bridge-oxygen connection density of the silicon-oxygen tetrahedron is closely related. The denser the network structure of the glass, the more the oxygen number of the silicon-oxygen tetrahedral bridge, the better the mechanical properties, and the greater the strength and modulus.

Al ₂ O ₃ is also a network intermediate of aluminosilicate glass fibers, which has an important influence on the structure and properties of aluminosilicate glass fibers. [AlO ₄ ] entering the glass network framework can improve the strength, temperature resistance, and chemical stability of the glass, and the introduction of an appropriate amount of [AlO ₆ ] can also improve the melting performance of the batch. However, if the content of Al ₂ O ₃ is too low, the mechanical properties of the glass will be affected; if the content of Al ₂ O ₃ is too high, [AlO ₆ ] will increase, which will significantly increase the viscosity and surface tension of the glass, and will also cause the crystallization temperature of the glass Elevated, resulting in difficulties in melting and drawing glass. Experimental research found that the reasonable Al ₂ O ₃ content should be limited to less than 26%, and the classic S, T and R glasses SiO2+Al ₂ O ₃ are all between 80-90%, which is difficult to melt. The content of Al ₂ O ₃ in the glass component of the present invention is 13-25wt%, the content of the optimized formula is 14-20wt%, and the content of SiO ₂ +Al _2O3 is about 80-85wt%, which can meet the requirements of traditional oxide refractory lining Melted in the pool kiln.

MgO and CaO act as important network modifiers in aluminosilicate glass fibers, they can provide free oxygen, which can be used to form aluminum-oxygen tetrahedrons, and also break the continuous spatial arrangement of silicon-oxygen tetrahedrons , so that the bridging oxygen attached to the silicon-oxygen tetrahedron is disconnected to form a non-bridging oxygen, which is connected to a modifier cation such as calcium or magnesium. Because calcium or magnesium forms ionic bonds with non-bridging oxygen, they cannot form network connections. Therefore, the presence of calcium oxide and magnesium oxide will destroy the continuous silicon-oxygen tetrahedral structure of glass fibers and produce structural terminations. Although the presence of MgO and CaO network modifiers is beneficial to the performance of glass fibers to a certain extent, for example, it can reduce the melting temperature, but the two functions in glass are not completely the same. Due to the strong Mg2+ ion field strength, the bond strength of Mg-O is higher than that of Ca-O, which plays an agglomeration role in the glass network structure and plays a key role in improving the strength and modulus of the glass. However, too much MgO increases the crystallization rate and crystallization tendency of the glass, and the glass is prone to devitrification. The introduction of CaO is particularly effective in reducing the high-temperature viscosity of the glass, but its excessive content will result in a decrease in the mechanical properties of the glass. Therefore, the present invention uses desalinated river sand to introduce SiO ₂ . After the desalinated river sand is introduced, the requirements for preparing glass fiber can be met by adjusting their dosage.

The introduction of Na ₂ O and K ₂ O is necessary, and alkali metal oxides play an important role in reducing the viscosity of the glass melt and improving the crystallization tendency of the glass. However, the field strength of alkali metal ions is low, which will depolymerize the structure of the glass and reduce the mechanical properties of the glass, so the amount introduced should be controlled within a certain range. In the optimized scheme of the present invention, the introduction amount of Na ₂ O and K ₂ O is less than 1.5 wt%.

It is better to control the content of iron oxide at 1-3wt%, and the Fe ³⁺ ion field strength is relatively large, so it can be filled into the gap of the glass network to make the structure dense, and at the same time, it can absorb SO ₂ gas generated by sulfide in the melting process to avoid pollution environment. However, if the content is too large, it will cause poor heat permeability of the glass. At the same time, during the melting process, Fe ²⁺ ions are easily formed to color the glass, and it will also oxidize the platinum nozzle and cause damage. Therefore, the content of iron oxide should be controlled in the production process. The content of iron oxides in the raw materials of the present invention is relatively large, and the raw materials need to be pretreated to reduce the content of iron oxides.

In addition, the content of TiO ₂ in the glass component is small, and it is mainly filled into the network structure with network modifiers. Its Ti-O single bond strength is the largest among the glass exosome ions. Therefore, the introduction of TiO ₂ has an effect on improving the strength modulus of glass fiber and reducing the high-temperature viscosity of glass. In addition, TiO ₂ has a prominent effect on improving the chemical corrosion resistance of glass.

Through the above analysis of raw material selection, the inventor uses fly ash as the main raw material and prepares glass fiber with desalinated river sand to improve the utilization rate of fly ash and river sand. At the same time, the relationship between the amount of raw materials is adjusted in order to Can form glass fiber with good performance.

