CN102079627B - Method for processing preformed pieces before precise mold pressing - Google Patents

Method for processing preformed pieces before precise mold pressing Download PDF

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Publication number
CN102079627B
CN102079627B CN 200910246800 CN200910246800A CN102079627B CN 102079627 B CN102079627 B CN 102079627B CN 200910246800 CN200910246800 CN 200910246800 CN 200910246800 A CN200910246800 A CN 200910246800A CN 102079627 B CN102079627 B CN 102079627B
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coating
glass
sio
sol
globe lens
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CN102079627A (en
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张广军
乔斯·西默
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Schott Glass Technologies Suzhou Co Ltd
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Schott Glass Technologies Suzhou Co Ltd
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Abstract

The invention discloses a method for processing preformed pieces before precise mold pressing, which is characterized by forming a protecting layer on the surface of a preformed piece by a chemical coating method. The method not only can improve the weather resistance, acid resistance and alkali resistance of mold pressed products, but also can prevent the preformed pieces from being bonded with a precise compression mold, thus the service life of the mold is prolonged.

Description

A kind of method of processing preformed pieces before precise mold pressing
Technical field
Usually, the present invention relates to the low melting glass accurate die pressing, specifically, the present invention relates to the method at processing preformed pieces before precise mold pressing, more particularly, the present invention relates to use chemical plating method to form protective layer on the preformed member surface.
Background technology
The optical glass lens compression molding technology is a kind of high-precision optical element processing technology, it is that low-melting glass is put into high-precision mould, under the condition of pressurization and anaerobic of heating, disposable direct compression molding goes out to reach the optical component of service requirements.The accurate die pressing technology from last century the eighties succeed in developing the so far history of existing two more than ten years mid-term, become now in the world one of state-of-the-art optical element manufacturing technology.Entered the production practical stage in many countries, applying of this technology will be the great revolution of opticglass part processing.The accurate die pressing technology can direct pressing moulding precision aspheric surface optical accessory, started the New Times that opticinstrument can extensively adopt aspheric surface glass optical element, brought new change and progress also for simultaneously the Optical System Design of photoelectric instrument, not only make photoelectric instrument dwindle volume, alleviated weight, saved material, reduced the workload of optical element plated film and workpiece assembling, reduced thus cost, greatly improve the performance of opticinstrument, improved the quality of optical imagery.
For obtaining to reach the optical element of service requirements, need the mold pressing lathe of design specialized, adopt high-quality mould and select rational processing parameter, forming method wherein, glass types and preformed member blank, moulding stock and Mold Making all are the gordian techniquies in the compression molding.In mold process, press temperature is higher, and than high about 20～60 ℃ of the transition temperature of glass precursor, pressure is also larger simultaneously.Mould produces easily burr and surface damage under high temperature and high pressure, and also can the mold damage surface from the Volatile chemical of glass preformed member, makes easily oxidized and corrosion of mould, thereby greatly reduced die life.Because mould therefor requires high, difficulty of processing is large, and cost is high, and therefore, it is most important to the cost of control product to prolong the mold use life-span.
In order to prolong the mold use life-span, should reduce as far as possible molding temperature.But, can only be low to moderate certain a bit, under this temperature, the viscosity of glass to be pressed still is enough to be suitable for described mould pressing process.Thereby, many opticglass supplier developments have the glass of low point of inversion Tg.
The another kind of method that prolongs die life is to improve mould pressing process or moulding stock, for example, operates molding apparatus under nitrogen atmosphere, prevents the oxidation of mould; Use ion plating or sputtering method to plate the coatings such as TiAlN, Pt base alloy, diamond-like carbon at die surface, such as disclosed method among the EP0191618A1, but the method cost is higher.
In addition, Japanese HOYA company adopts the physically splash plating method at preformed member plated surface SiO 2Film reduces volatile matter to the infringement of mould, to improve the mold use life-span, such as disclosed method among the clear 62-202824 of open special permission communique.Yet the technique of physical method plated film is complicated, and cost is higher, and the homogeneity of film and second-rate, so effect is not very remarkable.Particularly, the product of current accurate die pressing, such as mobile phone, camera lens and lens etc. can be exposed in the air mostly for a long time, more requires product to have better acidproof, alkaline-resisting and weathering resistance.
