A kind of On-line Measuring Method of self clean glass contact angle
[technical field]
The present invention relates to a kind of measuring method of self clean glass contact angle, be specially adapted to the on-line measurement of self clean glass contact angle.
[background technology]
In surface chemistry, the wetting and final process of sprawling is a most important content by liquid on the surface.To 20 th century later, development along with quantum electrodynamics and explication de texte process, for surface chemistry provides a large amount of analysis means, found between the different interfaces and micro details that interface contact angle is presented on along the line, movement mechanism when further having understood liquid process surface, thereby make in wetting and the research process sprawled, contact angle is carried out detailed research become possibility.
On solid surface, along with the difference of system character, liquid covers solid surface because of sprawling with fluid drips, or forms a drop and stop thereon.We describe the shape of liquid and the formed drop of surface with contact angle (contact angle).Contact angle is at solid, liquid, gas three-phase intersection accurately,, represents with θ usually through the angle of liquid internal to gas interface from solid-liquid interface.Contact angle is very important physicochemical property analyzing wetting state.
The Young's equation that concerns between equilibrium contact angle and three interfacial free energies also is called wetting equation, can be regarded as the result of three interfacial tension balances of three-phase intersection.This relation is applicable to three-phase intersection solid-liquid, solid gas interface tangent line system altogether.Usually our phenomenon that can launch liquid on solid surface calls wetting.Liquid is to the size of the wetting action of solid, the size of contact angle θ is represented to see also illustrated in figures 1 and 2 between available solid-liquid, Fig. 1 is the principle schematic of the contact angle θ of the nonwetting solid of liquid, and Fig. 2 is the principle schematic of the contact angle θ of the wetting solid of liquid energy, wherein: γ
G-sBe the surface tension between gas phase and solid phase; γ
1-sBe the surface tension between liquid phase and solid phase; γ
G-1Be the surface tension between gas phase and the liquid phase.
During balance, γ
G-s=γ
1-s+ γ
G-1Cos θ, this relational expression is the Young's equation of presentation surface tension force and contact angle relation.(1) as shown in Figure 1, if γ
G-s<γ
1-s, cos θ<0 then, θ〉and 90 °, the nonwetting solid of liquid.When θ=180 °.Then for nonwetting fully; (2) as shown in Figure 2, if γ
G-sγ
1-s, cos θ then〉and 0, θ<90 °,, liquid can wetting solid; (3) if γ
G-s-γ
1-s=γ
G-1, cos θ=1 then, θ=0 °, complete wetting, and reached the limit of balance.
Allly can be called solid hydrophilic, or not be called hydrophobic solid by the solid of water-wet by the solid of water-wet.Work as γ
G-s-γ
L-s-γ
G-1〉=0 o'clock, this moment, three kinds of power out of trim did not promptly still reach balance when making θ=0 °, and this moment, Young's equation can not be suitable for, and liquid is layered on solid surface fully, and this a kind of phenomenon is called to be sprawled, and the condition of sprawling is φ=γ
G-s-γ
1-s-γ
G-10.
In concrete the application, we are the important indicator of contact angle size as the judge wetting state.Usually contact angle is more little, and wetting state is also just good more.Traditionally, we ° are defined as whether wetting standard to θ=90.We are θ〉90 ° be nonwetting; θ<90 ° are wetting.Equilibrium contact angle does not exist or is 0, then for sprawling.And different liquids is also inequality at the contact angle of same solid surface; When liquid was deionized water, we claimed that contact angle is hydrophilic angle.
Glass surface belongs to high energy surface, and at 42 °-48 °, but treated glass surface plates the material that one deck contains metal oxide as at present more common at glass surface, and its surface free energy is reduced for the scope of the contact angle of deionized water.When the glass surface rete is glass with clean to the contact angle of water during at 20 °~5 °, be super hydrophilic glass during less than 5 °.For convenience, we generally measure the hydrophilic angle of glass with clean with deionized water, can certainly use different liquids/solvent to measure the contact angle of glass with clean.
In research to glass with clean and super hydrophilic glass, wherein a lot of to the research of production method, to the Measurement Study of the contact angle of glass with clean and super hydrophilic glass also seldom, and existing detection method the early stage of the control of the humidity of test environment, temperature, cleanliness factor, print handle and test detail on still have and need improved place, to improve precision of test result.
China's patent application 200410061082.7 discloses a kind of titanium dioxide film self-cleaning glass photo-induced super-hydrophilicity method of inspection, be the method that adopts sessile drops, by the contact angle instrument measure water droplet drop in through cleans, dry, leave standstill, the contact angle of the glass print surface formation of photo-irradiation treatment.Do not mention in the literary composition and calculate used mathematical model, and oven dry is essential step, so consumed time is longer, the method that adopts sessile drops in addition also has certain influence to the degree of accuracy of measurement result, and the scope of its relative error is bigger.
