CN118290033A - Preparation method of T-shaped glass fiber and high-strength transparent composite material thereof - Google Patents
Preparation method of T-shaped glass fiber and high-strength transparent composite material thereof Download PDFInfo
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- CN118290033A CN118290033A CN202410725217.2A CN202410725217A CN118290033A CN 118290033 A CN118290033 A CN 118290033A CN 202410725217 A CN202410725217 A CN 202410725217A CN 118290033 A CN118290033 A CN 118290033A
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 175
- 239000002131 composite material Substances 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000011521 glass Substances 0.000 claims abstract description 66
- 239000002994 raw material Substances 0.000 claims abstract description 55
- 238000002834 transmittance Methods 0.000 claims abstract description 45
- 239000003822 epoxy resin Substances 0.000 claims abstract description 28
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 28
- 239000004744 fabric Substances 0.000 claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 13
- 229910000629 Rh alloy Inorganic materials 0.000 claims abstract description 8
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000012535 impurity Substances 0.000 claims description 15
- 229910052681 coesite Inorganic materials 0.000 claims description 12
- 229910052906 cristobalite Inorganic materials 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 12
- 229910052682 stishovite Inorganic materials 0.000 claims description 12
- 229910052905 tridymite Inorganic materials 0.000 claims description 12
- 238000002844 melting Methods 0.000 claims description 9
- 230000008018 melting Effects 0.000 claims description 9
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 8
- 238000013329 compounding Methods 0.000 claims description 7
- 238000009941 weaving Methods 0.000 claims description 7
- 238000004804 winding Methods 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 229910004298 SiO 2 Inorganic materials 0.000 abstract description 3
- 229920005989 resin Polymers 0.000 description 21
- 239000011347 resin Substances 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- 239000003795 chemical substances by application Substances 0.000 description 13
- 239000004841 bisphenol A epoxy resin Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 11
- 238000002156 mixing Methods 0.000 description 11
- 239000000835 fiber Substances 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 9
- 238000004513 sizing Methods 0.000 description 9
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 6
- 239000000805 composite resin Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000002310 reflectometry Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- 238000005491 wire drawing Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- 238000000149 argon plasma sintering Methods 0.000 description 2
- 229910052810 boron oxide Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
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- 239000005304 optical glass Substances 0.000 description 2
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- 238000003723 Smelting Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
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- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
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- 239000011151 fibre-reinforced plastic Substances 0.000 description 1
- 239000005329 float glass Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 239000008782 xin-kang Substances 0.000 description 1
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Abstract
The invention relates to a preparation method of a T-shaped glass fiber and a high-strength transparent composite material thereof, wherein the T-shaped glass fiber comprises the following glass raw material components in percentage by mass based on the total amount of all glass raw materials in the T-shaped glass fiber: 10-12% of SiO 266~72%,Al2O30~7%,K2 O and Na 2 O, 10-14% of CaO and MgO, and 0-3% of La 2O30~3%,B2O3; after the uniformly mixed glass raw materials are melted, drawing wires through a platinum-rhodium alloy bushing plate to obtain T-shaped glass fibers; the glass fiber yarn is prepared by coating the T-shaped glass fiber with the impregnating compound, and is wound into a spindle to be woven into glass fiber fabric, and then the glass fiber fabric is compounded with epoxy resin to prepare the high-strength transparent composite material. The T-shaped glass fiber has a lower refractive index; the preparation method is simple; the preparation method of the high-strength transparent composite material can ensure high tensile strength and high transmittance.
Description
Technical Field
The invention belongs to the technical field of resin matrix composite materials, and relates to a T-shaped glass fiber and a preparation method of a high-strength transparent composite material.
Background
Resin-based glass fiber reinforced composite (GFRP), commonly known as glass fiber reinforced plastics, has good mechanical, chemical and heat resistance properties, and is widely applied to various structural reinforcing materials, such as vehicle frame structures of automobiles, airplanes, high-speed rails and the like, shells of electronic devices of mobile phones, televisions and the like, photovoltaics, wind power and the like. However, the glass fiber composites known today are either white or colored by adding colorants to the resin. If the resin-based composite material can be made into organic glass with high transparency, and has both mechanical and chemical properties of the composite material, the resin-based composite material can be widely applied to various structures.