Therefore, still need in this area a kind ofly can prolong die life, can improve again the new mould pressing method of acidproof, the alkaline-resisting and weathering resistance of product.
Summary of the invention
The present inventor is through long-term exploratory experiment; finally found a kind of method that adopts chemical plating method to form protective layer on glass preformed member surface; thereby can realize both having prolonged die life by the method, can improve again the purpose of acidproof, the alkaline-resisting and weathering resistance of product.
The invention discloses a kind of method at accurate die pressing pre-treatment glass preformed member, it is characterized in that using chemical plating method to form protective layer on glass preformed member surface.
According to method of the present invention, wherein said preformed member comprises that accurate die pressing drips moulding mixture, globe lens, bar, piece material or sheet material.
According to method of the present invention, wherein said preformed member is made by silicate glass, sulfate-phosphate glass, phosphate glass, borosilicate glass, fluorphosphate glass, lanthanide glass or other glass that is used for accurate die pressing.
According to method of the present invention, wherein said chemical process comprises sol-gel method (Sol-Ge1) and chemical vapour deposition (CVD), preferred sols-gel method.
According to method of the present invention, wherein said coating comprises SiO 2, Al 2O 3, ZrO 2, TiO 2, SnO 2And WO 3Preferred SiO 2And Al 2O 3Film.
The method of accurate die pressing pre-treatment glass preformed member of the present invention, both utilized glass premolding top coat to prevent that volatile element such as Li, Na, K, F, P are to the destruction of die surface, improve the mold use life-span, can also utilize the good physical and chemical performance of coating itself, improve weathering resistance, acid resistance and the alkali resistance of molded product.Compare with existing physical coating method, chemical process is relatively simple, cost homogeneity and quality lower, film is all better, and be better than physical method plated film to weathering resistance, acid resistance and the alkali-proof improved effect of product.
Description of drawings
Fig. 1 SiO 2Coating is on the acid proof impact of phosphate glass globe lens: (a) without SiO 2Coating; (b) magnetron sputtering plating SiO 2Coating; (c) Sol-gel method plating SiO 2Coating.
Fig. 2 SiO 2Coating is on the alkali-proof impact of phosphate glass globe lens: (a) without SiO 2Coating; (b) magnetron sputtering plating SiO 2Coating; (c) Sol-gel method plating SiO 2Coating.
Fig. 3 SiO 2Coating is on the impact of phosphate glass globe lens weathering resistance: (a) without SiO 2Coating; (b) magnetron sputtering plating SiO 2Coating; (c) Sol-gel method plating SiO 2Coating.
Fig. 4 Sol-gel method Al 2O 3The impact of coating thiophos silicate glass globe lens weathering resistance: (a) without Al 2O 3Layer; (b) Al is arranged 2O 3Coating.
Fig. 5 Sol-gel method Al 2O 3Coating is on the impact of silicate glass globe lens weathering resistance: (a) without Al 2O 3Coating; (b) Al is arranged 2O 3Coating.
Fig. 6 CVD method SiO 2The alkali-proof impact of coating thiophos silicate glass globe lens: (a) without SiO 2Coating; (b) SiO is arranged 2Coating.
