CN102092942A - Energy-saving environmental protection glass with high transmittance - Google Patents

Abstract

The invention relates to an energy-saving and environment-friendly glass with high transmittance, which is added Fe ₂ O ₃ , SnCl ₂ , Ce ₂ (CO ₃ ) ₃ , Nd ₂ (CO ₃ ) ₃ , elemental Se, the thickness of the melted glass is 4mm, the visible light transmittance is greater than 88%, the ultraviolet transmittance is less than 4%, and the infrared transmittance is less than 15%. This kind of glass can strongly absorb ultraviolet rays and infrared rays, and has a high transmittance of visible light. Using SnCl ₂ as a reducing agent, adding rare earth elements, and using physical decolorization methods not only improve the transmittance of the glass but also improve the glass’s resistance to light. The absorption rate of ultraviolet rays and infrared rays can be widely used in protective fields such as automobile glass, architectural glass, spectacle glass and experimental instruments.

Description

Energy-saving and environmentally friendly glass with high transmittance

Technical field:

The invention relates to an energy-saving and environment-friendly glass with high transmittance, which is widely used in automobile windshield, building glass, spectacle glass and experimental instruments, and belongs to the field of glass preparation.

Background technique:

In recent years, with the rapid development of our country's economy, the automobile and construction industries have also developed rapidly. However, the harmful gases emitted by heavy industries have caused the ozone layer to be damaged more and more seriously, the intensity of ultraviolet radiation has increased, and the luxury decoration in automobiles and buildings has been increasingly damaged by ultraviolet radiation. . In summer, cars and buildings are affected by the near-infrared rays of sunlight, and the temperature is high, which greatly increases the load of air conditioning and consumes a lot of energy. Some special experimental instruments need to work in an environment with low ultraviolet and infrared radiation and high visible light. Therefore, it is a major research direction in the field of glass to study a glass that can effectively prevent the transmission of ultraviolet and infrared rays and increase the transmission of visible light.

Several anti-ultraviolet and infrared-resistant glasses have been developed in the field of glass. For example, the patent applied by Nippon Panglass Co., Ltd. in China: CN 1336904A, a kind of infrared and ultraviolet radiation-absorbing glass with a green hue, more specifically, it has High transmittance and light blue-green tint, this glass contains the following components in weight %: soda lime-silica alkali glass, and some coloring components; the coloring components contain _0.40 % as _Fe2O3 to less than 0.58% total iron oxide (T-Fe ₂ O ₃ ), 0.05% to less than 0.5% CeO ₂ , 0 to 0.5% TiO ₂ and 0.0001% to 0.002% CoO, with 20% to less than 30% T -Fe ₂ O ₃ is FeO in terms of Fe ₂ O ₃ .

The patent applied by Japan Plate Glass Co., Ltd. in China: CN 1167093A discloses a green ultraviolet and infrared absorbing glass used for windows of automobiles or buildings. The glass includes by weight %: 65-80% SiO ₂ , 0-5% Al ₂ O ₃ , 0-10% MgO, 5-15% CaO, 10-18% Na ₂ O, 0-5% K ₂ O, 5-15% MgO+CaO, 10-20 _% Na ₂ O+K ₂ O, 0-5% B _{2 O 3} ; the dyeing component contains 0.40-0.70 total iron oxide (T -Fe ₂ O ₃ ), 1.4-1.7% CeO ₂ and 0-0.5% TiO ₂ , wherein 27-40% by weight of T—Fe ₂ O ₃ calculated as Fe ₂ O ₃ is FeO.

Shanghai Yaohua Pilkington Glass Co., Ltd. applied for a patent: CN 1451621A, which provides a green glass that strongly absorbs ultraviolet and infrared rays. It is a coloring agent added to the ordinary soda-lime-silicon flat glass composition. The ratio of the coloring agent Yes: the total iron content (Fe ₂ O ₃ ) in the colorant is between 0.5 and 0.9%, among which the content of ferrous (Fe ²⁺ ) in the total iron is 18 to 28%, and the content of TiO ₂ is 0.2 to 0.7% , the content of CeO ₂ is 0.05-0.15%. The color of this glass is dark green, and its advantage is that the transmittance of ultraviolet rays does not exceed 17%, the transmittance of infrared rays does not exceed 28%, and the transmittance of visible light exceeds 70%.