In the prior art, glass fiber reinforced resin has poor transparency, and the main reasons are as follows: the refractive index of the glass fiber is not matched with that of the resin matrix; when light enters one medium (e.g., glass fiber) into another medium (e.g., resin), if the refractive indices of the two mediums are not matched, the light will be reflected and refracted at the interface and will not pass smoothly. If light enters the glass from air, the surface reflectivity calculation formula of the light is shown as formula (1);
R= (n Glass -n Air-conditioner )2/(n Glass and n Air-conditioner )2 (1);
The refractive index n Glass of the common plate glass is 1.50, and n Air-conditioner is1, so that the surface reflectivity reaches 4%; the glass transmittance test is that the front and back glass surfaces of the glass sheet, so that the total reflectivity is 8%, and the glass transmittance with different thicknesses is calculated by introducing a formula (2) into the national standard GB 11614-2022 flat glass;
T2=92(T1/92)（D 2 /D 1 ） （2）；
Wherein T 1 is the transmittance of the sample in units of: the%; t 2 is the transmittance in terms of D 2 thickness, in units of: the%; d 1 is the sample thickness, unit: mm;
In the case of ordinary E glass fiber, the refractive index is 1.56, the single surface reflectivity R of the glass fiber reaches 4.79 percent, and the total transmittance of the two sides of the glass sheet is only 90.43 percent.
In order to improve the refractive index of the resin matrix, additional groups are required to be introduced, so that the ageing resistance is poor; in the manufacture of glass fibers, a layer of sizing is typically applied to improve the wettability and adhesion between the fiber and the resin. However, this sizing is difficult to remove completely when preparing GFRP, and forms an interface between the fibers and the resin, which not only affects the adhesion between the fibers and the resin, but also adversely affects the light transmittance. Light may scatter or reflect as it passes through this interface, thereby reducing the transparency of the GFRP.
There have been some studies in an attempt to solve the problem of poor transparency of glass fiber reinforced resins. For example, CN201310566036.1 discloses a transparent glass fiber reinforced polypropylene composite material and a preparation method thereof, and the transparent composite material is prepared by adding 5-25% of glass fiber, but the transmittance is not more than 80%, and when the glass fiber content reaches 25%, the tensile strength is 70 MPa, the transmittance is only 65%, and the transparent composite material cannot have higher transmittance at the same time of high tensile strength.
CN201810057510.0 discloses a transparent core rod made of fiber reinforced resin matrix composite material for overhead conductor and its preparation process, the patent uses carbon fiber and glass fiber to compound, and uses thermosetting resin to prepare the transparent core rod, the transparency is not explicitly mentioned in the patent, but the carbon fiber is black, its transparency is limited.
CN202311726012.8 discloses a high-light-transmission glass fiber reinforced epoxy resin composite material and a preparation method thereof, which uses E glass fiber or S glass fiber to realize high-light-transmission glass fiber reinforcement, uses epoxy resin as a matrix, treats a sizing agent through commercial fiber bundles, coats the sizing agent, and adds 30-70% by mass of glass fiber, the thickness of the prepared transparent composite material is only 0.40mm, and the transmittance converted into 2mm is only 77.5% according to 88.9% transmittance.
Therefore, the glass fiber resin composite material has very important significance in solving the problem that the glass fiber resin composite material in the prior art cannot have higher transmittance while having high tensile strength.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a T-shaped glass fiber and a preparation method of a high-strength transparent composite material thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The T-shaped glass fiber comprises the following glass raw material components in percentage by mass based on the total amount of all glass raw materials in the T-shaped glass fiber:
SiO2 66~72%；
Al2O3 0~7%；
10-12% of the total amount of K 2 O and Na 2 O;
10-14% of the total amount of CaO and MgO;
La2O3 0~3%；
B2O3 1~4%；
the total content (mass percent) of Fe 2O3 impurities in the glass raw material is less than or equal to 0.01%;
SiO 2 is 66-72%, and the tetrahedral network structure of the glass of the T-shaped glass fiber is mainly provided, so that the glass has good heat resistance and stability, and lower melting temperature and molding operability.
Al 2O3 is 0-7%, chemical stability of the T-shaped glass fiber is mainly provided, the T-shaped glass fiber is matched with SiO 2, crystallization tendency of glass is reduced, a fiber-forming wire drawing window is improved, qualification rate is improved, and the effect on improving strength is remarkable.
