CN117865495B - Color-changing glass fiber composition, preparation method thereof and glass fiber - Google Patents
Color-changing glass fiber composition, preparation method thereof and glass fiber Download PDFInfo
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- CN117865495B CN117865495B CN202311609189.XA CN202311609189A CN117865495B CN 117865495 B CN117865495 B CN 117865495B CN 202311609189 A CN202311609189 A CN 202311609189A CN 117865495 B CN117865495 B CN 117865495B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C13/00—Fibre or filament compositions
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B37/00—Manufacture or treatment of flakes, fibres, or filaments from softened glass, minerals, or slags
- C03B37/01—Manufacture of glass fibres or filaments
- C03B37/02—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor
- C03B37/022—Manufacture of glass fibres or filaments by drawing or extruding, e.g. direct drawing of molten glass from nozzles; Cooling fins therefor from molten glass in which the resultant product consists of different sorts of glass or is characterised by shape, e.g. hollow fibres, undulated fibres, fibres presenting a rough surface
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C4/00—Compositions for glass with special properties
- C03C4/02—Compositions for glass with special properties for coloured glass
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Abstract
The invention provides a color-changing glass fiber composition and a preparation method thereof, and glass fiber, wherein the color-changing glass fiber composition comprises, by mass, 63% -74% of SiO 2, 2% -7% of Al 2O3, 0.23% -1.4% of Fe 2O3, 2% -7% of CaO, 2% -6% of MgO, 0.1% -0.5% of K 2 O, 10% -17% of Na 2 O, 0.6% -6% of rare earth oxide, 0-0.5% of W, 0-0.5% of Pt and 0-0.1% of T iO 2, wherein the mass percentage of rare earth oxide and CaO+MgO satisfies the ratio of rare earth oxide/(CaO+MgO) =0.1-1.1, the mass percentage of rare earth oxide and W and Pt satisfies the ratio of rare earth oxide/(W and Pt) >2, and the mass percentage of SiO 2 and Al 2O3 satisfies the ratio of SiO 2 and Al 2O3 is more than or equal to 68%. According to the color-changing glass fiber composition, the preparation method thereof and the glass fiber, the thought of color-changing glass is applied to the glass fiber, so that the glass fiber can change the color of the glass fiber according to different illumination.
Description
Technical Field
The invention belongs to a glass fiber composition, and particularly relates to a color-changing glass fiber composition, a preparation method thereof and glass fibers.
Background
Glass fiber is an inorganic nonmetallic material with excellent performance, and has the advantages of good insulativity, strong heat resistance, good corrosion resistance and high mechanical strength, but has the disadvantages of brittle property and poor wear resistance. The diameter of the filaments is from a few micrometers to twenty meters and a few micrometers, which is equivalent to 1/20-1/5 of one hair filament, and each bundle of fiber precursor consists of hundreds or even thousands of filaments. Glass fibers are commonly used as reinforcing materials in composite materials, electrical and thermal insulation materials, circuit substrates, and the like in various areas of national economy.
The color-changing glass is glass which changes color under certain conditions such as illumination, temperature, electric field or current, surface pressure and the like, changes correspondingly with the change of the conditions, and can be reversibly and automatically restored to an initial state after the applied conditions disappear, and is also called as dimming glass.
The glass fiber is produced in China, and at present, high-strength glass fibers occupy a large proportion in the markets of glass fibers at home and abroad, but because the high-strength glass fibers are mostly light in color and poor in dyeability, the application range of the glass fibers is limited to a great extent, and sometimes, the glass fibers are enabled to show different color-changing properties under different illumination intensities for attractive appearance.
Therefore, the idea of how to apply the color-changing glass to the glass fiber can change the color of the glass fiber according to different illumination, and the technical problem to be solved by the scheme is mainly solved.
