CN105082670B - A kind of green sunshade type coated glass and preparation method thereof - Google Patents
A kind of green sunshade type coated glass and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of green sunshade type coated glass and preparation method thereof, the green sunshade type coated glass includes successively the closely glass substrate of overlapping, the first silico-aluminum film；Second nichrome film；3rd silver layer；4th nichrome film；5th sial metal film, the preparation method include step：1) sinter target；2) pretreatment of glass；3) coating film treatment.The present invention is that reflected colour is in green in the sun, can reach good decoration, energy-saving effect to low radiation coated glass obtained in interference of light on French green float glass substrate by various metal materials；Product can strange land processing, reduce processing enterprise manufacturing cost；Double glazing is may be made as, preferably control light, energy-saving effect is reached.
Description
Technical field
The present invention relates to a kind of coated glass preparation method and the coated glass prepared by the method, more particularly to a kind of low
The preparation method of radiation film coating glass and its low radiation coated glass of preparation.
Background technology
Coated glass (Reflective glass) is also referred to as reflecting glass.Coated glass be in one layer of glass surface coating or
Multiple layer metal, alloy or metal compound film, to change the optical property of glass, meet certain particular requirement.Coated glass
By the different qualities of product, following a few classes can be divided into：Heat-reflecting glass, low emissivity glass (Low-E), electropane etc..
The production method of coated glass is a lot, such as vacuum magnetic-control sputtering method, vacuum vapor deposition method, chemical vapour deposition technique and
Sol-gel process etc..Magnetron sputtering film glass can manufacture and design multilamellar complexity membrane system using magnetron sputtering technique, can be white
Multiple color is plated out in color glass substrate, the corrosion-resistant and anti-wear performance of film layer preferably, is produced at present and using most skills
Art.There is certain gap compared with magnetron sputtering film glass in the kind and quality of vacuum evaporation coating film glass, progressively by
Vacuum sputtering replaces.Chemical vapour deposition technique is that reacting gas is passed through on floatation glass production line in scorching hot glass surface
Decompose, be uniformly deposited on the technology that glass surface forms coated glass.The equipment investment of the method is few, easy-regulating, product into
This low, chemical stability is good, can hot-working, be one of production method most rising at present.Sol-gel process production plating
Film glass process is simple, good stability, weak point are that product transmittance is too high, ornamental poor.
Magnetron sputtering method is that application is at most in current world wide, technique is most stable, performance preferably (radiance E value≤
0.12) the coated glass production technology that, kind is most abundant, energy demand is relatively low.As this production technology need not be with
Floatation glass production line bundles use, you can so that float glass is separately carried out with coating film on glass technique, effectively
Reduce glass post-processing enterprise repeated construction floatation glass production line, reduce the energy of CO2 emissions and correlation
Consume.
The principle of magnetron sputtering plating is to add a quadrature field and electricity and anode between in sputtered target pole (negative electrode)
, be filled with high vacuum chamber required for noble gases (usually Ar gas), permanent magnet target surfaces formed 250～
The magnetic field of 350 Gausses, constitutes crossed electric and magnetic field with high voltage electric field.In the presence of electric field, argon is ionized into cation and electronics,
Added with certain negative high voltage on target, the electronics sent from target pole is increased with the ionization probability of working gas by the effect in magnetic field,
Highdensity plasma is formed about in negative electrode, Ar ions accelerate to fly to target surface in the presence of Lorentz force, with very high
Speed bombards target surface, and the atom being sputtered on target out departs from target surface with higher kinetic energy and flies to glass substrate and deposit film forming.
Apply most heat-reflecting glass and low emissivity glass substantially using vacuum magnetic-control sputtering method and chemical gas at present
Phase sedimentation is produced.Comparing famous vacuum magnetic-control sputtering method equipment manufacturer in the world has BOC Co. (U.S.) He Laibao
Company (Germany)；There is MB Group Plc (Britain) etc. in Chemical Vapor Deposition Equipment producer.At present, China has occurred hundreds of
Coated glass manufacturer of family, affects larger vacuum magnetic-control sputtering method manufacturer to have South China glass group company in the industry
With Shanghai Sunlight coated glass company etc., there are Shandong blue star glass company and the Changjiang river float glass process glass in chemical vapour deposition technique manufacturer
Glass company etc..
Few to the PRODUCTION TRAITS of green coated glass at present, the present invention uses French green bodies coloured glass as plating
The substrate of film, effectively make use of absorbing and filtering function of the body-tinted glass to sunlight middle-ultraviolet lamp, and the present invention is from special
The green sunshade type coated glass that fixed nickel chromium triangle, sial, silver are made for sputtering target material, bright in luster and easily dimmable, quality are steady
Fixed, make efficiency is high, but, what the method made is low radiation coated glass (LOW-E glass), only micro- in 4.5-25 to wavelength
Far infrared in the range of rice has higher reflectivity, solar absorptance and ultraviolet filtering, suitable life-time service.
The content of the invention
The primary and foremost purpose of the present invention is that the problem existed for above-mentioned existing coated glass technology of preparing provides a kind of green
The preparation method of sunshade type coated glass and the green sunshade type coated glass of preparation.Green sunshade type prepared by the inventive method
Coated glass in green, can reach good decorative effect in the sun；Visible light transmissivity is low, outdoor visible reflectance
The transmitance of high, solar energy is low, solar reflectance is high；And the present invention green low radiation control glass transition coefficient it is low,
Shading coefficient is low, thermal property is good, can effectively prevent heat energy from getting in, and reduces energy consumption for cooling；Double glazing need to be made, is controlled
Light energy-saving effect is more preferably.
To realize the purpose of the present invention, one aspect of the present invention provides a kind of green sunshade type coated glass, including tight successively
The glass substrate and metallic diaphragm of close overlapping：
Glass substrate；
First film layer, positioned at the surface of glass substrate, first film layer is silico-aluminum film；
Second film layer, positioned at the surface of first film layer, second film layer is nichrome film；
Third membrane layer, positioned at the surface of second film layer, the third membrane layer is silverskin；
4th film layer, positioned at the surface of the third membrane layer, the 4th film layer is nichrome film.
4th film layer, positioned at the surface of the 4th film layer, the 5th film layer is silico-aluminum film.
