Specification
TECHNICAL FIELD
The present invention is in relation to the field of spectroscopy, in particular Cavity Ring Down Spectroscopy (CRDS). CRDS has been explored for its utility as a tool for measuring permeability of materials in conjugation with a test chamber. Accordingly, the utility of the CRDS in conjugation with a test chamber has been ascertained in the measurement of permeability of materials which is <10"6 g/m2/day. The measurement of low values of permeability of materials is of great significance in the electronic industry, pharmaceutical industry and food industry.
The current method is simple with uncomplicated methodology and economical for adoption into the industries where measuring the permeability of barrier materials is required.
BACKGROUND
In the current world, the use of organic electronic devices has been ubiquitous. Usage of organic electronics can be found in various devices like transistors, solar cells, photovoltaic devices and the like. Organic electronic devices are sensitive to moisture and oxygen in its surrounding atmosphere and the repercussion is its degradation at a faster rate resulting in short life span. To overcome the said handicap, such devices are encapsulated by materials which act as barriers and insulate them from the surrounding atmosphere, thus imparting longevity to the organic electronic devices.
Also, barrier materials are required for encapsulating certain medicines and food products to increase their shelf life by avoiding degradation due to moisture and oxidation.
The challenge currently faced in this regard is development and identification of the right materials for encapsulation. The material used for encapsulation has to be an ultra low permeable material for the detrimental gases like water vapor, oxygen to protect the organic electronic devices, medicinal and food products from degradation. The proposed mechanisms till date differ with the nature of the detrimental gas as well as the extent to which it needs to be impermeable through the encapsulant. According to P. E. Burrows et al, Proc. SPIE 75, 4105, (2001), a water vapor transmission rate (WVTR) value of 1 x 10"6 g/m2/day and oxygen transmission rate (OTR) 1 x 10"3 cm3/m2/day has become the informal standard for the organic light emitting diodes (OLEDs) to obtain a device lifetime of greater than 10,000 hours. This value has been estimated by calculating the amount of oxygen and water needed to degrade the reactive cathode.
Apart from the development of such barrier materials, an important field of interest remains in the development a technique to measure the permeability of such materials. Current focus in said field is to develop a technique easy to use, scalable, provide highly sensitive reproducible results and flexible for adopting to analyze various detrimental gases.
Currently, evaluation of the encapsulant material is carried out either by evaluating the device under test (DUT) or by evaluating the permeation of the material. Most of the research is carried out by evaluating the performance of the DUT after encapsulation. However, it is important to study the performance of the encapsulant material directly instead of trying to understand its contribution to the shelf life of the device. The shelf life of a device can be dependent on various parameters including the encapsulant material.
The direct evaluation of the encapsulant is carried out by techniques as discussed below
a) Differential pressure method (MOCON)
o Equal pressure method employing infrared sensor (ASTM F1249) o Equal pressure method employing coulometric sensor
b) Calcium (degradation) test
c) Gravimetric method
d) Spectroscopic method
Differential pressure method
In the differential-pressure method, a higher-pressure chamber and a low-pressure chamber both containing pressure gauge are separated by the sample. The high-pressure chamber is filled with test gas of about 0.1 MPa and the low-pressure chamber has a known inner volume The low chamber is vaccumised to about zero after the sealing and then the pressure increment of the low-pressure chamber with a pressure gauge is measured. In this way, the gas permeance as a function of time, from high-pressure chambers to low-pressure chambers, is determined.
Equal pressure method employing infrared sensor
This method was a standard measurement process for a long time in barrier film industries. A dry chamber is separated from a wet chamber of known temperature and humidity by the
barrier material to be tested. The dry chamber and the wet chamber make up a diffusion cell in which the test film is sealed. Water vapor diffusing through the film mixes with the gas in the dry chamber and is carried to a pressure modulated infrared sensor. This sensor measures the fraction of infrared energy absorbed by the water vapor and produces an electrical signal, the amplitude of which is proportional to water vapor concentration. The amplitude of the electrical signal produced by the test film is then compared to the signal produced by measurement of a calibration film of known water vapor transmission rate. This information is then used to calculate the rate at which moisture is transmitted through the material being tested.
The test specimen is held such that it separates two sides of a test chamber. The "wet side" of the specimen is exposed to a high relative humidity atmosphere, while the "dry side" is subjected to a zero relative humidity atmosphere. Infrared sensors on the "dry side" detect the amount of water vapor present. Testing is complete when the concentration of water vapor in the dry side atmosphere is constant.