Disclosure of Invention
The invention aims to provide a color-changing glass fiber composition, a preparation method thereof and glass fibers, which solve the technical problem of how to apply the thought of color-changing glass to the glass fibers, so that the glass fibers can change the colors according to different illumination, not only realize the change of the color shades, but also have the switching of different colors, have quite remarkable effect and solve the problem that the glass fibers in the prior art need to be dyed.
The color-changing glass fiber composition comprises the following components in percentage by mass:
SiO2 63%-74%
Al2O3 2%-7%
Fe2O3 0.23%-1.4%
CaO 3%-7%
MgO 2%-6%
K2O 0.1%-0.5%
Na2O 10%-17%
0.1 to 6 percent of rare earth oxide
W 0-0.5%
Pt 0-0.5%
TiO2 0-0.1%;
Wherein, the mass percentage content of the rare earth oxide and CaO+MgO satisfies the condition that the rare earth oxide/(CaO+MgO) =0.1-1.1;
The mass percentage content of the rare earth oxide, W and Pt satisfies the rare earth oxide/(W+Pt) >2, and the mass percentage of SiO 2 and Al 2O3 satisfies the SiO 2+Al2O3 more than or equal to 68%.
The mass percentages of the Al 2O3, the rare earth oxide and the Fe 2O3 are as follows:
(Al 2O3 + rare earth oxide)/Fe 2O3 = 1.5-56.5.
The mass percentage of the TiO 2 and the rare earth oxide satisfies that TiO 2/rare earth oxide=0-0.8.
Also comprises 0-0.2% of PbO, wherein the mass percentage of the PbO and Fe 2O3 satisfies PbO/Fe 2O3 =0-0.85.
The mass percentages of TiO 2, W and Fe 2O3 meet that TiO 2+W/Fe2O3 =0-2.6.
Any one or at least two of SiO 2, al 2O3, tiO 2, fe 2O3, caO, mgO, K 2 O, na 2 O, rare earth oxide, W and Pt are nano powder materials.
The forming temperature of the color-changing glass fiber is between 1100 ℃ and 1300 ℃.
The rare earth oxide is at least one of La, ce, pr, nd, pm, sm, eu, gd, tb, dy, ho, er, tm, yb, lu, Y and oxide of Sc.
The preparation method of the color-changing glass fiber composition specifically comprises the following steps:
S1, weighing a basic batch SiO 2、Al2O3、Fe2O3、K2O、Na2 O, caO, mgO and rare earth oxide according to mass fraction, putting into a grinder, and adding any one or at least two of W, pt, pbO, tiO 2 into the grinder;
s2, adding the mixture in the step S1 into a kiln body, heating to 1100-1550 ℃ to form glass melt, preserving heat for a period of time, and melting and uniformly mixing all the components;
Step S3, enabling the glass melt in the step S2 to reach a constant temperature discharging device through a melt ascending channel;
And S4, enabling the glass melt to reach a wiredrawing forming device through a liquid outlet, and then performing high-speed rotary wiredrawing forming through the wiredrawing forming device to obtain the color-changing glass fiber.
A glass fiber is prepared from color-changing glass fiber composition.
Rare earth elements referred to in this scheme include lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), lutetium (Lu), and 17 elements in total, yttrium (Y) and scandium (Sc), which are closely related to 15 elements of the lanthanide series. As is well known to those skilled in the art, it is not described in detail herein.
Compared with the prior art, the glass fiber composition is mainly and innovatively characterized in that the rare earth oxide is introduced to match the comprehensive effect of W and Pt, meanwhile, the Tyndall effect is assisted, the mass percent of the rare earth oxide and CaO+MgO is adjusted to meet the requirement of rare earth oxide/(CaO+MgO) =0.1-1.1, the mass percent of the rare earth oxide and W and Pt is met to meet the requirement of rare earth oxide/(W+Pt) >2, the mass percent of SiO 2 and Al 2O3 is met to be SiO 2+Al2O3 and is more than or equal to 68%, the mass percent of Al 2O3, the rare earth oxide and Fe 2O3 is met to be (Al 2O3 +rare earth oxide)/Fe 2O3 =1.5-56.5, and the mass percent of TiO 2 and the rare earth oxide is met to be TiO 2/rare earth oxide=0-0.8.