Wherein, the thickness of the first silico-aluminum film layer is 56.0-60.0nm, preferably 57.8-59.2nm；Described
The thickness of two nichrome film layers is 7.0-8.0nm, preferably 7.3-7.6nm；The thickness of the 3rd silver film is 12.0-
13.0nm, preferably 12.4-12.6nm；The thickness of the 4th nichrome film layer is 7.0-8.0nm, preferably 7.6-
7.8nm；The thickness of the 5th nichrome film layer is 130.0-142.0nm, preferably 132.0-139.2nm.
Particularly, a surface of the glass substrate overlap successively from bottom to top the first silico-aluminum film layer,
Second nichrome film layer, the 3rd silver film, the 4th nichrome film layer, the 5th silico-aluminum film layer.
Wherein, green sunshade type coated glass face reflection colour 58≤L of value*≤ 70, -12≤a*≤ 0, -1.5≤b*≤4
Between.
Particularly, the glass substrate selects the green glass prepared using floating process；Floating process is adopted preferably
The French green glass (i.e. F- green glass, that is, French green float glass) of preparation.
Another aspect of the present invention provides a kind of preparation method of green sunshade type coated glass, including order below is carried out
Step：
1) sinter target
Silico-aluminum, nichrome, silver are sintered on the target position of vacuum sputtering room of glass film coating machine respectively, it is standby；
2) pretreatment of glass
The glass of film process to be plated is placed under vacuum state, the glass for treating coating film treatment carries out dehumidifying, degassing process,
The water and gas of glass surface deposition are reduced, dehumidifying, degassing glass is obtained；
3) coating film treatment
Dehumidifying, degassing glass are sent in the vacuum magnetic-control sputtering room of glass film coating machine, on dehumidifying, the surface of degassing glass
The first silico-aluminum of plating film layer, the second nichrome film layer, the 3rd silver film, the 4th nichrome film successively from bottom to top
Layer, silico-aluminum film layer.
Wherein, step 1) described in silico-aluminum to select sintering purity be that >=99.5%, density is >=2.1g/cm3, it is molten
Point is 580 DEG C of silico-aluminum, and Al content is 8-12 ± 2wt%, and remaining is Si；Described nichrome selects to sinter purity
>=99.7%, density is >=8.5g/cm3, the nichrome that fusing point is 1420 DEG C, wherein Cr contents be 20 ± 1wt%, remaining is
Ni；It is >=99.99% that the silver selects sintering purity, and density is >=10.5g/cm3；Fusing point is 960 DEG C of silver metal.
Particularly, the sintering time of the silico-aluminum is 90min；The sintering time of the nichrome is 60min；Institute
The sintering time for stating silver is 60min.
Especially, the silico-aluminum meets the component requirements of sial target in national sector standard JC/T2068-2011；Institute
State the component requirements that nichrome meets nickel chromium triangle target in national sector standard JC/T2068-2011；The silver meets national industry
The component requirements of silver-colored target in standard JC/T2068-2011.
Wherein, step 2) described in dehumidifying, degassing process reduce glass surface processing stage be by film glass to be plated point 2
The moisture content and gas of deposition, is obtained described dehumidifying, degassing glass.
Particularly, first during the dehumidifying, degassing process the absolute pressure in processing stage is higher than second processing rank
Absolute pressure in section.
Especially, the 1st processing stage during absolute pressure be 5.0-6.0 × 10- 2mbar；Process processing stage 2nd
In absolute pressure be 3.0-6.0 × 10-3mbar。
Particularly, the 1st processing stage treatment temperature be -135～-145 DEG C, glass treatment speed be 2.3-2.9m/
Min, preferably 2.5m/min；Treatment temperature processing stage 2nd is 80-100 DEG C, and glass treatment speed is 2.3-2.9m/
Min, preferably 2.5m/min.
Especially, the first dehumidifying, the process time in degassing process stage are 40-50s, preferably 45s；It is second dehumidifying, de-
The process time in gas disposal stage is 80-100s, preferably 90s.
Particularly, also including step 2A)：Treat coating film treatment glass carry out deionized water cleaning treatment after carry out institute again
The dehumidifying stated, degassing process.
Especially, the content≤5 μ/cm/m of the deionized water mineral2；Temperature is 35-40 DEG C；Cleaning speed is
1.5-2.5m/min, preferably 1.8-2.1m/min.
Particularly, step 2) described in film process to be plated glass select using floating process prepare green glass；It is excellent
Elect the French green glass (i.e. F- green glass, that is, French green float glass) prepared using floating process as
Particularly, step 3) absolute pressure during the coating film treatment in vacuum magnetic-control sputtering room remains 2.0-
4.0×10-3Mbar, preferably 3.0 × 10-3mbar；The speed of plating is 2.3-2.9m/min, preferably 2.5m/min；Temperature
For 80-100 DEG C.
Wherein, step 3) described in the first silico-aluminum film layer plating is formed at twice.
Particularly, in the coating process of the first silico-aluminum film layer, the vacuum magnetic-control sputtering of first time plating is electric
Press as 470.0-490.0V, preferably 475.0-485.0V；Electric current is 74.0-79.0A, preferably 75.0-77.0A, and power is
25.0-35.0Kw, preferably 28.0-31.0Kw；Second plating in the coating process of the first silico-aluminum film layer
Vacuum magnetic-control sputtering voltage be 475.0-485.0V, preferably 478.0-483.0V, electric current are 73.0-78.0A, preferably
75.0-77.0A, power is 27.0-32.0Kw, preferably 28.0-31.0Kw.
Wherein, during first, second plating of the first silico-aluminum film layer in vacuum magnetic-control sputtering room
Atmosphere is the mixed gas of nitrogen and argon.
Particularly, in the atmosphere, nitrogen and the ratio of the volume of argon are 18：11-12, preferably 18：11.
Especially, in the coating process of the first silico-aluminum film layer for the first time, it is true during second plating
In empty magnetron sputtering room, nitrogen and the ratio of the volume of argon are 18：11.
Particularly, the flow of the nitrogen is 900sc/cm, and the flow of argon is 550sc/cm.
Particularly, the coating film thickness of the first silico-aluminum film layer is 56.0-59.0nm, preferably 57.8-58.3nm.
Particularly, the thickness of the first time plating of the first silico-aluminum film is 28.0-30.0nm, preferably
28.9-29.5nm；The thickness of second plating of the first silico-aluminum film is 28.0-30.0nm, preferably 28.9-
29.7nm。
Wherein, step 3) described in the second nichrome film layer coating film treatment during vacuum magnetic-control sputtering voltage be
341.0-345V, preferably 343.0-344.0V；Electric current is 7.0-8A, preferably 7.4-7.8A；Power is 2.0-3.0Kw, excellent
Elect 2.5-2.8Kw as.
