CN101475318B - Corrosion resistant titanium silicide film coating glass and preparation thereof - Google Patents

Corrosion resistant titanium silicide film coating glass and preparation thereof Download PDF

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Publication number
CN101475318B
CN101475318B CN 200910095672 CN200910095672A CN101475318B CN 101475318 B CN101475318 B CN 101475318B CN 200910095672 CN200910095672 CN 200910095672 CN 200910095672 A CN200910095672 A CN 200910095672A CN 101475318 B CN101475318 B CN 101475318B
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glass
film
ticl
sih
titanium silicide
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CN101475318A (en
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杜丕一
任招娣
翁文剑
韩高荣
赵高凌
沈鸽
宋晨露
徐刚
张溪文
汪建勋
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The invention discloses anticorrosive titanium silicide (Ti5Si3) film-plated glass and a method for preparing the same. Silane and titanium tetrachloride are used as a reaction precursor; nitrogen gas is used as dilute gas and protective gas; and the reaction precursor is deposited on the surface of the glass at a temperature of between 650 and 740 DEG C to generate the Ti5Si3 film-plated glass. The prepared Ti5Si3 film-plated glass has thickness of between 200 and 300 nm, infrared reflectivity of between 85 and 93 percents and transmissivity in a visible light region of between 30 and 20 percents and is the anticorrosive titanium silicide film-plated glass with functions of light dimming, heat insulation and low radiation. Compared with the prior TiSi2 film-plated glass, the titanium silicide (Ti5Si3) film-plated glass has good corrosion resistance and wider application prospect. The preparation of the film-plated glass is carried out in a tin groove, a transition roller or the front end of an annealing furnace of a float glass production line, can be combined with a float online glass production process and saves energy.