According to the specific composition and the proportion control thereof, the glass fiber can be in a mixed crystallization state, the absolute dominant effect of a single crystal phase is avoided, the competitive growth of multiple crystal phases under a proper proportion can effectively reduce the rate of ion recombination arrangement, the rapid growth of the single crystal phase is avoided, so that colorful light rays can be generated on different crystal phases under illumination, and in the second aspect, the synergistic effect between rare earth oxide and W, pt can be improved, a better structural stacking effect is obtained, and the mechanical property of the glass is further improved.
Specifically, the invention has the following positive effects:
The rare earth element oxide is adopted in the scheme, so that various high-grade colored glasses are prepared for the colorant, the colored glass doped with the rare earth element has clear hue and bright color, and even the color can be changed under different light rays, and the reason is that when the wavelength of the light source is different, the light absorption of the glass is different, and different colors are displayed under the irradiation of different light sources;
In addition, the rare earth element is matched with W and Pt, so that the multicolor (color change) effect of the glass fiber under different light sources is more obvious, the coloring element in the glass fiber can absorb light waves selectively, especially when the coloring element is more, the energy level and the energy state number are more, the glass fiber can absorb visible light with multiple wavelengths, the glass fiber is colored, when the light sources are changed, the intensity ratio of the transmitted light wavelength is changed, the color is changed, and therefore, the rare earth element is matched with W and Pt, so that the glass fiber has multicolor and can be colored in multiple colors;
Fe 2O3 is taken as a typical thermochromic material, different illumination intensities can cause different temperatures to be red-dark red-reddish brown, so that the color change caused by rare earth element +W+Pt is complementary in a perfect matching way, the effect of the glass fiber polychromance is more remarkable, and in addition, the red color has the effect of preventing ultraviolet rays;
(3) The ionic valence state of Ti is three, namely Ti 4+、Ti3+、Ti2+, ti 4+ is generally present in silicate glass, ti 4+ is the valence state of Ti 4+, namely the outermost electron 3d24s2 of the titanium is completely lost, the titanium is completely empty in d orbitals, and the transition of'd-d' between electrons in d orbitals cannot occur, so Ti 4+ is colorless, however, since Ti 4+ ions strongly absorb ultraviolet rays, the absorption band of the ions often enters the purplish blue part of the visible light region, so that the ions actually appear yellow, although Ti 4+ alone does not cause darker colors, the transition elements of other valence states are strongly influenced to be colored, even though the transition element contents are small, particularly for iron, the transition element contents are particularly obvious, the quality evaluation index of the glass often comprises the contents of Fe 2O3 and TiO 2, and the transition of the transition element is brown when mixed with Fe 2O3, so that TiO 2 added in the scheme still has the effect of changing the color of the glass, and is only matched with other substances.
(4) PbO is orange-yellow solid, can lead the glass fiber to present pale yellow color under illumination, can greatly increase the refractive index of the glass fiber, presents good refraction and dispersion phenomena, has higher ornamental value, can realize the switching between the red color and the yellow color of the glass fiber under different illumination, and simultaneously, the PbO is combined with W, so that the yellow color is more prominent under specific illumination;
(5) The design component is nano powder material, so that the composite reinforcing effect on the glass fiber is realized, on the one hand, the nano structure increases the load capacity of the glass fiber on the thermochromic catalyst, and the corresponding catalytic performance and the thermochromic characteristic of the glass fiber are obviously improved;
the nano powder is also beneficial to generating a Tyndall effect, so that a clearer color layering effect is presented when the glass fiber is irradiated by light.
Drawings
FIG. 1 is a schematic view showing the structure of a white glass fiber according to the present invention.