Wherein, the atmosphere during the plating of the second nichrome film layer in vacuum magnetic-control sputtering room is argon
Gas.
Particularly, the flow of the argon is 1200sc/cm.
Particularly, the thickness of the plating of second nichrome film is 7.0-8.0nm, preferably 7.3-7.6nm.
Wherein, step 3) described in the 3rd silver film coating film treatment during, vacuum magnetic-control sputtering voltage be 380.0-
390.0V, preferably 382.0-389.0V；Electric current is 12.0-13.0A, preferably 12.1-12.9A；Power is 4.0-5.0Kw,
Preferably 4.7-5.0Kw.
Particularly, the atmosphere during the coating film treatment of the 3rd silver film in vacuum magnetic-control sputtering room is argon.
Especially, the flow of the argon is 1000sc/cm.
Particularly, the coating film thickness of the 3rd silver film is 12.0-13.0nm, preferably 12.4-12.6nm.
Wherein, step 3) described in the 4th nichrome film layer coating film treatment during vacuum magnetic-control sputtering voltage be
338.0-342.0V, preferably 339.1-341.0V；Electric current is 7.5-8.2A, preferably 7.7-8.1A；Power is 2.2-
3.0Kw, preferably 2.6-2.9Kw.
Wherein, the atmosphere during the plating of the second nichrome film layer in vacuum magnetic-control sputtering room is argon
Gas.
Particularly, the flow of the argon is 1200sc/cm.
Particularly, the thickness of the plating of second nichrome film is 7.0-8.0nm, preferably 7.6-7.8nm.
Wherein, step 3) described in the 5th silico-aluminum film layer plating is formed in five times.
Particularly, during the plating of the 5th silico-aluminum film layer, during first time plating, vacuum magnetic control splashes
Radio pressure is 490.0-495.0V, preferably 490.0-494.0V；Electric current is 67.0-70.0A, preferably 68.0-68.9A, work(
Rate is 26.5-27.5Kw, preferably 26.8-27.3Kw；Second plating during the plating of the 5th silico-aluminum film layer
During vacuum magnetic-control sputtering voltage be 475.0-480.0V, preferably 475.0-476.0V；Electric current is 68.0-70.0A, excellent
Elect 68.2-68.8A as；Power is 26.5-27.5Kw, preferably 27.1-27.3Kw；The plating process of the 5th silico-aluminum film layer
Vacuum magnetic-control sputtering voltage during middle third time plating is 435.0-440.0V, preferably 435.0-439.0V；Electricity
Flow for 75.0-76.0A, preferably 75.1-75.3A；Power is 26.5-27.5Kw, preferably 27.1-27.2Kw；5th sial
Vacuum magnetic-control sputtering voltage during the plating of alloy film layer during the 4th plating is 440.0-450.0V, preferably
For 435.0-455.0V；Electric current is 73.0-76.0A, preferably 73.0-75.0A；Power is 26.0-28.5Kw, preferably
26.5-28.0Kw；Vacuum magnetic-control sputtering electricity during the plating of the 5th silico-aluminum film layer during the 5th plating
Press as 460.0-470.0V, preferably 460.0-464.0V；Electric current is 71.0-73.5A, preferably 72.0-72.6A；Power is
27.0-28.5Kw, preferably 27.0-28.0Kw.
Wherein, it is true during the first, second, third, fourth, the 5th plating of the 5th silico-aluminum film layer
Atmosphere in empty magnetron sputtering room is the mixed gas of nitrogen and argon.
Particularly, Vacuum Magnetic during first and second plating in the coating process of the 5th silico-aluminum film layer
The indoor nitrogen of control sputtering is 18 with the ratio of the volume of argon：11.
Especially, the flow of the nitrogen is 900sc/cm, and the flow of argon is 550sc/cm.
Particularly, first and second plating coating film thickness of the 5th silico-aluminum film layer is 27.0-29.5nm, preferably
For 27.0-29.0nm.
Especially, in the coating process of the 5th silico-aluminum film layer, during third time plating, vacuum magnetic control splashes
The ratio that indoor nitrogen is penetrated with the volume of argon is 8.5：4.4.
Particularly, the flow of the nitrogen is 850sc/cm, and the flow of argon is 440sc/cm.
Particularly, the third time plating coating film thickness of the 5th silico-aluminum film layer is 22.0-25.0nm, preferably
22.0-24.0nm。
Especially, in the coating process of the 5th silico-aluminum film layer, during the 4th plating, vacuum magnetic control splashes
The ratio that indoor nitrogen is penetrated with the volume of argon is 8.5：5.
Particularly, the flow of the nitrogen is 850sc/cm, and the flow of argon is 500sc/cm.
Especially, in the coating process of the 5th silico-aluminum film layer, during the 5th plating, vacuum magnetic control splashes
The ratio that indoor nitrogen is penetrated with the volume of argon is 3：2.
Particularly, the flow of the nitrogen is 900sc/cm, and the flow of argon is 600sc/cm.
Particularly, the 4th plating coating film thickness of the 5th silico-aluminum film layer is 27.0-29.0nm, preferably
28.0-29.0nm；5th plating coating film thickness of the 5th silico-aluminum film layer is 27.0-29.0nm, preferably 28.0-
28.2nm。
Particularly, the coating film thickness of the first silico-aluminum film layer is 130.0-142.0nm, preferably 132.0-
139.2nm。
Particularly, also including step 4) buffered, the glass through coating film treatment is conveyed from vacuum magnetic-control sputtering room
To pressure buffer room, the indoor pressure of buffering is gradually stepped up, until it reaches normal pressure；The indoor temperature of buffering is reduced, interior is made
Temperature reaches 20-35 DEG C.
Another aspect of the present invention provides a kind of green sunshade type coated glass (SUN-E being prepared from according to the method described above
Glass).
The green sunshade type coated glass (SUN-E glass) of the present invention has the advantage that：
1st, green sunshade type coated glass prepared by the present invention is using floating in green by magnetron sputtering under vacuum conditions
The surface of method glass successively the first silico-aluminum of plating film, the second nichrome film, the 3rd silverskin, the 4th nichrome film,
Five silico-aluminum films, the composite membrane of glass surface are shown in green under outdoor solar light, using cheap silico-aluminum, nickel
Evanohm, silver are green sunshade type coated glass (SUN-E prepared by target and common French green body tinted float glass substrate
Glass) low production cost, promoting the use of beneficial to low emissivity glass.