In addition, the inventor firstly pretreated blast furnace slag and fly ash: take secondary fly ash particles (45 mesh sieve, sieve residue ≤ 25%), heat to about 650°C in a muffle furnace, and remove the raw materials moisture and carbon oxides. Then sieve the energized iron mesh at room temperature. The iron mesh grid standard is 40 mesh, and the magnetic field strength is 764-825KA/m. The strength is 568-647KA/m, the number of sieving is 3-5 times, and finally the powder is obtained as the experimental raw material. The purpose of this treatment is to remove iron oxides in the pellets, so as to meet the requirements of glass fiber production. Through this magnetic separation method, the magnetic separation efficiency is as high as 90%. The blast furnace slag processing method is also the same, so it is no longer described.

Beneficial effects of the present invention:

① The present invention uses fly ash and desalinated river sand as raw materials, through the pretreatment of fly ash raw materials, adding a small amount of blast furnace slag and magnesium oxide, can prepare high-performance glass fibers in commonly used refractory lining furnaces, and its strength and The elastic modulus is significantly higher than that of commonly used E glass, ECR, Advantex boron-free glass, etc.

②The preparation process of the boron-free high-performance glass fiber using fly ash and desalinated river sand as raw materials of the present invention is simple, the melting temperature is 1400-1420°C, and the difference between the fiber forming temperature and the liquidus temperature is above 70°C. It is 50°C higher than the minimum standard of glass fiber industrial production, and the production cost is low, which meets the glass fiber industrial production standard. And this component glass has higher chemical corrosion resistance and high temperature resistance than traditional E glass.

3. The raw materials used in the present invention are industrial raw materials and industrial waste residues (not analytically pure, and the price of analytically pure is high), and the requirements for raw materials are relatively low, and the effect is not affected, and can be used in large-scale production.

④ The boron-free high-performance glass fiber of the present invention, which uses fly ash and desalinated river sand as raw materials, does not contain boron, avoids the adverse effects of boron volatilization on the kiln, the environment and production costs during the production process, and has excellent performance and low technological parameters. Reasonable, low production cost and environment-friendly advantages.

Description of drawings

Fig. 1 is the infrared spectrogram of sample example 1 and E glass, Hiper-texTM glass;

Fig. 2 is the DSC differential thermal analysis chart of sample example 1 and E glass, Hiper-texTM glass;

FIG. 3 is a microscope measurement diagram of the glass filament diameter of Sample Example 1. FIG.

Detailed ways

In order to better understand the present invention, the content of the present invention is further illustrated below in conjunction with the examples, but the content of the present invention is not limited to the following examples, and the examples should not be regarded as limiting the protection scope of the present invention.

Example

In the following examples, the components of blast furnace slag, fly ash and quartz sand used are shown in Table 1 below.

The pellets are pretreated before being fired. In the following table, because the content of some components is small and the change is not large, they are not listed.

Table 1 Comparison of components of magnetic separation pellets

components SiO ₂ Al ₂ O ₃ CaO MgO iron oxide untreated fly ash 49.89 34.66 4.80 0.87 4.55 pre-treated fly ash 52.26 36.30 5.02 0.90 0.5

The raw materials of the present invention, that is, fly ash, blast furnace slag and desalinated river sand are common factory raw materials, and do not require special composition ratios, only magnesium oxide and calcium oxide are chemical raw materials. Fly ash blast furnace slag is pretreated before use, and then the raw materials are weighed according to the raw material formula in the following table 2, put into the lifting crucible electric furnace, and stop heating after melting at 1400-1480 ° C for 3-6 hours. When the glass forming temperature is above 20°C, the wire drawing test is carried out. By analyzing the fiberization performance of each component glass sample, including fiberization temperature, liquidus temperature and ΔT temperature, and testing the monofilament strength of the glass fiber at the same time, to show the industrial production and use of each component glass of the present invention Value; In addition, the structural analysis of the component glass samples fundamentally shows the high-strength and high-modulus properties of the glass fiber of the present invention.