Equal pressure method employing coulometric sensor
Coulometry is a method for measuring an unknown concentration of an analyte by completely converting the analyte from one oxidation state to another.Coulometry is an absolute measurement similar to gravimetry or titration and requires no chemical standards or calibration. It is therefore valuable for making absolute concentration determinations. Using the same protocol as ASTM 1249 but using an absolute coulometric sensor instead of the concentration-based pulse modulated infrared sensor. The sensitivity was about 5 x 10 g/m2/day.
The MOCON WVTR measurement device, which has been an industry standard, cannot give adequate measurements at the low levels of permeability required for organic photovoltaics and OLEDs.
Calcium Degradation Test
This technique is based on degradation of calcium. A thin calcium layer of defined volume is deposited on a glass substrate in an inert atmosphere and the barrier material of interest is used to encapsulate this metallic sensor. By exposing such a test cell to a defined relative
humidity and temperature the water vapor passing the barrier film oxidizes the metallic and opaque calcium to translucent CaO and Ca(OH)2, respectively. The time-dependent change in optical transmission is detected providing information about the remaining amount of calcium in the cell. From this amount, the water vapor transmission rate is calculated. However it does not discriminate between oxygen and water permeation.
In calcium degradation test another limitation in measuring permeability is the need for a better edge seal and the nature of the adhesive used for the lamination that can bring about discrepancies in the measurement of permeability values.
Gravimetric Method
The measuring instrument for gravimetric moisture determination consists of a radiator, a weighing cell, and a sample receiver which can be connected to the weighing cell. To determine the moisture content, the sample is dried and the weight of the sample is measured before and after the weighing process. Because the method is dependent on the measurement of change in volume, it has the disadvantage that very low permeability which causes small amounts of change in volume is difficult to measure.
The test accuracy and test repeatability using gravimetric method is also difficult. Spectroscopic method: TDLS
TDLS analyzers measures light intensity. The external environment affects TDLS performance. Further, moisture in the range of ppb can be detected and TDLS techniques. As a result, TDLS is not stable as Continuous-Wave Cavity Ring-down spectroscopy analyzers. And TDLS construction is more complex. Cost of TDLS is about 4 times more than CRDS units.
A comparative analysis of different methods of permeability measurement is given in Table 1.
The aforementioned testing methods are deficient in sensitivity of measurements, thus producing unreliable results in the low range of sensitivity. Lowest reliable quantity that can be measured is about 5 x 10"4 g/m2/day. Other methods of measurement and equipment are required to be developed which can provide highly accurate results.
For the said reasons, there has been intense interest in developing barrier/encapsulating
materials with much lower permeability and the techniques to measure the same at such a low
level.
CRDS technique has been used for trace gas sensing, quantitative absorption measurements
astro-chemistry, photo-chemistry, isotope ratio analysis, medical diagnosis. However, till
date it has not been explored for permeability measurement of gases through membranes.
To overcome the drawbacks of the known techniques in relation to the measurement of permeability, the present invention proposes to use 'Cavity Ring Down Spectroscopy-CRDS' as a tool for measuring permeability of encapsulating materials in conjugation with a test chamber.
STATEMENT OF INVENTION
Accordingly the present invention provides a setup (A) for measuring permeability of a material (10) for a gas, comprising (a)cavity ring down spectroscopic unit (B), and (b) test chamber (8), comprising chambered flange (16) with inlet (9) and outlet (14) mounted on a chambered flange (17) with inlet (11) and outlet (18), wherein, the outlet (18) of the chambered flange (17) is connected to inlet of the cavity ring down spectroscopic unit (B); a test chamber (8), comprising chambered flange (16) with inlet (9) and outlet(14) mounted on a chambered flange (17) with inlet (11) and outlet (18 ) for conjugating with the cavity ring down spectroscopic unit (B); and a method for measuring permeability of a material (10) using the setup (A), said method comprising acts of, (a) mounting a material to be tested for its permeability between flanges (16) and (17) of test chamber (8), (b) purging the flange (17) through inlet (11) with a carrier gas, (c) purging the flange (16) through inlet (9) with a gas for permeation into the flange (17) through the material to be tested; and (d) transporting the permeated gas into the cavity ring down spectroscopic unit (B) along with the carrier gas for analysis and measurement of permeability.
BRIEF DESCRIPTION OF FIGURES
The present invention will be readily understood by the following detailed description in
conjunction with the accompanying figures, wherein like reference numerals designate like
structural elements, and in which:
Figure 1: illustrates schematic diagram of CRDS working principle.