2nd, green sunshade type coated glass reflection colour prepared by the inventive method, in green, is in the industries such as current building
The appearance color that designer or owner appreciate, its principal visual physical parameter is in L*=58～70, a*=-12～0, b*=1.5～
Within 4, its outdoor in green, it is colorful, beautiful, attractive in appearance, can be widely applied in various buildings, imitate with good decoration
Really.
3rd, green sunshade type coated glass (SUN-E glass) prepared by the present invention, its optical property technical parameter value meet
GB/T18915.1-2002《Coated glass part 2：Low radiation coated glass》Standard, it is seen that transmittance tolerance is most
Be worth greatly it is little, well below the 3.0% of national standard, reach see transmittance tolerance maximum be less than 0.5%；Color even
Property it is high, less than 2.0CIELAB.
4th, double glazing made by green sunshade type coated glass prepared by the present invention, it is seen that light transmission rate is more than 30%,
Outdoor visible reflectance is less than 31%, and the transmitance of solar energy is less than 20%, and solar reflectance is higher than 15%, is suitable to build
Bright comfortable indoor and outdoors luminous environment；Meanwhile, its heat transfer coefficient winter is less than 1.75W/m2K, summer are less than 1.70W/
m2K, shading coefficient (Sc) is less than 0.30.Total transmitance of solar energy is less than 25%, and relative thermal increases less than 195w/m2, Re Gongxing
Can be good, can effectively block sunlight heat to indoor radiation, energy-efficient performance is good, reduces energy consumption for cooling, controls light energy-saving effect more preferably.
5th, green sunshade type coated glass of the invention can pass through the thickness for changing each plated film film layer in preparation process
The green sunshade type coated glass of different optically and thermally performances is obtained, different types of double glazing is may be made as, to adapt to
Market different demands.
6th, the heat stability of green sunshade type coated glass prepared by the present invention is high, it is possible to achieve strange land heat treatment process.
7th, the method that the present invention prepares green sunshade type coated glass is real on the French green float glass of mass colouring
The change of existing colors green, solves the problems, such as the high cost to target during plated film, and cost is relatively low, convenient and reliable.
Description of the drawings
Fig. 1 is the generalized section of green sunshade type coated glass of the invention.
Reference：1st, glass substrate；2nd, the first silico-aluminum film layer；3rd, the second nichrome film layer；4th, the 3rd metal
Silver film；5th, the 4th nichrome film layer；6th, the 5th silico-aluminum film layer.
Specific embodiment
The present invention is further described below by embodiment, advantages of the present invention and feature will be with description and
It is apparent.But these embodiments are only exemplary, do not constitute any restriction to the scope of the present invention.People in the art
Member is it should be understood that can enter to the details of technical solution of the present invention and form without departing from the spirit and scope of the invention
Row modification is replaced, but these modifications and replacement are each fallen within protection scope of the present invention.
As shown in figure 1, the green sunshade type coated glass of the present invention is successively by green float glass substrate 1, the first film layer
2nd, the second film layer 3, third membrane layer 4, the 4th film layer 5, the 5th film layer composition.First film layer 2 is fitted tightly over green glass substrate 1
Surface on, the second film layer 3 is fitted tightly in the first film layer 2, and third membrane layer 4 is fitted tightly in the second film layer 3, the 4th film
Layer 5 is fitted tightly in third membrane layer 4, and the 5th film layer 6 is fitted tightly in the 4th film layer 5.First film layer is silico-aluminum film,
Second film layer is nichrome film, and third membrane layer is silverskin, and the 4th nichrome film, the 5th film layer are silico-aluminum film.First
The thickness of silico-aluminum film layer is 56-59nm, preferably 57.8-58.3nm；The thickness of the second nichrome film layer is
7.0-8.0nm, preferably 7.3-7.6nm；The thickness of the 3rd silver film is 12.0-13.0nm, preferably 12.4-
12.6nm；The thickness of the 4th nichrome film layer is 7.0-8.0nm, preferably 7.6-7.8nm；5th nichrome
The thickness of film layer is 130-138nm, preferably 133-136nm.
Embodiment 1
1st, target sintering
In vacuum magnetron sputtering film plating machine (Xin Fuxing Glass Co., Ltd. of Fujian Province, model：XFXDM-01D first) to
In tenth target chamber, the target of pre-molding is sintered in the corresponding target position of the first to the tenth target chamber respectively, wherein：It is sintered in
First, the target on two, six-ten target chamber target position is that >=99.5%, density is >=2.1g/cm for sintering purity3, fusing point be 580 DEG C
Silicon-aluminium alloy target material, wherein Al content be 8-12 ± 2wt%, remaining is Si；The target being sintered on the three, the 5th target chamber target position
It is that >=99.7%, density is >=8.5g/cm that material is nichrome selection sintering purity3, the nichrome that fusing point is 1420 DEG C, its
Middle Cr contents are 20 ± 1wt%, and remaining is Ni；The target being sintered on the 4th target chamber target position is >=99.99% for sintering purity,
Density is >=10.5g/cm3；Fusing point is 960 DEG C of silver-colored target.
Wherein, the sintering time of silico-aluminum is 90min；The sintering time of nichrome is 90min；The sintering time of silver
For 60min.
Silico-aluminum meets the component requirements of sial target in national standard JC/T2068-2011；The nichrome meets
The component requirements of nickel chromium triangle target in national standard JC/T2068-2011；The silver meets the composition of silver-colored target in national standard nickel chromium triangle will
Ask.
2nd, clean glass
2A) French green glass original piece (i.e. French green float glass) prepared by the employing floating process that thickness is 6.0mm
It is placed in coating film on glass cleaning machine (German GTA companies production, model：GTA01-M, in), adopt temperature and contain for 37 DEG C, mineral
Amount≤5 μ/cm/m2Deionized water carry out cleaning treatment, cleaning speed is 2.5m/min；
In the present invention green float glass original piece except from thickness for 6mm French green float glass sheet in addition to,
The green float glass original piece of other thickness is also applied for the present invention.Glass is cleaned using deionized water, glass can not only be removed
The greasy dirt or other impurities on surface, it also avoid the problem for introducing other metal ions is cleaned with tap water.