Table 2 raw material composition (wt%)

sample example 1 Example 2 Example 3 Example 4 pre-treated fly ash 45 36 45 38 Pretreatment of blast furnace slag 10 8 5 0 desalination of river sand 39 44 40 47 magnesium oxide 3 8 7.5 10 Calcium Oxide 3 4 2.5 5

The chemical composition of the product obtained from the above raw materials is analyzed by X-ray fluorescence spectrum as shown in the following table 3, and the comparison data between the glass composition of the present invention and S-2 ^M , Advantex ^TM , E-glass fiber is shown in the following table:

Table 3 Composition and performance comparison between some samples and commonly used glass

Figure 1 shows the Fourier transform infrared spectrum of sample 1 and E glass, in which the vibration bands at 800-1300cm ^-1 represent the silicon-oxygen tetrahedral structural group, and the vibration bands at 400-600cm ^-1 represent the Si-O-Al Vibration, where Si comes from silicon-oxygen tetrahedrons, and Al comes from aluminum-oxygen tetrahedrons. In Example 1, the absorption intensity of the 800-1300cm ^-1 vibration band increases, narrows and shifts to high frequency, indicating that the bridge oxygen density of the silicon-oxygen tetrahedron in the glass structure is large; the 400-600cm ^-1 vibration band narrows and shifts to High-frequency movement means that the vibration of Si-O-Al is enhanced, more alumina tetrahedrons enter the network structure, and the glass network structure is denser. The denseness of the glass network structure enhances the mechanical properties of the glass, which is the fundamental reason for the increase in the strength of the glass.

Figure 2 shows the DSC differential thermal analysis spectra of sample 1 and E glass. The crystallization front temperature of the glass component sample is obtained from the differential thermal analysis spectrum, and its size can reflect the degree of polymerization of the network structure of the glass. Generally, the higher the crystallization temperature, the higher the degree of polymerization of the glass. This is because the structure undergoes orderly rearrangement during the glass crystallization process. The higher the degree of glass polymerization, the greater the Gibbs free energy, and the more energy required for rearrangement, that is, a higher temperature is required to obtain ion rearrangement. Greater kinetic energy overcomes the potential barrier. It can be seen from the figure that the glass transition temperature Tg of E glass is 729°C, and the crystallization peak temperature Tl is 1112°C. However, Sample 1 has no crystallization peak except for the glass transition temperature of 899°C. Because the crystallization temperature is relatively high, which exceeds the range of DSC, the peak range of crystallization is finally obtained at about 1310°C through the temperature gradient furnace test.

The strength of the new ecological monofilament is obtained through fine measurement technology: draw the monofilament, take 6 to 10 samples on a very long monofilament, each 25mm long sample; install the sample, and then measure the The tensile breaking strength of the sample. All these operations require that the fractured part of the sample should not be in contact with any material, and must be carried out within 10 minutes after the monofilament is pulled out. The environmental conditions for the measurement are usually 25°C and the relative humidity is less than or equal to 40%. The diameter of the glass is mainly obtained through microscope measurement. As shown in FIG. 3 , the diameter of the glass fiber in Sample 1 is 40.71 μm. The calculation formula of monofilament strength is as follows:

$\mathrm{<span\; class="notranslate">\; \&sigma;</span>}<span\; class="notranslate">\; =</span>\frac{\mathrm{<span\; class="notranslate">\; 4</span>}\mathrm{<span\; class="notranslate">\; f</span>}<span\; class="notranslate">\; \&times;</span>{\mathrm{<span\; class="notranslate">\; 10</span>}}^{\mathrm{<span\; class="notranslate">\; 4</span>}}}{{\mathrm{<span\; class="notranslate">\; \&pi;d</span>}}^{\mathrm{<span\; class="notranslate">\; 2</span>}}}$

σ: tensile strength, unit MPa;

F: monofilament tensile force, unit cN;

d: diameter of monofilament, unit μm.

The strength of the new ecological monofilament can directly reflect the high-strength performance of glass fibers, and is the most intuitive feedback on the mechanical properties of high-performance glass. The new ecological strength of monofilament is calculated by the above formula, which directly reflects whether the glass fiber of the present invention can be used as an important basis for high-strength glass fiber. It is necessary to explain here that the reason why the new ecological strength of the glass is higher than that in normal use is that the strength of the freshly drawn glass fiber has not been damaged; as it is exposed to the air for a period of time, it is affected by hydration and other aspects, and at the same time Due to factors such as frictional damage during the winding process, the strength will eventually decrease. The new ecological monofilament strength of E glass fiber is about 3700MPa, which is higher than that of carbon fiber. But after a period of time, the strength of E glass fiber dropped to 1200MPa.

It can be obtained from Table 3 and the above analysis that the glass fiber prepared by using the high-performance glass fiber composition of the present invention has simple ingredients and few expensive chemical raw materials, and the molding temperature of the glass fiber is about 1370°C. The crystallization peak temperature of the glass is around 1290°C, which overcomes the high melting temperature of high-performance glass fiber and the disadvantages of expensive production equipment. The material is lined with the furnace for pool kiln wire drawing, and at the same time, it also overcomes the harsh preparation process of S-2 ^TM and other high-performance glass wire drawing, which greatly reduces the manufacturing cost of high-performance glass fiber.