Description

A kind of corrosion resistant titanium silicide film coating glass and preparation method thereof
Technical field
The present invention relates to a kind of titanium silicide film coating glass and preparation method thereof, especially relate to a kind of corrosion-resistant Ti 5Si 3Coated glass and preparation method thereof.
Background technology
The energy consumption of residential housing is occupied suitable proportion in building energy consumption, and the window sensitive part that is the buildings thermal energy exchange is very crucial to building energy conservation.Simple glass is very low to the reflectivity of the infrared emanation more than the 2.5 μ m; Specific absorption is very high; Make that winter, indoor infrared emanation was easy to be delivered to outdoor through window, summer, outdoor infrared emanation was easy to be delivered to indoor, had increased and heated winter and refrigerating energy consumption in summer.Compare with simple glass, low radiation (LOW-E) glass has very high reflectivity to infrared light, and its heat transfer coefficient can reduce by 33.9%, so that as low emissivity glass, can stop indoor infrared emanation to reach heat insulation effect through glass to outdoor diffusion; Common light modulation heat insulation (Solar control) coated glass then stops in the outdoor optical radiation energy inlet chamber in summer influences room temp, realizes effect of heat insulation, thereby reduces the residential housing energy consumption.If can be one, then will play very big pushing effect to the application of coated glass with hanging down heat insulation two the function collection of radiation and light modulation.Yet; Have the complex thin film structure that this coated glass of two kinds of functions normally adopts the light modulation thermal insulation film to combine and process with low radiation film concurrently; This has not singly increased the complicacy of technology, and to coated glass separately the performance of performance also can have a negative impact.Thereby, having sunlight control and low radiation functions in the novel unitary film functional plating film glass of one, sunlight is controlled and the development of the energy-conservation coated glass of low radiation functions will produce very big influence to having concurrently.
In fact, integrate sunlight control and caused people's attention with the multi-function membrane of low radiance and the research of relevant coated glass thereof.According to classical electromagnetic theory, known film with high conductivity, its reflectivity to infrared wave is just high, also is that the radiant ratio of film is just low, and heat preservation and insulation is good more.Titanium silicide is because its extremely low resistivity; High chemistry and thermostability and self soft visible light absorption; Can prepare and both had the sunlight control characteristic, have the novel rete of low radiation characteristic again, be a kind of novel integrating sunlight control and hang down the functional membrane of radiation.At present, titanium silicide is used to prepare coated glass has had related application gradually, has applied for relevant TiSi like Gordon 2The patent US5167986 of coated glass and WO89/10209 have introduced TiSi 2Coated glass is as the application and the online preparation thereof of light modulation heat-protecting glass, and it adopts SiH 4-TiCl 4-He system has formed TiSi at 650～680 ℃ 2Film, the coated glass that has obtained to have neutralc tint and higher near infrared reflectivity.The big first-class new SiH that adopts shuts out 4-TiCl 4-N 2System is at preparation TiSi on glass 2Film has obtained Chinese patent ZL200510049828.7.
Yet, in titanium silicide, except TiSi 2Phase, the compound of other Si and Ti is (like Ti 5Si 3) to have resistivity equally low, advantages such as Heat stability is good, thereby be expected to be used for low radiation coated glass equally.Ti particularly 5Si 3Be the intermetallic compound of a kind of typical Si and Ti, resistivity very low (being merely 50～120 μ Ω cm) not only, and have characteristics such as fusing point height (2403K), hot strength are big, corrosion resistance and good.Usually be used as the resistance to high temperature oxidation coating of Ti alloy or other nitride, its antioxidant property is far superior to TiSi 2Phase.Therefore, use Ti 5Si 3As the rete of coated glass, not only have high ir reflectance, but also, solve problems such as anti-oxidant owing to its good high-temperature and antioxidant property are expected to be used for rigorous environment owing to its low-resistivity makes the coated glass that is obtained.
At present, Ti in the existing research 5Si 3Usually use from spreading method synthetic at high temperature, or deposited by electron beam evaporation method or prepare with aumospheric pressure cvd (CVD) method.What the former prepared is powder, and second kind can deposit resist on the Ti alloy, and the third can prepare the inducing layer that a kind of catalyst-free forms the TiSi nano wire, or also can prepare the anti-oxidation protection layer.Yet, be used for the Ti of this difunctional energy-conservation coated glass 5Si 3Film particularly utilizes float glass online production prepared Ti 5Si 3Film is to research is not also arranged at present.
Summary of the invention
The object of the present invention is to provide a kind of corrosion resistant titanium silicide (Ti 5Si 3) coated glass and preparation method thereof, use chemical Vapor deposition process, through the concentration and the temperature of Controlling Source gas, on simple glass, prepared the Ti of hexagonal structure 5Si 3Film.
The technical solution adopted for the present invention to solve the technical problems is following:
One, a kind of corrosion resistant titanium silicide (Ti 5Si 3) coated glass (Ti 5Si 3) coated glass:
The amorphous layer that on a side of common float-glass substrate, has one deck Si and Ti to constitute, and then the Ti of another layer hexagonal structure is arranged on the amorphous layer of Si and Ti formation 5Si 3The phase thin film layer.
Two, a kind of corrosion resistant titanium silicide (Ti 5Si 3) preparation method of coated glass, the step of this method is following:
1) Si source and Ti source are respectively gasiform SiH 4TiCl with liquid state 4, use N 2As diluents and shielding gas;
2) TiCl of liquid state 4Obtain its steam through heating, use N 2As carrier gas;
3) gasiform SiH 4, TiCl 4Steam, and N 2In mixing chamber, mix the back and introduce participation reaction in the reaction chamber; Wherein, SiH 4And TiCl 4Shared molar percentage is in total gas:
a)SiH 4：0.03～0.26％
b)TiCl 4：0.29～0.06％
4) reaction gas pressure maintains 8.00 * 10 4～1.01 * 10 5Between the Pa;
5) be reflected on the glass surface and carry out, in order to obtain required coated glass, the control of deposition parameter is following: when reacting gas concentration compares SiH 4/ TiCl 4=0.1～2.5 o'clock, depositing temperature was 650～740 ℃; When reacting gas concentration compares SiH 4/ TiCl 4=2.5～4 o'clock, depositing temperature was 650～700 ℃; Depositing time is 2～15 seconds;
6) the control reacting gas concentration ratio through step 5), depositing temperature and depositing time are regulated the thickness of the titanium silicide film that deposits;
7) waste gas is handled the back discharging through absorbing.
Described coated glass carries out in the fixed sediment chamber, or at the molten tin bath of floatation glass production line or transition roller closes or the annealing furnace front end carries out.
The prepared Ti that obtains 5Si 3Coated glass, its thickness are 200～300nm, and ir reflectance is 85～93%, and the visible region transmitance is 30～20%, corrosion resistance and good.
The present invention compares the beneficial effect that has with background technology:
1, successfully obtained the Ti of hexagonal structure 5Si 3Phase;
2, resulting Ti 5Si 3Coated glass has ir reflectance between 85～93%, and visible light transmissivity is adjustable between 30～20%;
3, the Ti that obtains 5Si 3Coated glass has good anti-corrosion, is expected to be used for severe rugged environment.
4, can coated glass technology be combined with floatation glass production line, make preparation technology's procedure of coated glass, thus effective save energy.
Description of drawings
Accompanying drawing is the three-decker synoptic diagram of coated glass of the present invention.
Among the figure: 1, common float-glass substrate, 2, amorphous layer, 3, thin film layer.
Embodiment
Shown in accompanying drawing, the present invention has the amorphous layer 2 of one deck Si and Ti formation on a side of common float-glass substrate 1, and then on the amorphous layer 2 of Si and Ti formation, the Ti of another layer hexagonal structure is arranged 5Si 3Phase thin film layer 3.
Embodiment 1:
Reaction source gas throughput ratio SiH 4/ TiCl 4=1, SiH 4Concentration is 0.16%, TiCl 4Concentration is 0.16%, depositing temperature T=740 ℃, and depositing time 5s, the reaction chamber internal pressure is 8.00 * 10 4Pa has formed Ti on glass substrate 5Si 3Film.This Ti 5Si 3Film thickness is 250nm, and the visible light transmissivity at 550nm place is that the ir reflectance at 28%, 22.5 μ m place is 90%, and is corrosion-resistant.
Embodiment 2:
Reaction source gas throughput ratio SiH 4/ TiCl 4=1, SiH 4Concentration is 0.16%, TiCl 4Concentration is 0.16%, depositing temperature T=690 ℃, and depositing time 12s, the reaction chamber internal pressure is 8.00 * 10 4Pa has formed Ti on glass substrate 5Si 3Film.This Ti 5Si 3Film thickness is 230nm, and the visible light transmissivity at 550nm place is that the ir reflectance at 29%, 22.5 μ m place is 86%, and is corrosion-resistant.
Embodiment 3:
Reaction source gas throughput ratio SiH 4/ TiCl 4=1, SiH 4Concentration is 0.16%, TiCl 4Concentration is 0.16%, depositing temperature T=710 ℃, and depositing time 10s, the reaction chamber internal pressure is 9.00 * 10 4Pa has formed Ti on glass substrate 5Si 3Film.This Ti 5Si 3Film thickness is 260nm, and the visible light transmissivity at 550nm place is that the ir reflectance at 27%, 22.5 μ m place is 88%, and is corrosion-resistant.。
Embodiment 4:
Reaction source gas throughput ratio SiH 4/ TiCl 4=2, SiH 4Concentration is 0.21%, TiCl 4Concentration is 0.11%, depositing temperature T=720 ℃, and depositing time 15s, the reaction chamber internal pressure is 8.00 * 10 4Pa has formed Ti on glass substrate 5Si 3Film.This Ti 5Si 3Film thickness is 300nm, and the visible light transmissivity at 550nm place is that the ir reflectance at 20%, 22.5 μ m place is 92%, and is corrosion-resistant.
Embodiment 5:
Reaction source gas throughput ratio SiH 4/ TiCl 4=0.5, SiH 4Concentration is 0.11%, TiCl 4Concentration is 0.21%, depositing temperature T=730 ℃, and depositing time 10s, the reaction chamber internal pressure is 8.00 * 10 4Pa has formed Ti on glass substrate 5Si 3Film.This Ti 5Si 3Film thickness is 260nm, and the visible light transmissivity at 550nm place is that the ir reflectance at 26%, 22.5 μ m place is 88%, and is corrosion-resistant.
Embodiment 6:
Reaction source gas throughput ratio SiH 4/ TiCl 4=4, SiH 4Concentration is 0.26%, TiCl 4Concentration is 0.06%, depositing temperature T=690 ℃, and depositing time 8s, the reaction chamber internal pressure is 8.00 * 10 4Pa forms Ti on glass substrate 5Si 3Film.This Ti 5Si 3Film thickness is 240nm, and the visible light transmissivity at 550nm place is that the ir reflectance at 28%, 22.5 μ m place is 87%, and is corrosion-resistant.
Embodiment 7:
Reaction source gas throughput ratio SiH 4/ TiCl 4=2.5, SiH 4Concentration is 0.23%, TiCl 4Concentration is 0.09%, depositing temperature T=700 ℃, and depositing time 12s, the reaction chamber internal pressure is 1.01 * 10 5Pa forms Ti on glass substrate 5Si 3Film.This Ti 5Si 3Film thickness is 280nm, and the visible light transmissivity at 550nm place is that the ir reflectance at 25%, 22.5 μ m place is 89%, and is corrosion-resistant.
Embodiment 8:
Reaction source gas throughput ratio SiH 4/ TiCl 4=3, SiH 4Concentration is 0.24%, TiCl 4Concentration is 0.08%, depositing temperature T=670 ℃, and depositing time 8s, the reaction chamber internal pressure is 8.00 * 10 4Pa has formed Ti on glass substrate 5Si 3Film.This Ti 5Si 3Film thickness is 200nm, and the visible light transmissivity at 550nm place is that the ir reflectance at 30%, 22.5 μ m place is 86%, and is corrosion-resistant.