The patent applied by American PPG company in China: CN 1165788A, provides a kind of green glass, which adopts the standard soda-lime-silicate glass composition as the iron, cerium, chromium and any Titanium of choice. The green glass contains 0.50-1.0% by weight total iron _, about 0.35-0.65% by weight _Fe2O3 , about 0.8-1.5% by weight _CeO2 , and about _{20-150PPMCr2O3 .} The composition has a light transmission (LTA) of at least about 65%, a total solar ultraviolet transmission (TSV) of not more than 38%, a total solar infrared transmission (TSIR) of not more than about 35%. The glasses of the present invention have a green color with a dominant wavelength in the range of 500-550 nm and a color purity of not more than about 5%.

The ZL 97104961.0 patent applied by PPG in China involves a kind of "infrared and ultraviolet radiation absorbing green glass composition", which uses standard soda-lime-silica glass base composition and iron as infrared and ultraviolet absorbing substances and colorants, Cerium, Chromium and optionally Titanium. The glass has a light transmission (LAT) of at least about 65% and a total solar ultraviolet transmission (TSU) of not more than about 38%.

Most of the above inventions use a large amount of iron oxide, cerium oxide and titanium oxide to achieve coloring and absorb ultraviolet and infrared effects. It is found in experiments that cerium oxide and titanium oxide have a certain absorption effect on ultraviolet rays, but basically have no effect on near infrared rays. Absorption, it is Fe ²⁺ that absorbs infrared rays, but most of the iron in the glass exists as Fe ³⁺ . If you want to get Fe ²⁺ , you must add a high-temperature reducing agent. However, the Fe ²⁺ in the glass Both Fe 3+ and Fe ³⁺ will color the glass and reduce the transmittance of the glass.

Invention content:

The object of the present invention is to provide an energy-saving and environment-friendly glass with high transmittance which has high transmittance of visible light and can strongly absorb ultraviolet rays and infrared rays.

Technical solution:

The present invention is based on the composition of ordinary soda-lime-silicate float glass, and Fe ₂ O ₃ , SnCl ₂ , Ce ₂ (CO ₃ ) ₃ , Nd ₂ (CO ₃ ) ₃ , and elemental Se are added to the ingredients, and the distribution ratio of each component is In percent by weight:

Silicon oxide SiO ₂ : 64～85%

Sodium oxide Na ₂ O: 6～14%

Calcium Oxide CaO: 4-12%

Magnesium Oxide MgO: 2～7%

Aluminum oxide Al ₂ O ₃ : 0~3%

Iron oxide Fe ₂ O ₃ : 0.1～0.2%

Tin protochloride SnCl ₂ : 0.2～0.4%

Cerium carbonate Ce ₂ (CO ₃ ) ₃ : 0.05～0.08%

Neodymium carbonate Nd ₂ (CO ₃ ) ₃ : 0.03～0.05%

Elemental Selenium Se: 0.02～0.04%

The 4mm thick glass has a visible light transmittance greater than 89% at a wavelength of 380-780nm, an ultraviolet transmittance at a wavelength of 280-380nm of less than 25%, and a near-infrared transmittance at a wavelength of 780-2500nm of less than 60%. .

Another embodiment of the present invention: energy-saving and environment-friendly glass with high transmittance, adding Fe ₂ O ₃ , SnCl ₂ , Ce ₂ (CO ₃ ) ₃ , Nd ₂ (CO ₃ ) ₃ , Elemental Se, the distribution ratio of each group is by weight percentage:

Silicon oxide SiO ₂ : 64～85%

Sodium oxide Na ₂ O: 6～14%

Calcium Oxide CaO: 4-12%

Magnesium Oxide MgO: 2～7%

Aluminum oxide Al ₂ O ₃ : 0~3%

Iron oxide Fe ₂ O ₃ : 0.2～0.4%

Tin protochloride SnCl ₂ : 0.4～0.7%

Cerium carbonate Ce ₂ (CO ₃ ) ₃ : 0.08～0.1%

Neodymium carbonate Nd ₂ (CO ₃ ) ₃ : 0.05～0.07%

Elemental Selenium Se: 0.04～0.06%

The 4mm thick glass has a visible light transmittance greater than 88% at a wavelength of 380-780nm, an ultraviolet transmittance at a wavelength of 280-380nm of less than 12%, and a near-infrared transmittance at a wavelength of 780-2500nm of less than 45%. .