The total amount of K 2 O and Na 2 O is 10-12%, the fluxing agent of the T-shaped glass fiber can also improve the conductivity of the T-shaped glass fiber while reducing the melting temperature, and the total content of K 2 O and Na 2 O is not more than 12% in order to reduce the dielectric constant, wherein the transmittance and the refractive index can be improved by K 2 O.
Since the content of alkali metal is limited, alkaline earth metal oxide is added to promote smelting, and meanwhile, mgO can also improve the strength of a glass network body, improve the mechanical property of glass fiber and has a good regulating effect on improving the strength of T glass fiber.
La 2O3 is 0-3%, and the oxide is mainly used for adjusting the refractive index of the T-shaped glass fiber, and the transmittance of the high-strength transparent composite material is directly influenced by the matching of the refractive indexes, so that the precise allocation of the refractive index is realized through the fine adjustment of the La 2O3 content.
B 2O3 is 1-4%, boron oxide has the effects of further reducing the melting temperature and improving the heat resistance of the glass fiber, and has the effect of reducing the refractive index of the glass, and the effects of the boron oxide are remarkable in the aspects of blending the refractive index and the melting temperature.
The total content of Fe 2O3 impurities in the glass raw material is less than or equal to 0.01 percent, and the content of Fe 2O3 is strictly controlled so as to reduce the absorption coefficient of the glass to visible light and ultraviolet rays.
The refractive index of the T-shaped glass fiber is 1.502-1.512.
As a preferable technical scheme:
the T-shaped glass fiber comprises the following glass raw material components in percentage by mass based on the total amount of all glass raw materials in the T-shaped glass fiber:
SiO2 68%；
Al2O3 6%；
11% of the total amount of K 2 O and Na 2 O;
13% of the total amount of CaO and MgO;
La2O3 1%；
B2O3 1%；
The total content of Fe 2O3 impurities in the glass raw material is 0.006%.
The T-shaped glass fiber comprises the following glass raw material components in percentage by mass based on the total amount of all glass raw materials in the T-shaped glass fiber:
SiO2 72%；
Al2O3 1%
11% of the total amount of K 2 O and Na 2 O;
13% of the total amount of CaO and MgO;
B2O3 3%；
the total content of Fe 2O3 impurities in the glass raw material was 0.08%.
The invention also provides a preparation method of the T-shaped glass fiber, which is characterized in that after the uniformly mixed glass raw materials are melted for 3-4 hours at 1450-1550 ℃, the T-shaped glass fiber is prepared by wire drawing of a platinum-rhodium alloy bushing.
The invention also provides a preparation method of the high-strength transparent composite material, which comprises the steps of preparing glass fiber yarns after the T-shaped glass fibers are coated with the impregnating compound, and carrying out spindle weaving on the glass fiber yarns to obtain glass fiber fabrics with the thickness of 20-50 microns, and then compounding the glass fiber fabrics with epoxy resin to prepare the high-strength transparent composite material;
the impregnating compound is epoxy resin with the refractive index of 1.502-1.512;
the thickness of the high-strength transparent composite material is 2mm, the tensile strength is more than 250MPa, and the transmittance is more than 85%.
As a preferable technical scheme:
According to the preparation method of the high-strength transparent composite material, the coating amount of the impregnating compound is 0.1-0.5wt%.
According to the preparation method of the high-strength transparent composite material, the glass fiber fabric accounts for 10-50wt% of the high-strength transparent composite material.
The principle of the invention:
The iron element in the traditional glass fiber affects the transmittance, and the invention improves the transmittance of the glass fiber by reducing the content of iron impurities. According to the ultra white float glass industry standard JC/T2128-2012: the content of Fe 2O3 in the composition is not more than 0.015%. In order to prepare the high-transmittance T-shaped glass fiber, the invention is realized by strictly controlling the content of Fe 2O3 in the raw material, so that the total content of Fe 2O3 impurities in the glass raw material is controlled to be less than or equal to 0.01 percent.
The glass fiber yarns are refracted due to different refractive indexes, and the impregnating compound which has almost the same refractive index as the T-shaped glass fibers is adopted, so that the refractive indexes of the prepared glass fiber yarns are the same, and the refraction is reduced;
reflection and refraction can be generated between the glass fiber yarns and the resin matrix due to different refractive indexes, and the transparency is further improved by ensuring that the refractive indexes are basically the same, eliminating the reflection and the refraction;
The impregnating compound in the fiber yarns in the traditional transparent composite material cannot be removed cleanly or cannot be removed, so that light reflection and loss are caused.