The float glass after cleaning is dried into process at 50 DEG C 2B), wherein rate of drying is 2.5m/min, is removed
The water droplet of glass surface, is obtained dry original sheet glass.
3rd, dehumidifying, degassing process
Dry original sheet glass rollgang 3A) is sent to the first vacuum chamber of vacuum magnetron sputtering film plating machine, to dry glass
Glass original piece carries out first time dehumidifying, degassing process, and wherein first time dehumidifying, the time of degassing process is 45s, and transmission speed is
2.5m/min；First time dehumidifying, the temperature of degassing process are -140 DEG C, and absolute pressure is 5.0 × 10- 2mbar；
The dry original sheet glass of process first time dehumidifying, degassing process is delivered to into the second vacuum chamber 3B), second row is carried out
Wet, degassing process, wherein second dehumidifying, the time of degassing process are 90s；Transmission speed is 2.5m/min；Second dehumidifying,
The temperature of degassing process is 90 DEG C, and absolute pressure is 3.5 × 10-3Mbar, is obtained film glass to be plated；
In the present invention, glass transmission speed is illustrated by taking 2.5m/min as an example, and glass transmission speed is 2.3-2.9m/min
It is applied to the present invention.
During the multiple dehumidifying, degassing process carried out to green float glass original piece, treatment temperature gradually rises,
Relative pressure is reduced successively, is especially accordingly extended process time in the second dehumidifying, degassing process stage, is eliminated and be deposited on glass
The aqueous vapor and gas on glass surface so that the clean surface of float glass to be coated, increased the attached of glass surface and plated film interlayer
Put forth effort, make institute's film plating layer difficult for drop-off；Meanwhile, 2 dehumidifying, degassing process, when float glass sheet is in magnetron sputtering
Under identical environmental condition, it is easy to the carrying out of subsequent operation, shortens the coating film on glass time, there is provided the efficiency of coating film on glass.
4th, coating film treatment
The power supply of the sputtering chamber of vacuum magnetron sputtering film plating machine is opened 4A), heating makes sputtering chamber (including first to the tenth
Target chamber) in temperature reach 80-100 DEG C, absolute pressure is reduced as 2.0-4.0 × 10-3Mbar (absolute pressures in the embodiment of the present invention
Power is with 3.0 × 10-3Illustrate as a example by mbar), from first to the tenth target chamber of film glass to be plated carries out magnetron sputtering plating successively
Process；
4B) will be sequentially sent to the transfer rate of 2.5m/min through film glass to be plated obtained in 2 dehumidifying, degassing process
The first of film coating sputtering room carries out coating film treatment to the tenth target chamber, and coated glass is obtained, and technological parameter is as shown in table 1, its
In：
French green float glass sheet to be coated carries out first time coating film treatment in the first target chamber, that is, carry out the first sial
The first time plating of alloy film, is passed through nitrogen and argon in the first target chamber, the flow of nitrogen is 900sc/cm, the stream of argon
Measure as 550sc/cm, during first time plating, vacuum magnetic-control sputtering voltage is 479.0V, electric current is 76.4A, power is
29.0Kw；Absolute pressure in first target chamber is 2.0-4.0 × 10-33.0 × 10 are selected (within mbar-3mbar)；First target chamber
The metallic atom of the silicon-aluminium alloy target material sintered on target position is sputtered from the surface of target, is deposited on float glass original sheet glass
Surface, the first plated thickness of the first silico-aluminum film layer is 29.0nm, and the first filming glass is obtained；
The first filming glass carries out second plating in the second target chamber, that is, carry out the second of the first silico-aluminum film
Secondary plating, is passed through nitrogen and argon in the second target chamber, the flow of nitrogen is 900sc/cm, and the flow of argon is 550sc/
Cm, during second plating, vacuum magnetic-control sputtering voltage is 481.0V, and electric current is 76.6A, and power is 29.1Kw；Second
Absolute pressure in target chamber is 2.0-4.0 × 10-33.0 × 10 are selected (within mbar-3mbar)；Sinter on second target chamber target position
The metallic atom of silicon-aluminium alloy target material sputter from the surface of target, be deposited on the surface of the first filming glass, the first sial
Second plated thickness of alloy film layer is 29.0nm, forms the first silico-aluminum film layer that gross thickness is 58.0nm, prepared the
Two coated glasses；
Second coated glass carries out third time coating film treatment in the 3rd target chamber, that is, carry out the plating of the second nichrome film layer
Process is covered, argon in the 3rd target chamber, is passed through, the flow of argon is 1200sc/cm, magnetron sputtering voltage is 343.0V, electric current is
7.4A, power are 2.5Kw, and it is 2.0-4.0 × 10 to control the absolute pressure in the 3rd target chamber-3Mbar (selects 3.0 × 10- 3Mbar within)；The metallic atom of the nichrome target sintered on the 3rd target chamber target position is sputtered from the surface of target, deposition
On the surface of the second coated glass, the plated thickness for controlling the 3rd nichrome film layer is 7.4nm, and the 3rd coated glass is obtained；
3rd coated glass carries out the 4th silver-plated film process in the 4th target chamber, that is, carry out at the plating of the 3rd silver film
Reason, is passed through argon in the 4th target chamber, the flow of argon is 1000sc/cm, and magnetron sputtering voltage is 385.0V, and electric current is 12.7A,
Power is 4.9Kw, and it is 2.0-4.0 × 10 to control absolute pressure in the 4th target chamber-3mbar(3.0×10-3Mbar within)；4th
The atom of the silver-colored target sintered on target chamber target position is projected from the surface of target, is deposited on the surface of the 3rd coated glass, control the
The plated thickness of three silver films is 12.6nm, and the 4th coated glass is obtained；
4th coated glass carries out the 5th coating film treatment in the 5th target chamber, that is, carry out the plating of the 4th nichrome film layer
Process is covered, argon in the 5th target chamber, is passed through, the flow of argon is 1200sc/cm, magnetron sputtering voltage is 339.1V, electric current is
7.7A, power are 2.6Kw, and it is 2.0-4.0 × 10 to control the absolute pressure in the 5th target chamber-3mbar(3.0×10-3Mbar) it
It is interior；The metallic atom of the nichrome target sintered on the 5th target chamber target position is projected from the surface of target, is deposited on the 4th plated film
The surface of glass, the plated thickness for controlling the 4th nichrome film layer are 7.7nm, and the 5th coated glass is obtained.