Figure 2: illustrates set-up of the present invention wherein test chamber (8) is connected to
CRDS unit (B).
Figure 3 A: illustrates the cross sectional view of test chamber (8), and
Figure 3B: illustrates the side view of test chamber (8).
DETAILED DESCRIPTION OF INVENTION
The present invention will now be described more fully with reference to the accompanying figures. However, this invention should not be construed as limited to the embodiments set forth herein as many modifications and variations are possible in light of this disclosure for a person skilje4 in tfie art to which the invention belongs in view of tjie drawings, description and claims.
Like numbers refer to like elements throughout. It may further be noted that as used herein and in the appended claims, the singular forms "a", "an", and "the" include plural reference unless the context clearly dictates otherwise.
Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by person skilled in the art to which the invention belongs. Well-known functions or constructions will not necessarily be described in detail for brevity and/or clarity.
The present invention is in relation to a setup (A) for measuring permeability of a material (10) for a gas, comprising
(a) cavity ring down spectroscopic unit (B); and
(b) test chamber (8), comprising chambered flange (16) with inlet (9) and outlet(14) mounted on a chambered flange (17) with inlet (11) and outlet 18);
wherein, the outlet (18) of the chambered flange (17) is connected to inlet of the cavity ring
down spectroscopic unit (B).
In another embodiment of the present invention, the test chamber (8) is fabricated with
stainless steel.
In still another embodiment of the present invention the material (10) is mounted in between
the flanges (16) and (17).
The present invention is also in relation to a test chamber (8) comprising chambered flange
(16) with inlet (9) and outlet(14) mounted on a chambered flange (17) with inlet (11) and
outlet (18 ) for conjugating with cavity ring down spectroscopic unit (B).
The present invention is also in relation to a method for measuring permeability of a material
(10) using the setup (A), said method comprising acts of,
a) mounting a material(lO) to be tested for its permeability between flanges (16) and (17) of test chamber (8);
b) purging the flange (17) through inlet (11) with a carrier gas;
c) purging the flange (16) through inlet (9) with a gas for permeation into the flange (17) through the material (10) to be tested; and
d) transporting the permeated gas into the cavity ring down spectroscopic unit along with the carrier gas for analysis and measurement of permeability.
In still another embodiment of the present invention the permeability is ranging from about 1000 g/m2/day to about 10"6g/m2/day.
In still another embodiment of the present invention, the carrier gas is selected from a group comprising nitrogen (N2), oxygen (02), compressed air, carbon dioxide (C02), carbon-monoxide (CO), nitrogen dioxide (N02), nitrous oxide (N20), methane (CH4), acetylene (C2H2), hydrogen fluoride (HF) and hydrogen chloride (HC1).
In still another embodiment of the present invention, the gas is selected from a group comprising water vapor, oxygen, carbon dioxide, acetylene, carbon monoxide, nitrogen dioxide, nitrous oxide, methane, hydrogen fluoride and hydrogen chloride. In yet another embodiment of the present invention, the gas is preferably water vapor.
Cavity ring-down spectroscopy is a rapidly developing technology in which radiation from a narrow bandwidth laser is introduced into a high finesse cavity. The cavity has two highly reflective (99.999%) coated-quartz dielectric mirrors separated by a distance d form an optical resonator. When the cavity is in resonance with laser light, the laser beam is abruptly turned off using an acousto-optic modulator. As the laser light is reflected back and forth between the mirrors, the light intensity decays due to mirror reflectance losses, scattering effects, and absorption of light by moisture in the cavity. As the light intensity in the cavity decays, the small fraction of the light that leaks out through the back mirror is measured with a fast detector. Figure-1 provides the schematic of the CRDS working principle. Accordingly, the numerals therein indicate the following.
(1) Computer
(2) Laser source
(3) Mirrors
(4) Cavity
(5) High reflectivity mirror
(6) Detectors
(7) CRDS Signal
The CRDS signal is a simple exponential decay characterized by the ring-down decay time constant (x). As losses due to reflectance and Raleigh scattering effects are constant and extremely low, absorption due to the moisture of sample in the cavity can be detected with high sensitivity.
The signal decay time constant x of an empty and sample filled cell, respectively, is given by,
Where x(v) is the ring-down time at frequency v, d is the mirror spacing or cell path length, c is the speed of light, R is the mirror reflectivity, a(v) is the absorption cross section of the particular molecules that absorb radiation at frequency v, and N is their number density, which is proportional to the absolute concentration. The moisture concentration is inversely proportional to the difference between the signal decay time constants measured with and without the presence of sample in the cavity.