The refractive index of the T-shaped glass fiber is 1.502-1.512, which is lower than that of the common glass fiber by 1.54-1.57, so that the T-shaped glass fiber is easier to match with resin with the same refractive index, the stability of the composite material is improved, and the yellowing phenomenon is reduced.
In conclusion, the high-strength transparent composite material prepared by the method ensures that the tensile strength is more than 250MPa and the transmittance is more than 85%.
The beneficial effects are that:
(1) According to the T-shaped glass fiber, the total content of Fe 2O3 impurities in the glass raw material is less than or equal to 0.01%, so that the T-shaped glass fiber has a lower refractive index and a higher transmittance;
(2) The preparation method of the T-shaped glass fiber is simple in process and convenient to operate;
(3) According to the preparation method of the high-strength transparent composite material, the impregnating compound with the same refractive index as that of the T-shaped glass fiber is adopted, so that the refractive index among glass fiber yarns is the same, the refraction is reduced, the impregnating compound is not required to be removed, the preparation process is simplified, and the high-strength transparent composite material has good stability and yellowing resistance;
(4) According to the preparation method of the high-strength transparent composite material, the optical performance is obviously improved on the premise of ensuring the mechanical performance, and the prepared high-strength transparent composite material can ensure that the tensile strength is more than 250MPa and the transmittance is more than 85%.
Drawings
FIG. 1 is a graph showing the transmittance of the high strength transparent composites of examples 6-10; wherein T1 is example 6, T2 is example 7, T3 is example 8, T4 is example 9, and T5 is example 10.
Detailed Description
The application is further described below in conjunction with the detailed description. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and such equivalents are intended to fall within the scope of the application as defined in the appended claims.
The test methods related to the performance indexes in the embodiment and the comparative example of the invention are as follows:
Glass fiber density: reference is made to GB/T5432-2008 "glass Density determination buoyancy method".
Refractive index of glass fiber: reference GB/T7962.1-2010 colorless optical glass test method part 1: refractive index and dispersion coefficient.
Glass fiber transmittance: reference GB/T7962.12-2010 colorless optical glass test method part 12: transmittance in the spectrum, and average value of transmittance in the visible light wave band in GB/T2680-2021 standard were measured.
Glass fiber tensile strength: reference is made to the measurement of the tensile properties of GB/T31290-2022 carbon fibre monofilaments.
Modulus of elasticity of glass fiber: reference is made to the measurement of the tensile properties of GB/T31290-2022 carbon fibre monofilaments.
Tensile strength of the composite: reference is made to GB/T1447-2005 method for testing tensile properties of fiber reinforced plastics.
Transmittance of the composite material: with reference to the measurement of the transmittance and haze of the GB/T2410-2008 transparent plastic, the average value of the transmittance in the visible light band in the GB/T2680-2021 standard is measured.
Example 1
A preparation method of T-shaped glass fiber comprises the following specific steps:
(1) Based on the total amount of all glass raw materials in the T-shaped glass fiber, the T-shaped glass fiber comprises the following glass raw material components in percentage by mass:
SiO2 68%；
Al2O3 6%；
K2O 1%；
Na2O 10%；
CaO 10%；
MgO 3%；
La2O3 1%；
B2O3 1%；
The total content of Fe 2O3 impurities in the glass raw material is 0.006%;
(2) And (3) melting the uniformly mixed glass raw materials for 4 hours at 1480 ℃, and then drawing wires through a platinum-rhodium alloy bushing plate to obtain the T-shaped glass fiber.
The refractive index of the obtained T-shaped glass fiber was 1.508.
Example 2
A preparation method of T-shaped glass fiber comprises the following specific steps:
(1) Based on the total amount of all glass raw materials in the T-shaped glass fiber, the T-shaped glass fiber comprises the following glass raw material components in percentage by mass:
SiO2 68%；
Al2O3 5%；
Na2O 10%；
CaO 12%；
La2O3 3%；
B2O3 2%；
The total content of Fe 2O3 impurities in the glass raw material is 0.008%;
(2) And (3) melting the uniformly mixed glass raw materials for 3.5 hours at 1530 ℃, and then drawing wires through a platinum-rhodium alloy bushing plate to obtain the T-shaped glass fiber.