Embodiment
Embodiment 1
Magnetron sputtering and Sol-gel method plating SiO 2Film is on the impact of phosphate glass globe lens acid resistance, alkali resistance and weathering resistance
Select phosphate glass (P-PK53, the SCHOTT) globe lens of diameter 4.00mm, adopt respectively magnetron sputtering and Sol-gel method at its plated surface SiO 2Film.Magnetron sputtering SiO 2Film carries out at TXZ500-2 type rf magnetron sputtering coating equipment, and target adopts the silicon single crystal of (111) direction, and sputtering atmosphere is that purity is 99.9% argon gas, and reactivity gas is 99.9% oxygen, and the distance of target and globe lens is 60mm.The phosphate glass globe lens respectively cleans 20min with deionized water, acetone and alcohol first in Ultrasonic Cleaners, put into immediately coating chamber after the oven dry.Coating chamber is evacuated to 1.0 * 10 -3Pa, sputtering pressure are 1.2Pa.With the pre-sputtering target material of argon gas surface 20 minutes, then oxide compound and other impurity to remove the surface passed into oxygen, after aura is stable, open baffle plate, rotate the substrate rotating disk, Place lens sputter coating in aura first.The ratio of oxygen and argon gas is controlled with mass flowmeter in the sputter procedure, and the ratio of flow is the ratio of two partial pressures in the sputter procedure.
Adopt the sol-gel method at identical phosphate glass globe lens plated surface SiO 2Coating, concrete steps are as follows:
(1) with tetraethoxy and ethanol (available from Sigma-Aldrich, below if no special instructions, the pharmaceutical chemicals of all uses is all from Sigma-Aldrich) mix in container by 1: 16 mass ratio, the hydrochloric acid soln that dropwise adds 0.1mol/L after fully stirring, the pH value to 1 of regulator solution～2 make SiO 2Colloidal sol is for subsequent use;
(2) the phosphate glass globe lens is placed on the commercially available common filter paper, then with SiO 2Colloidal sol evenly is poured on the globe lens and passes through filter paper;
(3) with Teflon film (Dupont, USA) globe lens and filter paper are separated, globe lens was placed air drying 2 hours at the Teflon film; With
(4) after the sample surface coating drying, globe lens transferred in the quartz crucible anneal.Annealing conditions is 300 ℃ of lower insulations 1 hour.
To there be SiO 2Coating (No.1), magnetron sputtering (No.2) and Sol-gel method (No.3) are coated with SiO 2The phosphate glass globe lens of coating is in protruding spherical mould (body material is stainless steel, and core rod is the wolfram varbide of mirror finish), at identical mold pressing parameter (2%H 2+ 98%N 2Atmosphere in, 430 ℃ of molding temperatures, pressure 250kg/cm 2, 40 seconds clamping times) under be molded into finished product, then carry out the test of acid resistance, alkali resistance and weathering resistance.
Test condition is respectively as follows: under the room temperature sample being placed pH value is that 4.6 acetum corrodes 100 minutes (acid resistance); Place 0.01mol/L NaOH solution to corrode 15 minutes (alkali resistance) in sample under the room temperature; Sample at temperature 70 C, is placed 25 hours (weathering resistance) under the condition of humidity 95%.
Fig. 1 is the surperficial Photomicrograph of observing under opticmicroscope after No.1, No.2 and the test of No.3 sample acid resistance.From Fig. 1 (a), can find out there is not SiO 2The phosphate glass globe lens sample surfaces of coating has obvious corrosion pit; And be coated with SiO 2The corrosion pit of the sample surfaces of coating obviously reduces and diminishes, such as Fig. 1 (b) and (c), and find and sample (c) than the corrosion pit of sample (b) sample surfaces still less.The result shows, SiO 2Coating can obviously be improved the acid resistance of phosphate glass globe lens, and Sol-gel method plating SiO 2Coating is improved the acid proof effect of sample and significantly is better than magnetron sputtering method.
Fig. 2 is the surperficial Photomicrograph of observing under opticmicroscope after No.1, No.2 and the test of No.3 sample alkali resistance.From Fig. 2 (a), can find out there is not SiO 2The phosphate glass globe lens sample surfaces of coating has significantly deeply and clearly long corrosion pit; And magnetron sputtering is coated with SiO 2The corrosion striped of the sample surfaces of coating obviously shoals, shown in Fig. 2 (b); Sol-gel method plating SiO 2The sample surfaces of coating does not observe obvious corrosion striped basically, shown in Fig. 2 (c).The result shows, SiO 2Coating can obviously be improved the alkali resistance of phosphate glass globe lens, and Sol-gel method plating SiO 2Coating is improved the alkali-proof effect of sample and is better than magnetron sputtering method.