The third embodiment of the present invention: energy-saving and environment-friendly glass with high transmittance is obtained by adding Fe ₂ O ₃ , SnCl ₂ , Ce ₂ (CO ₃ ) ₃ , Nd ₂ (CO ₃ ) to ordinary soda-lime-silicate float glass _3. Elemental Se, the distribution ratio of each component is calculated by weight percentage:

Silicon oxide SiO ₂ : 64～85%

Sodium oxide Na ₂ O: 6～14%

Calcium Oxide CaO: 4-12%

Magnesium Oxide MgO: 2～7%

Aluminum oxide Al ₂ O ₃ : 0~3%

Iron oxide Fe ₂ O ₃ : 0.4～0.6%

Tin protochloride SnCl ₂ : 0.6～0.8%

Cerium carbonate Ce ₂ (CO ₃ ) ₃ : 0.1～0.12%

Neodymium carbonate Nd ₂ (CO ₃ ) ₃ : 0.07～0.1%

Elemental Selenium Se: 0.06～0.09%

This 4mm thick glass has a visible light transmittance greater than 88% at a wavelength of 380-780nm, an ultraviolet transmittance at a wavelength of 280-380nm of less than 8%, and a near-infrared transmittance at a wavelength of 780-2500nm of less than 18%. .

The fourth embodiment of the present invention: energy-saving and environment-friendly glass with high transmittance, adding Fe ₂ O ₃ , SnCl ₂ , Ce ₂ (CO ₃ ) ₃ , Nd ₂ (CO ₃ ) ₃ to ordinary soda-lime-silicate float glass , elemental Se, each group distribution ratio is by weight percentage:

Silicon oxide SiO ₂ : 64～85%

Sodium oxide Na ₂ O: 6～14%

Calcium Oxide CaO: 4-12%

Magnesium Oxide MgO: 2～7%

Aluminum oxide Al ₂ O ₃ : 0~3%

Iron oxide Fe ₂ O ₃ : 0.6～0.8%

Tin protochloride SnCl ₂ : 0.8～1%

Cerium carbonate Ce ₂ (CO ₃ ) ₃ : 0.12～0.15%

Neodymium carbonate Nd ₂ (CO ₃ ) ₃ : 0.1～0.14%

Elemental Selenium Se: 0.09～0.12%

The 4mm thick glass has a visible light transmittance greater than 88% at a wavelength of 380-780nm, an ultraviolet transmittance at a wavelength of 280-380nm of less than 4%, and a near-infrared transmittance at a wavelength of 780-2500nm of less than 15%. .

The reasons for limiting the composition of the energy-saving and environment-friendly glass with high transmittance will be described below, and all percentages below are percentages by weight.

SiO ₂ is the main component of the glass skeleton, which can reduce the thermal expansion coefficient of the glass and improve the thermal stability, chemical stability, softening temperature, heat resistance, hardness, mechanical strength and viscosity of the glass. If the content is too low, various properties of the glass will decrease; if the content is too high, the raw materials will be difficult to melt.

Na ₂ O is an oxide of the outer body of the glass network, which can reduce the viscosity of the glass and make the glass easy to melt. Mechanical strength, so it cannot be introduced too much, generally no more than 18%, if the introduction is too small, the melting effect of the glass will be poor.

CaO is an oxide of the outer body of the glass network. Its main function in the glass is to be a stabilizer, that is, to increase the chemical stability and mechanical strength of the glass. However, when the content is high, the crystallization tendency of the glass will increase, and it is easy to make the glass brittle. , generally not more than 12.5%.

Iron oxide is an impurity contained in sandstone. It exists in two forms: FeO and Fe ₂ O _3. FeO will make the glass green, and Fe ₂ O ₃ will make the glass yellow green. The coloring ability of low-priced iron About 10 times the coloring ability of high-valent iron. Whether it is high-priced iron or low-priced iron, it will reduce the transparency of the glass, so the increase of iron content in the glass will reduce the transparency and gloss, and affect the quality of the glass. Both Fe ²⁺ and Fe ³⁺ have a strong absorption effect on ultraviolet rays, but Fe ²⁺ has a strong absorption effect on infrared rays, and Fe ³⁺ has basically no absorption effect on infrared rays.

Tin protochloride is a colorless or white oblique crystal. The relative density is 2.710. The melting point is 37.7°C. It decomposes into hydrochloric acid and basic salts at the melting point. It is gradually oxidized to insoluble oxychloride in the air. It is also a reducing agent that can completely reduce most of the Fe ₂ O ₃ in the glass to FeO, but the cost is relatively high.