5th coated glass carries out the 6th coating film treatment in the 6th target chamber, and nitrogen, argon, nitrogen are passed through in the 6th target chamber
The flow of gas is 900sc/cm, and the flow of argon is 550sc/cm, and voltage is 491.0V, and electric current is 68.8A, and power is
27.1Kw, it is 2.0-4.0 × 10 to control the absolute pressure in the 6th target chamber-3mbar(3.0×10-3Mbar within)；6th target chamber
The atom of the silicon-aluminium alloy target material sintered on target position is projected from the surface of target, is deposited on the surface of the 5th coated glass, and the 6th
Silicon-aluminium alloy target material magnetron sputtering film process in target chamber is the first time plating of the 5th silico-aluminum film layer, wherein controlling
The first time plated thickness for making the 5th silico-aluminum film layer is 27.0nm, and the 6th coated glass is obtained.
6th coated glass carries out the 7th coating film treatment in the 7th target chamber, and nitrogen, argon, nitrogen are passed through in the 7th target chamber
The flow of gas is 900sc/cm, and the flow of argon is 550sc/cm, and magnetron sputtering voltage is 476.0V, and electric current is 68.8A, power
For 27.2Kw, it is 2.0-4.0 × 10 to control the absolute pressure in the 7th target chamber-3mbar(3.0×10-3Mbar within)；7th target
The atom of the silicon-aluminium alloy target material sintered on the target position of room is projected from the surface of target, is deposited on the surface of the 6th coated glass, the
Silicon-aluminium alloy target material magnetron sputtering film process in seven target chambers is second plating of the 5th silico-aluminum film layer, wherein
Second plated thickness for controlling the 5th silico-aluminum film layer is 27.0nm, and the 7th coated glass is obtained；
7th coated glass carries out the 8th coating film treatment in the 8th target chamber, and nitrogen, argon, nitrogen are passed through in the 8th target chamber
The flow of gas is 850sc/cm, and the flow of argon is 440sc/cm, and magnetron sputtering voltage is 437.0V, and electric current is 75.1A, power
For 27.1Kw, it is 2.0-4.0 × 10 to control the absolute pressure in the 8th target chamber-3mbar(3.0×10-3Mbar within)；8th target
The atom of the silicon-aluminium alloy target material sintered on the target position of room is projected from the surface of target, is deposited on the surface of the 7th coated glass, the
Silicon-aluminium alloy target material magnetron sputtering film process in eight target chambers is the third time plating of the 5th silico-aluminum film layer, wherein
The third time plated thickness for controlling the 5th silico-aluminum film layer is 24.0nm, and the 8th coated glass is obtained；
8th coated glass carries out the 9th coating film treatment in the 9th target chamber, and nitrogen, argon, nitrogen are passed through in the 9th target chamber
The flow of gas is 850sc/cm, and the flow of argon is 500sc/cm, and voltage is 445.0V, and electric current is 75.0A, and power is
28.0Kw, it is 2.0-4.0 × 10 to control the absolute pressure in the 9th target chamber-3mbar(3.0×10-3Mbar within)；9th target chamber
The atom of the silicon-aluminium alloy target material sintered on target position is projected from the surface of target, is deposited on the surface of the 8th coated glass, and the 9th
Silicon-aluminium alloy target material magnetron sputtering film process in target chamber is the 4th plating of the 5th silico-aluminum film layer, wherein controlling
The 4th plated thickness for making the 5th silico-aluminum film layer is 28.0nm, and the 9th coated glass is obtained；
9th coated glass carries out the tenth coating film treatment in the tenth target chamber, and nitrogen, argon, nitrogen are passed through in the tenth target chamber
The flow of gas is 900sc/cm, and the flow of argon is 600sc/cm, and voltage is 464.0V, and electric current is 72.6A, and power is
28.0Kw, it is 2.0-4.0 × 10 to control absolute pressure when the in target chamber-3mbar(3.0×10-3Mbar within)；Tenth target chamber
The atom of the silicon-aluminium alloy target material sintered on target position is projected from the surface of target, is deposited on the surface of the 9th coated glass, and the tenth
Silicon-aluminium alloy target material magnetron sputtering film process in target chamber is the 5th plating of the 5th silico-aluminum film layer, wherein controlling
The 5th plated thickness for making the 5th silico-aluminum film layer is 28.0nm, forms the 5th silico-aluminum film that thickness is 134.0nm
Layer, obtains final product the tenth coated glass.
Wherein, the first silico-aluminum of plating film layer is caused to be formed on the surface of original sheet glass and is firmly combined with glass surface
Basal layer, and the formation place mat effect to glass colour；Plating the second nichrome film layer improves the brightness of glass colour, right
Second silico-aluminum film layer carries out magnetron sputtering plating twice and processes solving plating energy to consume big, coating film thickness uneven
Even defect, plays bottom protective effect to the 4th silver film, and the silver film deposited in nichrome film layer is that the present invention is green
The functional layer of color sunshade type coated glass, deposits the 4th nichrome film layer protection silver layer on the surface of silver film, prevents silver layer
During long-time use, cause glass colour to change because there is oxidation defect；In the table of nichrome film layer
Face depositing zinc oxide aluminium alloy film layer adjusts color, plays the bonding effect of silver layer and silico-aluminum layer, in the deep processing of product
Play a protective role in journey, while acting on the interference of light so that product is presented green.
In embodiment 1, the technological parameter of coating film treatment is as shown in table 1.
The process parameter table of 1 embodiment of table, 1 coating film treatment
5th, buffered
5th coated glass is transported in pressure buffer room from sputtering chamber, the indoor pressure of buffering and reduction is gradually stepped up
The indoor temperature of buffering, when the indoor pressure of buffering is finally reached normal pressure, and buffering indoor temperature reaches 20-35 DEG C, by the tenth plating
Film glass is discharged, warehouse-in, that is, obtain green sunshade type coated glass.
6th, make double glazing
By the monolithic of preparation green sunshade type coated glass make structure for 6- greens sunshade type coated glass (glass)+
The double glazing of 12-Air+6-glass (white glass).
Embodiment 2
1st, target sintering
It is same as Example 1.