FIG. 2 is a schematic view showing the structure of the glass fiber in the sunlight of 100Lux according to example 2 (group I).
FIG. 3 is a schematic view showing the structure of glass fiber in daylight of 1000Lux according to example 2 (group I).
FIG. 4 is a schematic view showing the structure of the glass fiber in the sunlight of 100Lux according to example 2 (group II).
FIG. 5 is a schematic view showing the structure of glass fiber in daylight of 1000Lux according to example 2 (group II).
FIG. 6 is a schematic view showing the structure of the glass fiber in the sunlight of 100Lux according to example 2 (group III).
FIG. 7 is a schematic view showing the structure of glass fiber in daylight of 1000Lux according to example 2 (group III).
Detailed Description
In order to more clearly describe the technical characteristics of the present solution, the present solution is described below by means of specific embodiments.
The preparation method of the color-changing glass fiber composition specifically comprises the following steps:
S1, weighing a basic batch SiO 2、Al2O3、Fe2O3、K2O、Na2 O, caO, mgO and rare earth oxide according to mass fraction, putting into a grinder, and adding any one or at least two of W, pt, pbO, tiO 2 into the grinder;
s2, adding the mixture in the step S1 into a kiln body, heating to 1100-1550 ℃ to form glass melt, preserving heat for a period of time, and melting and uniformly mixing all the components;
Step S3, enabling the glass melt in the step S2 to reach a constant temperature discharging device through a melt ascending channel;
And S4, enabling the glass melt to reach a wiredrawing forming device through a liquid outlet, and then performing high-speed rotary wiredrawing forming through the wiredrawing forming device to obtain the color-changing glass fiber.
Example 1:
The color-changing glass fiber composition comprises, by mass, 63% -74% of SiO 2, 2% -7% of Al 2O3 , 0.23% -1.4% of Fe 2O3, 3% -7% of CaO, 2% -6% of MgO, 0.1% -0.5% of K 2 O and 10% -17% of Na 2 O;
The mass percentage of SiO 2 and Al 2O3 satisfies that SiO 2+Al2O3 is more than or equal to 68 percent.
And the total content of the above components is equal to 95.5%. It should be noted that, each embodiment in this scheme is not limited to the specific components disclosed in this scheme, and under different components, the body color of the glass fiber will be affected necessarily, but the realization of the color change of the glass fiber under different illumination is not affected, so only for illustrating the color change effect of the glass fiber, this scheme will not be listed in detail for other components of the glass fiber. Table 1 shows the color change of the glass fiber under each component in example 1.
Table 1 shows the color change of the glass fiber under each component in example 1
| Case item | Example 1 (group one) | Example 1 (group two) | Example 1 (group three) | Comparative example |
| SiO2 | 64.5 | 65.0 | 64.6 | 68.66 |
| Al2O3 | 5.5 | 5.0 | 5.4 | 4.5 |
| Fe2O3 | 1 | 0.9 | 1 | 0.74 |
| CaO | 6 | 5.8 | 6.1 | 5.0 |
| MgO | 5 | 5.3 | 4.9 | 4.0 |
| K2O | 0.5 | 0.5 | 0.4 | 0.3 |
| Na2O | 13 | 13 | 13.1 | 12.3 |
| Forming temperature | 1250°C | 1260°C | 1253°C | 1285°C |
| Sunlight 100Lux | White color | White color | White color | White color |
| Sunlight 1000Lux | White color | White color | White color | White color |
Example 2:
On the basis of the embodiment 1, the rare earth oxide/CaO/MgO composite material preferably further comprises 2-3% of rare earth oxide, 0-0.5% of W and 0-0.5% of Pt, wherein the mass percentage content of the rare earth oxide and CaO/MgO composite material satisfies the condition that the mass percentage content of the rare earth oxide/CaO/MgO) =0.2-0.3, and the mass percentage content of the rare earth oxide and W and Pt satisfies the condition that the mass percentage content of the rare earth oxide/W+Pt) =2.0-5.0;
The mass percentages of the Al 2O3, the rare earth oxide and the Fe 2O3 are as follows:
(Al 2O3 + rare earth oxide)/Fe 2O3 = 7.8-9.0. Table 2 shows the color change of the glass fibers of example 2, see FIGS. 1-7.