The refractive index of the prepared T-shaped glass fiber is 1.511.
Example 3
A preparation method of T-shaped glass fiber comprises the following specific steps:
(1) Based on the total amount of all glass raw materials in the T-shaped glass fiber, the T-shaped glass fiber comprises the following glass raw material components in percentage by mass:
SiO2 72%；
Al2O3 1%；
K2O 1%；
Na2O 10%；
CaO 8%；
MgO 5%；
B2O3 3%；
The total content of Fe 2O3 impurities in the glass raw material is 0.008%;
(2) After the uniformly mixed glass raw materials are melted for 3 hours at 1520 ℃, the T-shaped glass fiber is prepared by wire drawing through a platinum-rhodium alloy bushing.
The refractive index of the obtained T-shaped glass fiber was 1.502.
Comparative example 1
A method for producing E-type glass fiber, which is basically the same as in example 3, except that the E-type glass fiber comprises the following glass raw material components in mass percent based on the total amount of all glass raw materials in the E-type glass fiber:
SiO2 54%；
Al2O3 16%；
Na2O 0.5%；
CaO 17%；
MgO 4.4%；
B2O3 8%；
Fe2O3 0.1%。
the refractive index of the E-type glass fiber is 1.560, and the internal transmittance is only 92%.
Comparing comparative example 1 with example 3, it was found that the E-type glass fiber has a high refractive index and low internal transmittance, because the E-type glass fiber contains a small amount of Fe 2O3 as a raw material, and the glass fiber is formed to have an off-white color due to light scattering caused by a smaller diameter, and thus has a low internal transmittance.
Example 4
A preparation method of T-shaped glass fiber comprises the following specific steps:
(1) Based on the total amount of all glass raw materials in the T-shaped glass fiber, the T-shaped glass fiber comprises the following glass raw material components in percentage by mass:
SiO2 70%；
Al2O3 1%；
Na2O 12%；
CaO 10%；
MgO 2%；
La2O3 1%；
B2O3 4%；
The total content of Fe 2O3 impurities in the glass raw material is 0.008%;
(2) And (3) melting the uniformly mixed glass raw materials for 3 hours at 1550 ℃, and drawing wires through a platinum-rhodium alloy bushing plate to obtain the T-shaped glass fiber.
The refractive index of the obtained T-shaped glass fiber was 1.506.
Example 5
A preparation method of T-shaped glass fiber comprises the following specific steps:
(1) Based on the total amount of all glass raw materials in the T-shaped glass fiber, the T-shaped glass fiber comprises the following glass raw material components in percentage by mass:
SiO2 66%；
Al2O3 7%；
Na2O 10%；
CaO 11%；
MgO 2%；
La2O3 1.0 %；
B2O3 3%；
the total content of Fe 2O3 impurities in the glass raw material is 0.009%;
(2) And (3) melting the uniformly mixed glass raw materials for 4 hours at 1450 ℃, and drawing wires through a platinum-rhodium alloy bushing plate to obtain the T-shaped glass fiber.
The refractive index of the obtained T-shaped glass fiber was 1.504.
The detailed performance data for examples 1-5 are shown in Table 1:
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Glass fiber Density/g.cm -3 | 2.512 | 2.521 | 2.506 | 2.516 | 2.518 |
| Refractive index/% | 1.508 | 1.511 | 1.502 | 1.506 | 1.504 |
| Transmittance/%in glass fiber | 99% | 99% | 99% | 99% | 99% |
| Tensile strength of glass fiber/MPa | 1268 | 1524 | 1366 | 1380 | 1257 |
| Elastic modulus of glass fiber/GPa | 72 | 76 | 71 | 72 | 75 |
Example 6
A preparation method of a high-strength transparent composite material comprises the following specific steps:
(1) Preparation of raw materials:
the T-glass fiber of example 1;
Impregnating agent: the composite epoxy resin with the refractive index of 1.508 is prepared by mixing two hydrogenated bisphenol A epoxy resins of I102215 and P464946 in a mass ratio of 45:55, and manufacturers of I102215 and P464946: shanghai Ala Biochemical technologies Co., ltd., CAS:80-04-6;
Epoxy resin: the composite epoxy resin with the refractive index of 1.508 is prepared by mixing two hydrogenated bisphenol A epoxy resins of I102215 and P464946 in a mass ratio of 45:55, and manufacturers of I102215 and P464946: shanghai Ala Biochemical technologies Co., ltd., CAS:80-04-6;
(2) Preparing glass fiber yarns after coating a sizing agent on T-shaped glass fibers, and weaving glass fiber yarns into glass fiber fabrics with the thickness of 35 microns by winding the glass fiber yarns into spindle yarns, and then compounding the spindle yarns with epoxy resin to prepare a high-strength transparent composite material;
The coating amount of the impregnating compound is 0.15wt%; the glass fiber fabric in the high strength transparent composite was 20 wt%.