Fig. 3 is the surperficial Photomicrograph of observing under opticmicroscope after No.1, No.2 and the test of No.3 sample weathering resistance.From Fig. 3 (a), can find out there is not SiO 2The phosphate glass globe lens sample surfaces of coating demonstrates obvious vaporific mildew; And be coated with SiO 2The vaporific mildew of the sample surfaces of coating greatly reduces, and such as Fig. 3 (b) with (c), and Fig. 3 sample (c) than the surperficial vaporific mildew of sample (b) still less.The result shows, SiO 2Coating can obviously be improved the weathering resistance of phosphate glass globe lens, and Sol-gel method plating SiO 2The effect that coating is improved the sample weathering resistance significantly is better than magnetron sputtering method.
In sum, SiO on phosphate glass globe lens plated surface 2Coating can obviously be improved acid resistance, alkali resistance and the weathering resistance, particularly chemical method (Sol-gel method) of molded product and plate SiO 2The effect of improving of coating significantly is better than Physical (magnetron sputtering).
Embodiment 2
Al 2O 3The impact of coating thiophos silicate glass globe lens weathering resistance
Select the sulfate-phosphate glass (P of diameter 4.00mm 2O 5-SO 3-ZnO) globe lens adopts the Sol-gel method at its plated surface Al 2O 3Coating.Concrete steps are as follows:
(1) selecting aluminum isopropylate (Shenyang chemical reagents corporation) is presoma.200ml distilled water is heated to 50 ℃, slowly adds while stirring levigate 20g aluminum isopropylate behind the constant temperature, add rear return stirring 2.5h, form precipitation.Then be warming up to 80 ℃, add a certain amount of peptizing agent (salpeter solution of 0.1mol/L), precipitation is disperseed again, wore out 30 minutes at 80 ℃ of lower return stirrings at last, make the Al of stable transparent 2O 3Colloidal sol is for subsequent use.
(2) the sulfate-phosphate glass sphere lens is placed on the commercially available common filter paper, then with Al 2O 3Colloidal sol evenly be poured on the globe lens and pass through filter paper.
(3) with the Teflon film globe lens and filter paper are separated, globe lens was placed air drying 2 hours at the Teflon film.
(4) after the sample surface coating drying, globe lens transferred in the quartz crucible anneal.Annealing conditions is 360 ℃ of lower insulations 3 hours.
To be coated with Al 2O 3Coating and do not have Al 2O 3The sulfate-phosphate glass sphere lens of coating (2%H under identical mold pressing parameter 2+ 98%N 2Atmosphere in, 450 ℃ of molding temperatures, pressure 200kg/cm 2, 30 seconds clamping times) and be molded into finished product, and carry out the weathering resistance test, testing method is with embodiment 1.
Fig. 4 is the surperficial Photomicrograph that the sulfate-phosphate glass sample is observed under opticmicroscope after the weathering resistance test.From Fig. 4 (a), can find out there is not Al 2O 3The sulfate-phosphate glass sphere lens sample surfaces of coating demonstrates obvious vaporific mildew; And be coated with Al 2O 3The sample surfaces of coating does not almost observe vaporific mildew, shown in Fig. 1 (b).The result shows, Al 2O 3Coating can obviously be improved the weathering resistance of sulfate-phosphate glass sphere lens.
Embodiment 3
Al 2O 3Coating is on the impact of silicate glass globe lens weathering resistance
Select silicate glass (P-SK57, the SCHOTT) globe lens of diameter 4.00mm, adopt equally the Sol-gel method at its plated surface Al 2O 3Coating, concrete steps such as embodiment 2.To be coated with Al 2O 3Coating and do not have Al 2O 3The silicate glass globe lens of coating is at identical mold pressing parameter (2%H 2+ 98%N 2Atmosphere in, 540 ℃ of molding temperatures, pressure 250kg/cm 2, 30 seconds clamping times) under be molded into finished product, and carry out weathering resistance test, testing method is with embodiment 1.