Table 2 shows the color change of the glass fiber under each component in example 2.
| Case item | Example 2 (group I) | Example 2 (group two) | Example 2 (group three) | Comparative example |
| SiO2 | 64.5 | 65.0 | 64.6 | 68.66 |
| Al2O3 | 5.5 | 5.0 | 5.4 | 4.5 |
| Fe2O3 | 1 | 0.9 | 1 | 0.74 |
| CaO | 6 | 5.8 | 6.1 | 5.0 |
| MgO | 5 | 5.3 | 4.9 | 4.0 |
| K2O | 0.5 | 0.5 | 0.4 | 0.3 |
| Na2O | 13 | 13 | 13.1 | 12.3 |
| Nd | 2.5 | 2.7 | 2.9 | |
| WO2.90 | 0.5 | 0.4 | 0.3 | |
| Pt | 0.5 | 0.4 | 0.3 | |
| Forming temperature | 1246°C | 1254°C | 1248°C | 1285°C |
| Sunlight 100Lux | Deep blue, light purple | Bluish violet | Bluish purple | White color |
| Sunlight 1000Lux | Light blue, light purple red | Light blue, purple red | Mauve color | White color |
Example 3:
Based on the embodiment 1 and the embodiment 2, the composite material further comprises 0-0.1% of TiO 2, wherein the mass percentage of TiO 2 and the mass percentage of rare earth oxide meet that TiO 2/rare earth oxide=0.02-0.04. Table 3 shows the color change of the glass fiber under each component in example 3.
Table 3 shows the color change of the glass fiber under each component in example 3
| Case item | Example 3 (group I) | Example 3 (group two) | Example 3 (group three) | Comparative example |
| SiO2 | 64.5 | 65.0 | 64.6 | 68.66 |
| Al2O3 | 5.5 | 5.0 | 5.4 | 4.5 |
| Fe2O3 | 1 | 0.9 | 1 | 0.74 |
| CaO | 6 | 5.8 | 6.1 | 5.0 |
| MgO | 5 | 5.3 | 4.9 | 4.0 |
| K2O | 0.5 | 0.5 | 0.4 | 0.3 |
| Na2O | 13 | 13 | 13.1 | 12.3 |
| Nd | 2.5 | 2.7 | 2.9 | |
| WO2.90 | 0.5 | 0.4 | 0.3 | |
| Pt | 0.5 | 0.4 | 0.3 | |
| TiO2 | 0.1 | 0.08 | 0.09 | |
| Forming temperature | 1244°C | 1253°C | 1246°C | 1285°C |
| Sunlight 100Lux | Bluish green and purplish | Bluish violet | Bluish purple | White color |
| Sunlight 1000Lux | Light green, light mauve, dark brown | Pale green, purple, pale brown | Mauve, bright color | White color |
Example 4:
On the basis of the embodiment 1, the embodiment 2 and the embodiment 3, the alloy also comprises 0-0.2% of PbO, wherein the mass percentage of the PbO and the Fe 2O3 satisfies the condition that PbO/Fe 2O3 =0.1-0.2. Table 4 shows the color change of the glass fiber under each component in example 4.