The present invention sets about from the various aspects that may influence the contact angle test result, makes the test result accuracy higher, can measure the contact angle of smaller angle, and error can be below 1 °; And can effectively shorten detection time, can on-line measurement.
[summary of the invention]
Primary technical matters to be solved by this invention provides a kind of method of on-line measurement of self clean glass contact angle, consuming time less, the precision height, be specially adapted to on-line measurement, it may further comprise the steps:
A. sampling: will promptly flow to the vertical direction of direction with glass plate along horizontal direction and equidistantly take a sample except that former of the float glass after the trimming portion, quantity of sampling quantity is decided on former width of float glass;
B. handle the early stage of print: promptly number, clean, cool off, described cleaning step adopts absorbent cotton or cotton gauze to be stained with tap water and cleans print, washes with test solution again;
C. illumination: print is the ultra violet lamp 1 hour of 365nm with 500W ± 50W, centre wavelength, to activate the rete material;
D. cooling;
E. connect and adjust the contact angle test macro: adjust the end platform of tester and sample stage to the horizontal line position, adjust the focal length and the brightness of optical system, adjust the sample stage height then, the sample separatrix is overlapped with the separatrix of computer testing system;
F. adjust humidity and temperature: at whole test period, guarantee that surrounding relative humidity is 50% ± 5%, range of humidity variation ± 2%, temperature is 23 ± 1 ℃;
G. measure and calculate: add quantitative test solution in the injector, adopt sessile drop method that drop is dropped in the print upper surface, choose 4 different position measurements at the print upper surface, computing system through computing machine carries out the calculating of contact angle, gets the measured value of the mean value of 4 measurement results as this print contact angle.
Wherein, the sampling gained print described in the step a is a square, and its size is 150mm * 150mm or 100mm * 100mm or 50mm * 50mm.
Wherein, the illumination described in the step c is to carry out in controllable temperature drying baker or lighting box.
Wherein, the cooling described in the steps d is meant that print is cooled to room temperature in dustless cooling tank.
Wherein, the tester described in the step e is a SL series contact angle tester.
Wherein, the calculating described in the step g is to select for use the mathematical model of θ/2 methods to carry out.
Wherein, selected test position is meant that the vertical range to four edges is 4 points of the symmetry of 30-100mm at the center of described print in the step g.
Wherein, what adopt in the step g is the sessile drop method that drop poises the upper surface that is parked in solid of dripping from top to bottom, and the volume of test droplets is 2 μ l.
Wherein, when measuring hydrophilic angle, the test solution described in the step g is a deionized water; When measuring the contact angle of glass with clean, the test solution described in the step g is other liquid except that deionized water, and described liquid comprises ethanol, propyl alcohol, acetone, benzene, toluene, phenmethylol, n-decane, methylene chloride, ethyl acetate.
Wherein, the injector described in the step g is auto injection or two kinds of forms of hand sampling
Wherein, the contact angle tester described in the step e is meant SL series contact angle tester.
Compared with prior art, the present invention has the following advantages:
(1) the present invention adopts at horizontal direction and gathers print, than the homogeneity that is easier to verify on-line coating.
(2) the used instrument of the present invention is a SL series contact angle tester, this instrument is aspect the correction of horizontal line position, proofread and correct except adopting level meter, also adopt high-precision lifting table, control print platform horizontal line is consistent with the software level line, has promoted horizontal recognition capability with hardware mode.
(3) measuring system of the present invention mainly is by the image system images acquired, draws the test result of contact angle after selection θ/2 method mathematical models through mathematical computations by computer software.Its principle is simpler, and more easy to operate, and the error of calculation is littler.
(4) oven dry of the present invention, illumination step are finished simultaneously: prior art has adopted the step of oven for drying, and oven dry and illumination are separate operation; The present invention is in the controllable temperature lighting box, and oven dry is finished with the illumination process, and baking step has been saved the time, improved accuracy simultaneously.
(5) the present invention the early stage of the control of the humidity of test environment, temperature, cleanliness factor, print handle and test detail on done certain improvement, adopted sessile drop method, not only improved measuring accuracy, the on-line measurement when also being specially adapted to the online production glass with clean.
(6) the present invention can be less than or equal to 3 ° rete for contact angle, as the super-hydrophilic self-cleaning glass rete, measures more exactly.
[description of drawings]
The present invention is further illustrated in conjunction with the embodiments with reference to the accompanying drawings.
Fig. 1 is the principle schematic of the contact angle θ of the nonwetting solid of liquid.
Fig. 2 is the principle schematic of the contact angle θ of the wetting solid of liquid energy.
Fig. 3 is the position of implementing first group of selected test point of print in.
Fig. 4 is θ in the mathematical model/2 ratio juris figure.
[embodiment]
Embodiment one: the on-line measurement when being used for the online production glass with clean:
Below be the same batch of test result of producing print that application the present invention and other existing method record:
Get the print of three groups of 100mm * 100mm on former of the same float glass of production line altogether, every group of quantity is identical, does the contrast experiment.