The thickness of the finally prepared high-strength transparent composite material is 2mm, the tensile strength is 286MPa, and the transmittance is 86.6%.
Example 7
A preparation method of a high-strength transparent composite material comprises the following specific steps:
(1) Preparation of raw materials:
The T-glass fiber of example 2;
Impregnating agent: the composite epoxy resin with the refractive index of 1.511 is prepared by mixing two hydrogenated bisphenol A epoxy resins of I102215 and P464946 in a mass ratio of 24:76, and manufacturers of I102215 and P464946: shanghai Ala Biochemical technologies Co., ltd., CAS number: 80-04-6;
Epoxy resin: the composite epoxy resin with the refractive index of 1.511 is prepared by mixing two hydrogenated bisphenol A epoxy resins of I102215 and P464946 in a mass ratio of 24:76, and manufacturers of I102215 and P464946: shanghai Ala Biochemical technologies Co., ltd., CAS number: 80-04-6;
(2) Preparing glass fiber yarns after coating a sizing agent on T-shaped glass fibers, and weaving glass fiber yarns into glass fiber fabrics with the thickness of 50 microns by winding the glass fiber yarns into spindle yarns, and then compounding the spindle yarns with epoxy resin to prepare a high-strength transparent composite material;
The coating amount of the impregnating compound is 0.1wt%; the glass fiber fabric in the high strength transparent composite was 25wt%.
The thickness of the finally prepared high-strength transparent composite material is 2mm, the tensile strength is 269MPa, and the transmittance is 87.4% as shown in FIG. 1.
Example 8
A preparation method of a high-strength transparent composite material comprises the following specific steps:
(1) Preparation of raw materials:
The T-glass fiber of example 3;
impregnating agent: the composite epoxy resin with the refractive index of 1.502 is prepared by mixing two hydrogenated bisphenol A epoxy resins of I102215 and P464946 in a mass ratio of 76:24, and manufacturers of I102215 and P464946: shanghai Ala Biochemical technologies Co., ltd., CAS number: 80-04-6;
Epoxy resin: the composite epoxy resin with the refractive index of 1.502 is prepared by mixing two hydrogenated bisphenol A epoxy resins of I102215 and P464946 in a mass ratio of 76:24, and manufacturers of I102215 and P464946: shanghai Ala Biochemical technologies Co., ltd., CAS number: 80-04-6;
(2) Preparing glass fiber yarns after coating a sizing agent on T-shaped glass fibers, and weaving glass fiber yarns into glass fiber fabrics with the thickness of 30 microns by winding the glass fiber yarns into ingots, and then compounding the glass fiber fabrics with epoxy resin to prepare a high-strength transparent composite material;
The coating amount of the impregnating compound is 0.3wt%; the glass fiber fabric in the high strength transparent composite was 30 wt%.
The thickness of the finally prepared high-strength transparent composite material is 2mm, the tensile strength is 275MPa, and the transmittance is 86.2% as shown in figure 1.
Comparative example 2
A method of preparing a transparent composite material, substantially the same as in example 8, except that the T-type glass fiber was replaced with the E-type glass fiber of comparative example 1.
The thickness of the prepared transparent composite material is 2mm, the tensile strength is 234MPa, and the transmittance is 58.4%.
Comparing comparative example 2 with example 8, it was found that the optical transmittance of comparative example 2 was significantly reduced from 86.2% to 58.4%, because more Fe 2O3 contained in the glass fiber of comparative example 2 absorbed visible light, and the refractive index of the glass fiber was different due to the difference in composition, the refractive index difference between the glass fiber and the resin was large in comparative example 2, the interfacial reflection loss between the glass fiber and the resin was large, and light scattering was also caused, and the scattered light further reduced the glass transmittance.