Table 4 shows the color change of the glass fiber under each component in example 4
| Case item | Example 4 (group one) | Example 4 (group two) | Example 4 (group three) | Comparative example |
| SiO2 | 64.5 | 65.0 | 64.6 | 68.66 |
| Al2O3 | 5.5 | 5.0 | 5.4 | 4.5 |
| Fe2O3 | 1 | 0.9 | 1 | 0.74 |
| CaO | 6 | 5.8 | 6.1 | 5.0 |
| MgO | 5 | 5.3 | 4.9 | 4.0 |
| K2O | 0.5 | 0.5 | 0.4 | 0.3 |
| Na2O | 13 | 13 | 13.1 | 12.3 |
| Nd | 2.5 | 2.7 | 2.9 | |
| WO2.90 | 0.5 | 0.4 | 0.3 | |
| Pt | 0.5 | 0.4 | 0.3 | |
| TiO2 | 0.1 | 0.08 | 0.09 | |
| PbO | 0.1 | 0.12 | 0.15 | |
| Forming temperature | 1242°C | 1252°C | 1245°C | 1285°C |
| Sunlight 100Lux | Bluish green and purplish | Bluish violet | Bluish purple | White color |
| Sunlight 1000Lux | Light green, light mauve, dark brown | Pale green, purple, pale brown | Mauve, bright color | White color |
Example 5:
Based on example 1, example 2, example 3 and example 4, the mass percentages of TiO 2, W and Fe 2O3 satisfy that TiO 2+W/Fe2O3 =0.3 to 0.6. Table 5 shows the color change of the glass fiber under each component in example 5.
Table 5 shows the color change of the glass fiber under each component in example 5
| Case item | Example 5 (group one) | Example 5 (group two) | Example 5 (group three) | Comparative example |
| SiO2 | 64.5 | 65.0 | 64.6 | 68.66 |
| Al2O3 | 5.5 | 5.0 | 5.4 | 4.5 |
| Fe2O3 | 1 | 0.9 | 1 | 0.74 |
| CaO | 6 | 5.8 | 6.1 | 5.0 |
| MgO | 5 | 5.3 | 4.9 | 4.0 |
| K2O | 0.5 | 0.5 | 0.4 | 0.3 |
| Na2O | 13 | 13 | 13.1 | 12.3 |
| Nd | 2.5 | 2.7 | 2.9 | |
| WO2.90 | 0.5 | 0.4 | 0.3 | |
| Pt | 0.5 | 0.4 | 0.3 | |
| TiO2 | 0.1 | 0.08 | 0.09 | |
| PbO | 0.1 | 0.12 | 0.15 | |
| Forming temperature | 1242°C | 1252°C | 1245°C | 1285°C |
| Sunlight 100Lux | Bluish green and purplish | Bluish violet | Bluish purple | White color |
| Sunlight 1000Lux | Light green, light mauve, dark brown | Pale green, purple, pale brown | Mauve, bright color | White color |
For each example in this scenario, the specific analysis is as follows:
(1) Through experiments, the illumination intensity is 100 Lux and 1000Lux, the color depth and the color difference of the product in each embodiment are obviously changed, and under the same illumination intensity, different components also have the phenomenon of color change, so that the whole color of the glass fiber is the result of the comprehensive effect of the illumination intensity and the chemical components of each substance, and the color change effect of the glass fiber is illustrated only through limited experiments in the scheme, thereby being particularly illustrated.
(2) SiO 2 is a main oxide forming a glass skeleton, and compared with S glass, the content of SiO 2 is obviously improved on the basis of adding rare earth elements in order to improve the color-changing property of the glass. The glass fiber composition of the present invention has a weight percent SiO 2 content ranging from 63 to 74%. Preferably, the weight percentage content of SiO 2 may be defined as 64-68%. Although SiO 2 cannot emit light, various defects exist in the SiO 2 network structure, the defects have good light-emitting performance, and the existence of various defect centers with high-efficiency light emission makes SiO 2 a very important fluorescent light-emitting material, so that the emission spectrum can cover the whole visible light region from blue to red, and the special porous network center structure is very suitable for serving as a matrix of the rare earth ion doped fluorescent light-emitting material. Therefore, the SiO 2 is matched with rare earth elements, so that the brightness of different colors of glass fibers is improved.