2nd, clean glass
Except the deionized water temperature cleaned is 35 DEG C, cleaning speed is 3m/min, baking temperature for outside 45 DEG C, its
It is remaining same as Example 1；
3rd, dehumidifying, degassing process
Except the temperature of first time dehumidifying, degassing process is -135 DEG C, absolute pressure is 6.0 × 10- 2mbar；Arrange for second
The temperature of wet, degassing process is 80 DEG C, and absolute pressure is 6.0 × 10- 3Outside mbar, remaining is same as Example 1.
4th, coating film treatment
In addition to the technological parameter of coating film treatment is different from embodiment 1, remaining is same as Example 1, wherein at plated film
The technological parameter of reason is as shown in table 2.
The process parameter table of 2 embodiment of table, 2 coating film treatment
5th, buffered
It is same as Example 1.
6th, make double glazing
It is same as Example 1.
Embodiment 3
1st, target sintering
It is same as Example 1.
2nd, clean glass
It is 40 DEG C except cleaning deionized water temperature, cleaning speed is 5m/min, baking temperature is outside 55 DEG C, remaining
It is same as Example 1；
3rd, dehumidifying, degassing process
Except the temperature of first time dehumidifying, degassing process is -145 DEG C, second dehumidifying, the temperature of degassing process are 100
DEG C, absolute pressure is 3.0 × 10- 3Outside mbar, remaining is same as Example 1.
4th, coating film treatment
In addition to the technological parameter of coating film treatment is different from embodiment 1, remaining is same as Example 1, wherein at plated film
The technological parameter of reason is as shown in table 3.
The process parameter table of 3 embodiment of table, 3 coating film treatment
5th, buffered
It is same as Example 1.
6th, make double glazing
It is same as Example 1.
Reference examples 1
The French green float glass sheet of the Jing glass pretreatment described in embodiment 1-3 is made into structure for 6-glass (methods
State's green glass)+12Air+6-glass (white glass) double glazing as reference examples 1.
Reference examples 2
Using the French green float glass sheet of the Jing glass pretreatment described in embodiment 1-3 as reference examples 2.
1 color of test example, wearability, radiance test
According to GB/T2680-94《Building glass visible transmission ratio, the direct transmittance of sunlight, total solar energy transmittance,
Ultraviolet projection measure when about glass pane parameter》And GB/T18915.2-2002《Coated glass part 2：Low emissivity
Coated glass》Standard, is measured to the color parameter of embodiment 1-3 and the glass of reference examples 1-2, measurement result such as 4 institute of table
Show.
4 measured performance parameter result of table
The low-emission coated monolithic glass of green sunshade type and its double glazing prepared by the present invention, its principal visual physics are joined
Number is in L*=58～70, a*=-12～0, b*Between=- 1.5～4, its outdoor in green, it is colorful, beautiful, attractive in appearance, can be extensive
It is applied in various buildings.
2 optical property of test example is tested
According to GB/T2680-94《Building glass visible transmission ratio, the direct transmittance of sunlight, total solar energy transmittance,
Ultraviolet projection measure when about glass pane parameter》Glass obtained in embodiment 1-3 and reference examples 1-2 is carried out optical
The measure of energy, test result are as shown in table 5.
5 optical performance test result of table
The measurement result of table 5 shows：
1st, the visible light transmissivity of the double glazing that the present invention is prepared by green sunshade type coated glass is less than 36%, remote low
The double glazing prepared in the green float glass of common monolithic France and by common French green float glass, illustrates that the present invention can be effective
Control visible ray injects, it is to avoid indoor glare or excessively bright phenomenon；Outside visible ray room, reflectivity is less than 31%, higher than common list
The green float glass of piece France and its double glazing of preparation, illustrate that the coated glass of the present invention can reflect outdoor optical in a large number in outdoor
Line；And its visible ray indoor reflection ratio is higher than common monolithic France's green glass and its visible ray indoor reflection of double glazing
Than.
2nd, double glazing prepared by green sunshade type coated glass prepared by the present invention, its solar energy transmission are less than
18%, the double glazing prepared far below the green float glass of common monolithic France and by French green float glass illustrates the present invention
Green sunshade type coated glass be effectively controlled injecting for sunlight, the amount of heat that contains in reducing sunlight is entered
It is indoor；Outside its sunlight room, reflectance is more than 17%, far above the common monolithic green float glass of France and prepared therefrom hollow
Reflectance outside the sunlight room of glass, illustrates that reflecting brightness is high outside the green coated glass room of the present invention, and color is good；And the sun
Absorptivity is higher than 64%, the double glazing prepared higher than common French green float glass and by common French green float glass,
Illustrate that the green coated glass of the present invention can safeguard the ability of the light heat environment of indoor and outdoors by the regulation and control from fever of the body
It is stronger.
3rd, double glazing prepared by green sunshade type coated glass prepared by the present invention, the KShi transmitances of its ultraviolet,
ISO transmitances and transmitance, the double glazing for being substantially less than common France's green glass and being prepared by common French green glass are purple
Outside line has stronger sterilization colour fading function, and transmittance is lower, shows that the ability of the coated glass shielding of ultraviolet of the present invention is strong,
Avoid damage of the ultraviolet to indoor article.
4th, the optical property technical parameter value of green sunshade type coated glass prepared by the present invention meets GB/T18915.2-
2002《Coated glass part 2：Low radiation coated glass》Standard, it is seen that transmittance tolerance maximum is little, much
Less than the 2.0% of national standard, reach visible transmission and 0.5% is less than than tolerance maximum；Color homogeneity is high, is less than
2.0CIELAB。
Therefore, monolithic green sunshade type coated glass of the present invention and the double glazing for having its preparation are more beneficial for building bright
Comfortable indoor and outdoors luminous environment, monolithic make the using effect of double glazing more preferably using reaching good effect.
3 Thermal Performance Test of test example
The measure of thermal property is carried out to glass obtained in embodiment 1-3 and reference examples 1-2.
According to GB GB/T2680-94《Building glass visible transmission ratio, the direct transmittance of sunlight, solar energy are always saturating
Penetrate ratio, ultraviolet projection measure when about glass pane parameter》It is measured, by WINDOW6.2 window curtain wall thermal technology's property
Energy simulation softward is calculated.
Experimental condition is：Evening in winter：- 18 DEG C of outdoor temperature, 21 DEG C of indoor temperature, wind speed 5.5m/s, without sunlight；Summer
Daytime：32 DEG C of outdoor temperature, 24 DEG C of indoor temperature, wind speed 2.8m/s, solar radiation intensity are 783w/ ㎡.Measurement result such as table 6
It is shown.