The performance characteristics of the above-mentioned optimized glass component complexes are high strength, high modulus, monofilament tensile strength, temperature resistance, and chemical corrosion resistance are all higher than Advantex glass fibers; Glass fiber Hiper-tex ^TM glass (Chinese patents CN101300199A, CN101300200A) is similar, and its new ecological monofilament strength is 4100-4500MPa, and the softening point is 940-960°C. However, the production raw materials are cheap, the source is wide, and the manufacturing cost is low. Therefore, the resin compound using the high-performance glass fiber of the present invention as a reinforcing material has high strength, strong chemical corrosion resistance, high temperature resistance, and light weight, and is suitable for fields such as military industry, aviation, transportation, and wind power generation that require high strength.

Claims (9)

1. be raw material without a boron high-performance glass fiber with flyash and desalination river sand, it is characterized in that, be made up of the raw material of following weight percent:

Flyash 30-55%, blast-furnace slag 0-15%, desalination river sand 40-50%, magnesium oxide 0-12wt%, calcium oxide 0-6%.

2. according to claim 1 is raw material without boron high-performance glass fiber with flyash and desalination river sand, it is characterized in that, is made up of the raw material of following weight percent:

Flyash 35-48wt%, blast-furnace slag 0-10%, desalination river sand 36-48%, magnesium oxide 0-12wt%, calcium oxide 3-6wt%.

3. according to claim 1 and 2 is raw material without boron high-performance glass fiber with flyash and desalination river sand, it is characterized in that, also comprises finings;

Described finings is CeO ₂and Li ₂the mixture of O, wherein, CeO ₂<0.6wt%, Li ₂o<0.6wt%, CeO ₂+ Li ₂o<0.8wt%;

Or described finings is saltcake, the add-on < 1.6% of described saltcake.

4. according to claim 1-3 arbitrary described be raw material without boron high-performance glass fiber with flyash and desalination river sand, it is characterized in that, described with flyash with to desalinate the composition without boron high-performance glass fiber that river sand is raw material as follows: SiO ₂60-70wt%, Al ₂o ₃13-25wt%, CaO6-12wt%, MgO3-16wt%, Na ₂o0.15-0.40wt%, K ₂o0.5-0.9wt%, TiO ₂0.4-0.9wt%, ferriferous oxide 0.3-0.7wt%, S0.2-0.9wt%, other 0-1.6wt%.

5. according to claim 4 is raw material without boron high-performance glass fiber with flyash and desalination river sand, it is characterized in that, described with flyash with to desalinate the composition without boron high-performance glass fiber that river sand is raw material as follows: SiO ₂64-67wt%, Al ₂o ₃14-20wt%, CaO7-10wt%, MgO4-12wt%, Na ₂o0.23-0.4wt%, K ₂o0.5-0.8wt%, TiO ₂0.5-0.8wt%, ferriferous oxide 0.45-0.62wt%, S0.3-0.8wt%.

6. according to claim 1-5 arbitrary described be raw material without boron high-performance glass fiber with flyash and desalination river sand, it is characterized in that, the described mold temperature without boron high-performance glass fiber is about 1370 DEG C, the crystallization of glass reaches the standard grade temperature at about 1290 DEG C, difference >=70 DEG C of its glass fibre mold temperature and devitrification of glass ceiling temperature.

7., with the preparation method without boron high-performance glass fiber that flyash and desalination river sand are raw material, it is characterized in that, comprise the following steps:

(1) raw material is taken according to the arbitrary described weight percent of claim 1-3, flyash in raw material and blast-furnace slag are heated to 650 DEG C in retort furnace, once sieve with the iron net of energising, iron net mesh standard is 40 orders, then below grinding 200 order is carried out to the pellet that sieves, sieve with energising iron net secondary, the secondary number of times that sieves is 3-5 time, finally obtains powder as experimental raw;

(2) pretreated flyash, pretreated blast-furnace slag, desalination river sand, magnesium oxide and calcium oxide are mixed by proportioning, obtain glass metal 1450 DEG C of meltings, then glass metal is cooled to wire-drawing temperature, wire drawing, obtain without boron high-performance glass fiber.

8. the preparation method without boron high-performance continuous glass fibre according to claim 7, is characterized in that, the granularity of described feed particles is 45 mesh sieve margin≤25%.

9. the preparation method without boron high-performance continuous glass fibre according to claim 7, is characterized in that,

The magneticstrength of once sieving described in step (1) is 764-825KA/m;

The magneticstrength that described in step (1), secondary sieves is 568-647KA/m.