(3) Al 2O3 is also an oxide forming the glass skeleton and, when combined with SiO 2, can play a substantial role in the mechanical properties of the glass. If the content is too low, sufficiently high mechanical properties cannot be obtained, and if the content is too high, the risk of glass crystallization tends to be greatly increased. In the glass fiber composition, the content of the defined Al 2O3 in the glass fiber composition ranges from 2 to 7 percent by weight, more preferably ranges from 4 to 6 percent by weight, the glass melting time and the glass clarifying time are greatly shortened, but compared with the prior art, the content is still lower, but the radius of the added rare earth oxide ions is much larger than that of aluminum ions, and the rare earth oxide ions are difficult to form solid solution with Al 2O3, so that rare earth exists on the grain boundary of Al 2O3, the migration rate of the grain boundary is reduced, the grain growth is inhibited, a compact structure is formed, the strength of a glass phase is improved, and the low-content Al 2O3 has the effect of shortening the glass melting time and the glass clarifying time without affecting the mechanical property of the glass fiber;
Compared with the prior art, the method has the advantages that the component range of SiO 2 is adjusted to be high, the component range of Al 2O3 is adjusted to be low, rare earth elements are matched, and the mass percentages of SiO 2 and Al 2O3 are limited to be more than or equal to 68% as SiO 2+Al2O3, so that the color change effect of glass fibers can be ensured, and the strength and modulus of the glass fibers can be ensured;
(3) According to the invention, caO is 3-7%, mgO is 2-6%, compared with the prior art, the content ratio of CaO and MgO is greatly reduced, the content ratio is approximately the same, the thinking is completely different from the prior art, and on the premise that the proportion of MgO and CaO is not greatly different, the rare earth element is added, so that the microstructure of the glass fiber can be effectively improved, the air holes are reduced, and the density of the glass fiber is increased;
The content ratio of rare earth oxide to MgO and CaO is limited, the MgO and CaO have similar functions on glass fibers, and the influence on the melting temperature is double, so that on one hand, the initial melting temperature of microcrystalline glass can be increased, and on the other hand, the melting temperature under the high-temperature condition can be obviously reduced, but the effect of reducing the melting temperature gradually tends to be weakened along with the increase of the addition amount of MgO and CaO, the melting temperature of the microcrystalline glass is reduced, and then the microstructure of the glass fibers is effectively improved.
(4) The W can form four stable oxides, namely yellow oxide (WO 3), blue oxide (WO 2.90), purple oxide (WO 2.72) and brown oxide (WO 2), so that the range of color change is wider, rare earth oxide/(W+Pt) >2 is limited, and the rare earth color change effect is mainly prevented from being covered by the W+Pt color change effect, so that the glass fiber can not only show the color change effect of the rare earth element, but also show the color change effect of the W+Pt on the glass fiber.
(5) The color-changing range of Fe 2O3 is represented in red-deep red-reddish brown, and (Al 2O3 +rare earth oxide)/Fe 2O3 =1.5-56.5, in principle, on one hand, avoiding that red Fe 2O3 plays a decisive role in the color-changing effect of rare earth oxide, and on the other hand, the combination of Al 2O3, rare earth oxide and Fe 2O3 helps to promote corrosion resistance of glass fiber, helps to improve bonding strength between each component, and produces more benefits in performance of glass fiber.
(6) The high temperature phase of TiO 2 is rutile crystal form, the forbidden bandwidth is 2.8eV, compared with anatase TiO 2, the forbidden bandwidth is small, the light response wavelength moves to the long wave direction, the light absorption performance is excellent, the photocatalysis performance of TiO 2 is closely related to the luminescence property, the rare earth element has f electron, multi-electron configuration is easy to generate, the oxide also has polymorphism, strong adsorption selectivity, good thermal stability and electronic conductivity, the doping of the rare earth element can improve the compounding of TiO 2 to inhibit the photogenerated electron and hole, and further improve the luminescence property, and the influence of the rare earth oxide on the luminescence property of TiO 2 is more complex, and the influence on the luminescence property of TiO 2 can be realized only when the position of the XRD curve absorption peak of TiO 2 is changed due to the rare earth element.