Comparative example 3
A preparation method of a transparent composite material is basically the same as that in example 8, except that the impregnating compound is a composite epoxy resin with a refractive index of 1.544 compounded by hydrogenated bisphenol A epoxy resin (P464946, manufacturer: shanghai Ala Biochemical technology Co., ltd., CAS number: 80-04-6) and bisphenol A epoxy resin (E-03, manufacturer: hubei Xinkang pharmaceutical Co., ltd., CAS number: 25085-99-8) in a mass ratio of 30:70.
The thickness of the prepared transparent composite material is 2mm, the tensile strength is 215MPa, and the transmittance is 63.6%.
Comparing comparative example 3 with example 8, it can be seen that the tensile strength of the composite of comparative example 3 is reduced, the optical transmittance is significantly reduced, and also that significant texture of the fiberglass fabric can be seen, due to three factors: 1. because the refractive indexes of the impregnating compound coated by the glass fiber and the matrix resin are inconsistent, light is distorted, and therefore, the texture of the surface fabric of the composite material can be clearly seen; 2. the tensile properties are reduced due to the fact that the matrix resin is not tightly bonded to the fiber fabric due to the difference between the two resins; 3. because the refractive index of the glass fiber is different from that of the matrix resin, a plurality of interfaces are generated, on one hand, each interface has reflection, and meanwhile, each interface also generates refraction and scattering, so that the transmittance of the composite material is obviously reduced.
Example 9
A preparation method of a high-strength transparent composite material comprises the following specific steps:
(1) Preparation of raw materials:
the T-glass fiber of example 4;
Impregnating agent: the composite epoxy resin with the refractive index of 1.506 is prepared by mixing two hydrogenated bisphenol A epoxy resins of I102215 and P464946 in a mass ratio of 40:60, and manufacturers of I102215 and P464946: shanghai Ala Biochemical technologies Co., ltd., CAS:80-04-6;
Epoxy resin: the composite epoxy resin with the refractive index of 1.506 is prepared by mixing two hydrogenated bisphenol A epoxy resins of I102215 and P464946 in a mass ratio of 40:60, and manufacturers of I102215 and P464946: shanghai Ala Biochemical technologies Co., ltd., CAS:80-04-6;
(2) Preparing glass fiber yarns after coating a sizing agent on T-shaped glass fibers, and weaving glass fiber yarns into glass fiber fabrics with the thickness of 25 microns by winding the glass fiber yarns into spindle yarns, and then compounding the spindle yarns with epoxy resin to prepare a high-strength transparent composite material;
the coating amount of the impregnating compound is 0.2wt%; the glass fiber fabric in the high-strength transparent composite material accounts for 10 wt percent.
The thickness of the finally prepared high-strength transparent composite material is 2mm, the tensile strength is 256MPa, and the transmittance is 88.2% as shown in figure 1.
Example 10
A preparation method of a high-strength transparent composite material comprises the following specific steps:
(1) Preparation of raw materials:
the T-glass fiber of example 5;
Impregnating agent: the composite epoxy resin with the refractive index of 1.504 is prepared by mixing two hydrogenated bisphenol A epoxy resins of I102215 and P464946 in a mass ratio of 32:68, and manufacturers of I102215 and P464946: shanghai Ala Biochemical technologies Co., ltd., CAS:80-04-6;
Epoxy resin: the composite epoxy resin with the refractive index of 1.504 is prepared by mixing two hydrogenated bisphenol A epoxy resins of I102215 and P464946 in a mass ratio of 32:68, and manufacturers of I102215 and P464946: shanghai Ala Biochemical technologies Co., ltd., CAS:80-04-6;
(2) Preparing glass fiber yarns after coating a sizing agent on T-shaped glass fibers, and weaving glass fiber yarns into glass fiber fabrics with the thickness of 50 microns by winding the glass fiber yarns into spindle yarns, and then compounding the spindle yarns with epoxy resin to prepare a high-strength transparent composite material;
The coating amount of the impregnating compound is 0.5wt%; the glass fiber fabric in the high strength transparent composite material has a proportion of 50 wt%.
The thickness of the finally prepared high-strength transparent composite material is 2mm, the tensile strength is 266MPa, and the transmittance is 85.8% as shown in figure 1.