1) first group, adopts the inventive method test;
Relative humidity between test is 50% ± 5%, range of humidity variation ± 2%, and temperature is 23 ± 1 ℃.Method of testing adopts sessile drop method, and computing method adopt θ/2 methods.This group adopts SL series contact angle tester to measure, and it is the CAST software systems that described SL series contact angle tester adopts analytic system, and these software systems are installed in the computing machine, then the contact angle tester is connected with computing machine.
A numbers above-mentioned print, is stained with tap water with absorbent cotton and cleans repeatedly to there not being visible dirt, uses deionized water rinsing 3-5 minute again, is the ultra violet lamp 1 hour of 365nm with 500W, centre wavelength in the controllable temperature lighting box.It is standby to move in the dustless cooling tank cooling.
End platform level and sample stage that B adjusts tester arrive the horizontal line position, adjust the focal length and the brightness of optical system, are to adjust the sample stage height then, and the sample separatrix is overlapped with separatrix in the computer testing system.
C injects 20 μ l deionized waters in automatic sampler, as shown in Figure 3, the vertical range at 100mm * 100mm print center 1 to four edges 2 is the 50mm place, gets respectively at 4 and tests as test point 3, and each sample size is 2 μ l.
D writes down each measurement result, calculates with θ/2 methods, depends on that 4 mean values are as final testing result.θ/its principle of 2 methods as shown in Figure 4, L1 is a tangent line 1, L2 is a tangent line 2, L3 is liquid, the upper thread of demarcating admittedly, h is the height of drop at the formed spherical crown of solid surface drawout, r is the diameter of drop, then
θ=2×θ1
Tan?θ1=h/r
θ=2×tan
(-1)(h/r)
The CAST software systems that are installed in the computing machine can be measured the value (its numerical value is not concrete to be shown) of h and r automatically, and by calculating the value of θ automatically, see Table 1, twice test result of every group record.
E repeats B-D, tests other print.
2) second group, use the prior art test:
Temperature is controlled at 25 ℃, and relative temperature is controlled at 65%.Adopt the sessile drops method.
A numbers above-mentioned print, after deionized water and absolute ethyl alcohol flushing, cleans with absorbent cotton again, use deionized water rinsing 3-5 minute again, and, left standstill 2 hours after 30 minutes in the baking of 100 ℃ of baking ovens, be the ultra violet lamp 1 hour of 365nm again with 18W, centre wavelength.
Sample level after B will leave standstill places on the specimen mounting of seal box in the reactor, and adjusting uviol lamp is 10cm with the distance of trying magnetic, closes also all doors, the hole of sealed reactor, and covers reactor with the black flannelette, opens uviol lamp, irradiation sample 90 minutes.
C with the contact angle instrument be connected with computing machine again after reactor is connected, open contact angle instrument power supply then.To lay through the sample after the UV-irradiation and be positioned on the contact angle instrument platform, and be degree sample numbering.
D uses microsyringe at 4 diverse location instillation of specimen surface water droplet, adopt the contact angle instrument to measure the contact angle of the water of above-mentioned 4 diverse locations of specimen surface respectively, show and write down each measurement result by computing machine, get 4 mean values as final testing result.
E repeats B-D, tests other print, and test result sees Table 1.
3) the 3rd group, the test of simulation glass with clean actual operating conditions:
This group experimental procedure is compared with first group, only changes the illumination mode into daylight, and light application time changes 50 hours into, and other operation is constant.
Table 1
From test result as can be seen: first group the most approaching with the 3rd group of measured result, the hydrophilic angle of glass with clean under actual service conditions more approached at the hydrophilic angle that is method of testing gained of the present invention, then deviation is bigger at second group of hydrophilic angle that records, wherein to experimental result influence bigger be the cleaning and the drying course of sample, and this process also is the longest process consuming time, therefore makes this type of method of testing not have practical significance in online production.
Embodiment two: utilize the test of method of the present invention to the contact angle of super-hydrophilic self-cleaning glass.
The contact angle of super-hydrophilic self-cleaning glass is very little, also cries hydrophilic angle, is generally less than or equals 3 °, and general contact angle tester is worked as the contact angle of being surveyed when being less than or equal to 3 °, uses the general test method to be difficult to accurately measure; And measuring method of the present invention is also relatively more accurate to the measurement result of this situation, and error is below 1 °.Below be the application of the present invention in the hydrophilic angular measurement examination of test super-hydrophilic self-cleaning glass:
In the test at the hydrophilic angle of super hydrophilic membrane, in operation, need not to do any adjustment, measurement result sees Table 2, twice measurement result of table 2 record.
Table 2
From test result as can be seen: very near 3 °, therefore more accurate with the measured result of method of the present invention, provable method of the present invention also is applicable to the hydrophilic angle of test super-hydrophilic self-cleaning glass.