Fig. 5 is the surperficial Photomicrograph that the silicate glass sample is observed under opticmicroscope after the weathering resistance test.From Fig. 5 (a), can find out there is not Al 2O 3The silicate glass globe lens sample surfaces of coating demonstrates the vaporific mildew of obvious bulk; And be coated with Al 2O 3The vaporific mildew of the sample surfaces of coating obviously alleviates, such as Fig. 5 (b).Presentation of results, Al 2O 3Coating can significantly be improved the weathering resistance of silicate glass globe lens.
Embodiment 4
CVD method plating SiO 2The alkali-proof impact of coating thiophos silicate glass globe lens
Select the sulfate-phosphate glass sphere lens of diameter 4.00mm, adopt the atmospheric pressure cvd method at its plated surface SiO 2Coating.Concrete technology is as follows: adopting tetraethoxy (TEOS) is the silicon source, and nitrogen is as carrier gas.To be placed on the heating base of reaction chamber through the clean sulfate-phosphate glass sphere lens of ultrasonic cleaning, reaction chamber is evacuated to 400Pa, and sample is heated to 550 ℃, passes into 60 ℃ N 2Make the TEOS steam of carrier gas, reaction chamber wall and all the time water flowing of electrode interlayer cooling, depositing time is 30 minutes.
To there be SiO 2Coating and CVD method are coated with SiO 2The sulfate-phosphate glass sphere lens of coating is at identical mold pressing parameter (2%H 2+ 98%N 2Atmosphere in, 450 ℃ of molding temperatures, pressure 200kg/cm 2, 30 seconds clamping times) under be molded into finished product, and carry out alkali resistance test, test condition is with embodiment 1.
Fig. 6 is CVD method SiO 2The alkaline-resisting sex test result of coating thiophos silicate glass globe lens.From Fig. 6 (a), can find out there is not SiO 2The sulfate-phosphate glass sphere lens sample surfaces of coating has obvious corrosion pit; And the CVD method is coated with SiO 2The corrosion pit of the sample surfaces of coating obviously tails off, shown in Fig. 6 (b).
Embodiment 5
Al 2O 3Coating is on the impact of die life
Sol-gel method among the embodiment 2 is coated with Al 2O 3The sulphur phosphorus glass globe lens of coating carries out molded test, and the die matrix material is stainless steel, and core rod is the wolfram varbide of mirror finish, and mold pressing parameter is with embodiment 2.Found that, do not plate Al 2O 3Before the coating, on average through 1800～2000 times sulphur phosphorus glass globe lens mold pressing operation, mould need to be reprocessed once; And plating Al 2O 3After the coating, on average through 2200～2500 times sulphur phosphorus glass globe lens mold pressing operation, mould just need to be reprocessed once, and efficient improves about 25%.The result shows, Al 2O 3Coating helps to improve accurate die pressing and uses the mold use life-span.

Claims (6)

1. method at accurate die pressing pre-treatment glass preformed member; it is characterized in that using chemical plating method to form protective layer on glass preformed member surface; wherein said chemical plating method comprises sol-gel method and chemical vapour deposition, and described coating comprises SiO 2, Al 2O 3, ZrO 2, TiO 2, SnO 2And WO 3
2. the method for claim 1, wherein said glass preformed member comprises that accurate die pressing drips moulding mixture, globe lens, bar, piece material or sheet material.
3. method as claimed in claim 1 or 2, wherein said glass preformed member is made by silicate glass, sulfate-phosphate glass, phosphate glass, borosilicate glass, fluorphosphate glass, lanthanide glass or other glass that is used for accurate die pressing.
4. the method for claim 1, wherein said chemical plating method is sol-gel method.
5. the method for claim 1, wherein said coating is SiO 2Or Al 2O 3Coating.
6. method as claimed in claim 1 or 2 wherein uses sol-gel method to form SiO on glass preformed member surface 2Or Al 2O 3Coating.
CN 200910246800 2009-12-01 2009-12-01 Method for processing preformed pieces before precise mold pressing Expired - Fee Related CN102079627B (en)

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