Claims (3)

1. the preparation method of a corrosion resistant titanium silicide film coating glass is characterized in that the step of this method is following:
1) Si source and Ti source are respectively gasiform SiH 4TiCl with liquid state 4, use N 2As diluents and shielding gas;
2) TiCl of liquid state 4Obtain its steam through heating, use N 2As carrier gas;
3) gasiform SiH 4, TiCl 4Steam, and N 2In mixing chamber, mix the back and introduce participation reaction in the reaction chamber; Wherein, SiH 4And TiCl 4Shared molar percentage is in total gas:
a)SiH 4：0.03～0.26％
b)TiCl 4：0.29～0.06％
4) reaction gas pressure maintains 8.00 * 10 4～1.01 * 10 5Between the Pa;
5) be reflected on the glass surface and carry out, in order to obtain required coated glass, the control of deposition parameter is following: when reacting gas concentration compares SiH 4/ TiCl 4=0.1～2.5 o'clock, depositing temperature was 650～740 ℃; When reacting gas concentration compares SiH 4/ TiCl 4=2.5～4 o'clock, depositing temperature was 650～700 ℃; Depositing time is 2～15 seconds;
6) the control reacting gas concentration ratio through step 5), depositing temperature and depositing time are regulated the thickness of the titanium silicide film that deposits;
7) waste gas is handled the back discharging through absorbing.
2. the preparation method of a kind of corrosion resistant titanium silicide film coating glass according to claim 1, it is characterized in that: described coated glass carries out in the fixed sediment chamber, or at the molten tin bath of floatation glass production line or transition roller closes or the annealing furnace front end carries out.
3. the preparation method of a kind of corrosion resistant titanium silicide film coating glass according to claim 1 is characterized in that: the prepared Ti that obtains 5Si 3Coated glass, its thickness are 200～300nm, and ir reflectance is 85～93%, and the visible region transmitance is 30～20%, corrosion resistance and good.
CN 200910095672 2009-01-19 2009-01-19 Corrosion resistant titanium silicide film coating glass and preparation thereof Expired - Fee Related CN101475318B (en)

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CN107833939B (en) * 2017-11-22 2021-09-03 绍兴文理学院 Two-dimensional photonic crystal selective radiator and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989010209A1 (en) * 1988-04-15 1989-11-02 Gordon Roy G Titanium silicide-coated glass windows
CN1699235A (en) * 2005-05-25 2005-11-23 浙江大学 Titanium silicide coated glass with compound functions prepared by nitrogen protection under normal pressure and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1989010209A1 (en) * 1988-04-15 1989-11-02 Gordon Roy G Titanium silicide-coated glass windows
CN1699235A (en) * 2005-05-25 2005-11-23 浙江大学 Titanium silicide coated glass with compound functions prepared by nitrogen protection under normal pressure and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
常压化学气相沉积法制备Ti5Si3薄膜及其镀膜玻璃;黄燕飞等;《硅酸盐学报》;20091031;第1694-1699页 *
黄燕飞等.常压化学气相沉积法制备Ti5Si3薄膜及其镀膜玻璃.《硅酸盐学报》.2009,第1694-1699页.

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