Claims (7)
1. A T-glass fiber, characterized in that: based on the total amount of all glass raw materials in the T-shaped glass fiber, the T-shaped glass fiber comprises the following glass raw material components in percentage by mass:
SiO2 66~72%；
Al2O3 0~7%；
10-12% of the total amount of K 2 O and Na 2 O;
10-14% of the total amount of CaO and MgO;
La2O3 0~3%;B2O3 1~4%；
The total content of Fe 2O3 impurities in the glass raw material is less than or equal to 0.01 percent;
The refractive index of the T-shaped glass fiber is 1.502-1.512.
2. A T-glass fiber according to claim 1, wherein the T-glass fiber comprises the following glass raw material components in mass percent based on the total amount of all glass raw materials in the T-glass fiber:
SiO2 68%；
Al2O3 6%
11% of the total amount of K 2 O and Na 2 O;
13% of the total amount of CaO and MgO;
La2O3 1%；
B2O3 1%；
the total content of Fe 2O3 impurities in the glass raw material is 0.006%.
3. A T-glass fiber according to claim 1, wherein the T-glass fiber comprises the following glass raw material components in mass percent based on the total amount of all glass raw materials in the T-glass fiber:
SiO2 72%；
Al2O3 1%；
11% of the total amount of K 2 O and Na 2 O;
13% of the total amount of CaO and MgO;
B2O3 3%；
the total content of Fe 2O3 impurities in the glass raw material is 0.008%.
4. A method for preparing a T-glass fiber according to any one of claims 1 to 3, wherein: and melting the uniformly mixed glass raw materials at 1450-1550 ℃ for 3-4 hours, and drawing wires through a platinum-rhodium alloy bushing plate to obtain the T-shaped glass fiber.
5. A preparation method of a high-strength transparent composite material is characterized by comprising the following steps: preparing glass fiber yarns after coating the impregnating compound on the T-shaped glass fibers according to any one of claims 1-3, and weaving the glass fiber yarns into glass fiber fabrics with the thickness of 20-50 microns by winding, and then compounding the glass fiber fabrics with epoxy resin to prepare a high-strength transparent composite material;
the impregnating compound is epoxy resin with the refractive index of 1.502-1.512;
the thickness of the high-strength transparent composite material is 2mm, the tensile strength is more than 250MPa, and the transmittance is more than 85%.
6. The method for preparing a high-strength transparent composite material according to claim 5, wherein the coating amount of the impregnating compound is 0.1-0.5wt%.
7. The method for preparing the high-strength transparent composite material according to claim 5, wherein the glass fiber fabric in the high-strength transparent composite material accounts for 10-50wt%.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049834A (en) * | 1989-08-11 | 1991-03-13 | 伊索福圣戈班公司 | The glass fibre that can in Physiological Medium, decompose |
| RU2036869C1 (en) * | 1993-02-04 | 1995-06-09 | Научно-производственное объединение "Стеклопластик" | Glass for glass fiber |
| JP2006312706A (en) * | 2005-04-08 | 2006-11-16 | Asahi Fiber Glass Co Ltd | Cyclic polyolefin resin composition and molded product thereof |
| JP2012082297A (en) * | 2010-10-08 | 2012-04-26 | Sumitomo Bakelite Co Ltd | Resin cured product, transparent composite substrate, and display element substrate |
| CN109790061A (en) * | 2016-11-10 | 2019-05-21 | 日本板硝子株式会社 | Glass filler and its manufacturing method |
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- 2024-06-06 CN CN202410725217.2A patent/CN118290033B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1049834A (en) * | 1989-08-11 | 1991-03-13 | 伊索福圣戈班公司 | The glass fibre that can in Physiological Medium, decompose |
| RU2036869C1 (en) * | 1993-02-04 | 1995-06-09 | Научно-производственное объединение "Стеклопластик" | Glass for glass fiber |
| JP2006312706A (en) * | 2005-04-08 | 2006-11-16 | Asahi Fiber Glass Co Ltd | Cyclic polyolefin resin composition and molded product thereof |
| JP2012082297A (en) * | 2010-10-08 | 2012-04-26 | Sumitomo Bakelite Co Ltd | Resin cured product, transparent composite substrate, and display element substrate |
| CN109790061A (en) * | 2016-11-10 | 2019-05-21 | 日本板硝子株式会社 | Glass filler and its manufacturing method |
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