(7) The mass percent of PbO and Fe 2O3 is limited to meet the requirement that PbO/Fe 2O3 =0-0.85, on one hand, pbO can lower the melting point of glass fiber, on the other hand, the PbO has higher refractive index, higher refraction and dispersion degree, the higher dispersion degree is, more dispersed colors can generate brilliant colors, so that the glass fiber can show excellent color change effect by adding PbO, and in addition, pbO/Fe 2O3 =0-0.85, the ratio can ensure that PbO and Fe 2O3 do not influence each other when the color change effect is exerted;
PbO is yellow or reddish yellow powder or fine flaky crystals, and is easy to change color when meeting light, so that the color change effect of the glass fiber is increased;
(8) The mass percentages of TiO 2, W and Fe 2O3 are defined to be that TiO 2+W/Fe2O3 =0-2.6, while Ti 4+ alone does not cause a darker color, the Ti 4+ can strongly influence the color of other valence transition elements, even though the transition elements are less, the transition elements still can be colored, and the quality evaluation index of the glass raw material is particularly obvious for iron, often comprises the contents of Fe 2O3 and TiO 2, and the glass raw material is brown when mixed with Fe 2O3, so that the added TiO 2 still has the effect of changing the color of glass, but is matched with other substances.
The W is added into the silver-free glass, and the glass fiber is subjected to illumination, especially under the action of ultraviolet rays, so that the glass fiber presents photochromic performance, namely presents the characteristic of light-shade conversion under different illumination conditions.
In this scheme, a comparative example is provided, the composition ratio of which is greatly different from that of other examples, in order to explore the color-changing performance of glass fiber under different illumination intensities when the main composition is greatly different, while the composition variation ranges of examples 1,2 and 3 are smaller, in order to explore the color-changing effect of glass fiber under different illumination intensities when the trace composition is changed.
The technical features of the present invention that are not described in the present invention may be implemented by or using the prior art, and are not described in detail herein, but the above description is not intended to limit the present invention, and the present invention is not limited to the above examples, but is also intended to be within the scope of the present invention by those skilled in the art.
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| CN102276153A (en) * | 2011-07-27 | 2011-12-14 | 中材科技股份有限公司 | Composition for high-property heat-resisting corrosion-resisting glass fiber |
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| DE1811968B2 (en) * | 1968-11-30 | 1972-02-10 | Jenaer Glaswerk Schott & Gen, 6500 Mainz | PHOTOTROPIC FIBERS PROCESS FOR THEIR PRODUCTION AND USE |
| AT338451B (en) * | 1972-05-15 | 1977-08-25 | Jenaer Glaswerk Schott & Gen | PHOTOTROPIC GLASS, SUITABLE AS SUTURE MATERIAL FOR FUSING WITH PHOTOTROPIC FOCUS LENSES FOR MULTIFOCAL LENSES |
| PT3093276T (en) * | 2015-01-20 | 2018-12-24 | Jushi Group Co Ltd | Glass fiber composition and glass fiber and composite material thereof |
| CN104986960A (en) * | 2015-07-02 | 2015-10-21 | 东华大学 | Colored glass fiber and preparation method thereof |
| WO2017033246A1 (en) * | 2015-08-21 | 2017-03-02 | 日東紡績株式会社 | Glass composition for glass fibers |
| CN113003941B (en) * | 2021-03-15 | 2022-12-06 | 南京玻璃纤维研究设计院有限公司 | Glass composition, glass fiber, glass fiber wool, fiber blended yarn and preparation method |
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| CN102276153A (en) * | 2011-07-27 | 2011-12-14 | 中材科技股份有限公司 | Composition for high-property heat-resisting corrosion-resisting glass fiber |
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