Ce ₂ (CO ₃ ) ₃ can be decomposed into CeO ₂ at high temperature, and CeO ₂ can absorb ultraviolet rays in glass. In the present invention, Ce(CO ₃ ) ₂ is selected instead of CeO ₂ directly because Ce ₂ (CO ₃ ) ₃ pyrolysis releases CO ₂ gas, which can accelerate the escape of bubbles in the glass, replace part of Glauber's salt, and reduce environmental pollution.

_CeO2 can continue to decompose at high temperature, the chemical formula is as follows:

CeO ₂ acts as an oxidizing agent in the high temperature reaction, which can reduce the iron oxide and weaken the coloring ability of iron, and can also clarify and absorb ultraviolet rays. However, the content of _CeO2 should not be too high, otherwise it will easily increase the content of high-valent iron and make the glass appear light yellow.

Nd ₂ (CO _{3 ) 3} can decompose into Nd ₂ O ₃ at high temperature, and at the same time release CO ₂ gas, which accelerates the clarification process of glass liquid _. Blue-green neutralization, strong absorption of 568-590nm yellow light, and Nd ₂ O ₃ has a certain absorption effect on ultraviolet rays.

Elemental selenium can exist in glass under neutral conditions, producing lavender red, mixed with _CeO2 , it can oxidize selenium into colorless selenate in the process of glass melting, under reducing atmosphere, no Chromoselenate decomposes to form purple elemental selenium, which makes the glass purple, which is just complementary to the turquoise of Fe ²⁺ .

The energy-saving and environment-friendly glass with high transmittance of the present invention has high visible light transmittance, can strongly absorb ultraviolet rays and infrared rays, and can directly carry out component design on the basis of ordinary float glass ingredients, and can realize industrial production with low cost. Low, economical and environmentally friendly, it is the best choice for protective glass such as automobiles, buildings, glasses and experimental instruments.

Detailed ways

The present invention will be described in more detail by the following examples, but the present invention is not limited to the following examples.

All use the basic batching of ordinary float glass in the following examples, and the contents of each component are as shown in Table 1:

Table 1 Example basic batching composition table/% (by weight percentage)

Introduce the basic components of the glass through sandstone, dolomite, limestone, soda ash and Glauber's salt, and add the required Fe ₂ O ₃ , SnCl ₂ , Ce ₂ (CO ₃ ) ₃ , Nd ₂ (CO ₃ ) ₃ , and elemental Se, see Table 1 . Fully mix the batch materials, the total mass is 100g, and put them into a corundum crucible. Put it on the platform in the glass melting furnace. After 5 hours, cast the molten glass onto the steel plate coated with zirconium powder, and then put it into a holding furnace at 550°C for annealing. The thickness of the prepared sample is about 6mm, and the thickness is 4mm after rough grinding and polishing.

Each piece of polished glass with a thickness of 4 mm was measured with a BTF-1 visible light transmittance tester, a TV-1901I double-beam ultraviolet-visible spectrophotometer and a Fourier near-infrared transmittance tester to measure the visible light transmittance and ultraviolet transmittance. The transmittance and near-infrared transmittance are shown in Table 2.

The test result of table 2 embodiment glass

As can be seen from the above table, the glass with a thickness of 4 mm has a visible light transmittance greater than 89% at a wavelength of 380 to 780 nm; an ultraviolet transmittance at a wavelength of 280 to 380 nm is less than 25%, preferably at a wavelength of 280 to 380 nm The transmittance of ultraviolet rays is less than 4%; the transmittance of near-infrared rays at a wavelength of 780-2500nm is less than 60%, preferably less than 15%, and the effect is very ideal.

Industrial applicability:

As described in detail above, the glass produced by the present invention has high visible light transmittance and strong ultraviolet and infrared absorption, and without changing the production process of float glass, large-scale industrial production can be realized by directly adding required additives, and can be widely used In the fields of automobile and architectural window and spectacle glass.

Claims (8)

1. the high permeability energy-saving environment-friendly glass is characterized in that, adds Fe in common sodium calcium silicon float glass ₂O ₃, SnCl ₂, Ce ₂(CO ₃) ₃, Nd ₂(CO ₃) ₃, simple substance Se is as ultraviolet ray and ultrared absorption agent, each set of dispense is than percentage meter by weight:

Silicon oxide sio ₂: 64～85%

Sodium oxide Na ₂O:6～14%

Calcium oxide CaO:4～12%

Magnesium oxide MgO:2～7%

Aluminium oxide Al ₂O ₃: 0～3%

Ferric oxide Fe ₂O ₃: 0.1～0.2%

Tin protochloride SnCl ₂: 0.2～0.4%

Cerous carbonate Ce ₂(CO ₃) ₃: 0.05～0.08%

Neodymium carbonate Nd ₂(CO ₃) ₃: 0.03～0.05%

Simple substance selenium Se:0.02～0.04%.