6 thermal performance test result of table
The measurement result of table 6 shows：
The energy saving of the double glazing of the green sunshade type coated glass preparation that the 1st, prepared by the present invention, either summer
The energy saving in Ji Baitian or evening in winter is below the green float glass of common monolithic France and by common French green float glass process
The double glazing of glass preparation, shows that the green sunshade type coated glass of present invention preparation can reduce different transfer of heat.
2nd, double glazing prepared by present invention green sunshade type coated glass, its shading coefficient are less than 0.283；Solar energy is total
Transmittance is less than 24.6%, is substantially less than common French green float glass and the double glazing made by which, shading coefficient and
Total solar energy transmittance is all the important references factor during building energy conservation is calculated, and its value is less, stops the performance of solar radiation
It is better, therefore show that the green sunshade type coated glass and double glazing prepared therefrom of present invention preparation can effectively prevent the sun
Can get in and be converted into heat energy, so as to reduce energy consumption for cooling.
3rd, the relative thermal of double glazing prepared by present invention green sunshade type coated glass increases less than 192W/m2, it is significantly low
Increase in the relative thermal of common French green float glass and double glazing prepared therefrom, it is to consider different transfer of heat that relative thermal increases
With solar radiation to indoor impact, obtained by glass and dispersed heat sum, relative thermal increment is less, then show to pass through
The heat that glass gets in is fewer, more advantageously reduces energy consumption for cooling, the green green sunshade type coated glass of the present invention
Relative thermal increment is little, shows that the green sunshade type coated glass of present invention preparation has good energy-saving effect.
In a word, the green sunshade type coated glass that prepared by the present invention, more effectively can hinder than simple glass and its double glazing
Only heat energy gets in, and while reducing energy consumption for cooling, has reached the purpose of energy-conserving and environment-protective, and after making double glazing, effect is more
It is good.
In sum, the green sunshade type coated glass that prepared by the present invention, than test example：Not only good looking appearance, color
It is beautiful, with decorative effect；And advantageously form comfortable pleasant light thermal environment, be particularly well-suited to summer or southern temperature compared with
High city.Making double glazing has more satisfactory effect.
Claims (9)
1. a kind of green sunshade type coated glass, including the glass substrate and metallic diaphragm that overlap successively, is characterized in that：
Glass substrate (1)；
First film layer (2), positioned at the surface of glass substrate, first film layer is silico-aluminum film；
Second film layer (3), positioned at the surface of first film layer, second film layer is nichrome film；
Third membrane layer (4), positioned at the surface of second film layer, the third membrane layer is silverskin；
4th film layer (5), positioned at the surface of the third membrane layer, the 4th film layer is nichrome film；
5th film layer (6), positioned at the surface of the 4th film layer, the 5th film layer is silico-aluminum film, wherein：In glass base
One surface of piece (1) overlap successively from bottom to top the first silico-aluminum film layer (2), the second nichrome film layer (3),
Three silver films (4), the 4th nichrome film layer (5), the 5th silico-aluminum film layer (6).
2. coated glass as claimed in claim 1, is characterized in that the thickness of first film layer is 56.0-60.0nm；It is described
The thickness of the second film layer is 7.0-8.0nm；The thickness of the third membrane layer is 12.0-13.0nm；The thickness of the 4th film layer
For 7.0-8.0nm；The thickness of the 5th film layer is 130.0-142.0nm.
3. the step of a kind of preparation method of green sunshade type coated glass, including order below is carried out：
1) sinter target
Silico-aluminum, nichrome, silver are sintered on the target position of vacuum sputtering room of glass film coating machine respectively, it is standby；
2) pretreatment of glass
The glass of film process to be plated is placed under vacuum state, the glass for treating coating film treatment carries out dehumidifying, degassing process, is reduced
The moisture content and gas of glass surface deposition, is obtained dehumidifying, degassing glass；
3) coating film treatment
By dehumidifying, degassing glass send into glass film coating machine vacuum magnetic-control sputtering room in, dehumidifying, degassing glass surface under
And on successively the first silico-aluminum of plating film layer, the second nichrome film layer, the 3rd silver film, the 4th nichrome film layer,
Five silico-aluminum film layers.
4. preparation method as claimed in claim 3, is characterized in that step 3) described in the first silico-aluminum film layer plate at twice
Cover process to form.
5. preparation method as claimed in claim 4, is characterized in that the first time plating of the first silico-aluminum film layer
During vacuum magnetic-control sputtering voltage be 470.0-490.0V, electric current is 74.0-79.0A, and power is 25.0-35.0kW；Second
During secondary plating, vacuum magnetic-control sputtering voltage is 475.0-485.0V, and electric current is 73.0-78.0A, and power is 27.0-
32.0kW。
6. preparation method as claimed in claim 3, is characterized in that step 3) described in the 5th silico-aluminum film layer point 5 plating
Process is formed.
7. preparation method as claimed in claim 3, is characterized in that step 3) described in the second nichrome film layer plated film at
During reason, vacuum magnetic-control sputtering voltage is 341.0-345V, and electric current is 7.0-8A, and power is 2.0-3.0kW；3rd silver medal
During the coating film treatment of film layer, vacuum magnetic-control sputtering voltage is 380.0-390.0V, and electric current is 12.0-13.0A, and power is
4.0-5.0Kw；During the plating of the 4th nichrome film layer vacuum magnetic-control sputtering voltage be 338.0-342.0V, electric current
For 7.5-8.2A, power is 2.2-3.0kW.
8. the preparation method as described in claim 3 or 4, is characterized in that step 2) described in dehumidifying, degassing process is will be to be plated
The moisture content and gas of glass surface deposition are reduced processing stage film glass points 2, described dehumidifying, degassing glass is obtained.
9. preparation method as claimed in claim 8, is characterized in that, processing stage first during the dehumidifying, degassing process
In absolute pressure higher than the absolute pressure in the second processing stage.
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| CN101244898B (en) * | 2008-01-25 | 2011-05-11 | 东莞南玻工程玻璃有限公司 | Golden low radiation film coating glass and manufacturing method thereof |
| CN102079629A (en) * | 2010-12-09 | 2011-06-01 | 上海耀华皮尔金顿玻璃股份有限公司 | High-transmittance coated glass coated with compound dielectric layer and compound antireflection layers and production technique thereof |
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