2. by the described high permeability energy-saving environment-friendly glass of claim 1, it is characterized in that: this kind 4mm heavy sheet glass has visible light transmissivity at 380～780nm wavelength greater than 89%, at the ultraviolet ray transmissivity of 280～380nm wavelength less than 25%; In the near infrared transmitance of 780～2500nm wavelength less than 60%.

3. the high permeability energy-saving environment-friendly glass is characterized in that: add Fe at common sodium calcium silicon float glass ₂O ₃, SnCl ₂, Ce ₂(CO ₃) ₃, Nd ₂(CO ₃) ₃, simple substance Se, each set of dispense is than percentage meter by weight:

Silicon oxide sio ₂: 64～85%

Sodium oxide Na ₂O:6～14%

Calcium oxide CaO:4～12%

Magnesium oxide MgO:2～7%

Aluminium oxide Al ₂O ₃: 0～3%

Ferric oxide Fe ₂O ₃: 0.2～0.4%

Tin protochloride SnCl ₂: 0.4～0.7%

Cerous carbonate Ce ₂(CO ₃) ₃: 0.08～0.1%

Neodymium carbonate Nd ₂(CO ₃) ₃: 0.05～0.07%

Simple substance selenium Se:0.04～0.06%.

4. by the described high permeability energy-saving environment-friendly glass of claim 3, it is characterized in that: this kind 4mm heavy sheet glass has visible light transmissivity at 380～780nm wavelength greater than 88%, at the ultraviolet ray transmissivity of 280～380nm wavelength less than 12%; In the near infrared transmitance of 780～2500nm wavelength less than 45%.

5. the high permeability energy-saving environment-friendly glass is characterized in that: add Fe at common sodium calcium silicon float glass ₂O ₃, SnCl ₂, Ce ₂(CO ₃) ₃, Nd ₂(CO ₃) ₃, simple substance Se, each set of dispense is than percentage meter by weight::

Silicon oxide sio ₂: 64～85%

Sodium oxide Na ₂O:6～14%

Calcium oxide CaO:4～12%

Magnesium oxide MgO:2～7%

Aluminium oxide Al ₂O ₃: 0～3%

Ferric oxide Fe ₂O ₃: 0.4～0.6%

Tin protochloride SnCl ₂: 0.6～0.8%

Cerous carbonate Ce ₂(CO ₃) ₃: 0.1～0.12%

Neodymium carbonate Nd ₂(CO ₃) ₃: 0.07～0.1%

Simple substance selenium Se:0.06～0.09%.

6. by the described high permeability energy-saving environment-friendly glass of claim 5, it is characterized in that: this kind 4mm heavy sheet glass has visible light transmissivity at 380～780nm wavelength greater than 88%, at the ultraviolet ray transmissivity of 280～380nm wavelength less than 8%; In the near infrared transmitance of 780～2500nm wavelength less than 18%.

7. the high permeability energy-saving environment-friendly glass is characterized in that: add Fe at common sodium calcium silicon float glass ₂O ₃, SnCl ₂, Ce ₂(CO ₃) ₃, Nd ₂(CO ₃) ₃, simple substance Se, each composition accounts for glass weight per-cent and is:

Silicon oxide sio ₂: 64～85%

Sodium oxide Na ₂O:6～14%

Calcium oxide CaO:4～12%

Magnesium oxide MgO:2～7%

Aluminium oxide Al ₂O ₃: 0～3%

Ferric oxide Fe ₂O ₃: 0.6～0.8%

Tin protochloride SnCl ₂: 0.8～1%

Cerous carbonate Ce ₂(CO ₃) ₃: 0.12～0.15%

Neodymium carbonate Nd ₂(CO ₃) ₃: 0.1～0.14%

Simple substance selenium Se:0.09～0.12%.

8. by the described high permeability energy-saving environment-friendly glass of claim 7, it is characterized in that: this kind 4mm heavy sheet glass has visible light transmissivity at 380～780nm wavelength greater than 88%, at the ultraviolet ray transmissivity of 280～380nm wavelength less than 4%; In the near infrared transmitance of 780～2500nm wavelength less than 15%.