1 ( 1 1 1
C100 run) is present, permeability measurements can be obtained. However, in CRDS permeability measurements can be measured for a longer time. In the example 3 permeability measurements obtained from CRDS is shown in the following figure (Graph 7A). Permeability measurements by calcium degradation test were carried out only until 30 minutes as calcium layer degraded after that
period. Whereas, by using CRDS permeability were measured up to 5 hours illustrating the actual permeation behavior over time (Graph 7B).
Graph 7B - CRDS result for PVB based solution casted films for a longer duration.
The above example substantiates the advantage of the present invention over the calcium degradation test as follows-
• In case of calcium test we need to depend on calcium thickness which is one of the major problem in the test, normally when Ca thickness reaches <100 nm, then the resistivity will not be constant. Whereas in CRDS the sensor is laser based spectroscopic, which is highly sensitive, and no chance of degradation.
• In calcium degradation test, permeability can be calculated for the lifetime of deposited calcium, while in CRDS the permeability of a test film till a longer period of time as there is no chance of the sensor degradation like calcium test.
• In calcium degradation test oxygen can also degrade calcium as well, which cannot be distinguished from moisture degradation. However, in CRDS as the sensor is laser based and is specific to the wavelength, where moisture absorbs. Therefore, oxygen cannot interfere, and hence the result obtained is truly moisture permeability.
• Calculation method is based on assumption of homogeneous calcium degradation.
• Needs better glue for sealing in calcium degradation test to achieve lower limit of permeability.
• Calculation method assumes only permeation through a film area window of (1 x b) of the calcium layer, which is not the actual situation.
• Calcium test is indirect method of calculating permeability based on degradation of calcium. Whereas CRDS is an absolute method of measurement.
Example 4:
Sample analyzed: PVB composite film fabricated by solution casting
The example 4 is related to solution casted composite films, prepared in lab using PVB (Polyvinylbutyral) as a polymer matrix and functionalized mesoporous silica as a filler matrix. Two samples with different thickness in the film were analyzed and the trends in permeability obtained from CRDS are shown. The results shows a similar trend of permeability for both but PVB SiC>2 composite 1 (1) has a relatively more WVTR than PVB Si02 composite 1 (2) due to the variation of thickness of the composite films used. PVB SiC>2 composite 1 (1) was having a thickness of 220 urn while PVB SiC<2 composite 1 (2) was having a relatively higher thickness of 250 urn.
The composite films also a similar permeation behavior. The difference in the values is due to the variation in the film thickness.The lowest permeability values observed in the example is as follows- lower limit is 0.001 (PVB Si02 composite 1) to 0.002 g/m2/day (PVB Si02 composite 2).
The values obtained for WVTR in all the above mentioned examples can be easily envisaged by the Y-axis in the respective curves.
It will be apparent that other variations and modifications apart from the above mentioned may also be made to the above described exemplary embodiments and functionality, with the attainment of some or all of their advantages.
It is an object of the appended claims to cover all such variations and modifications that come within the true spirit and scope of the invention.
WE CLAIM:
1. A setup (A) for measuring permeability of a material ( 10) for a gas, comprising
(a) cavity ring down spectroscopic unit (B); and
(b) test chamber (8), comprising chambered flange (16) with inlet (9) and outlet(14)
mounted on a chambered flange (17) with inlet (11) and outlet (18 );
wherein, the outlet (18) of the chambered flange (17) is connected to inlet of the cavity ring down spectroscopic unit (B).
2. The setup (A) as claimed in claim 1, wherein the test chamber (8) is fabricated with stainless steel.
3. The setup (A) as claimed in claim 1, wherein the material (10) is mounted in between the flanges (16) and (17).
4. A test chamber (8) comprising chambered flange (16) with inlet (9) and outlet(14) mounted on a chambered flange (17) with inlet (11) and outlet (18 ) for conjugating with cavity ring down spectroscopic unit (B).
5. A method for measuring permeability of a material (10) using the setup (A), said method comprising acts of,
a) mounting a material(l 0) to be tested for its permeability between flanges (16) and (17) of test chamber (8);
b) purging the flange (17) through inlet (11) with a carrier gas;
c) purging the flange (16) through inlet (9) with a gas for permeation into the flange (17) through the material (10) to be tested; and
d) transporting the permeated gas into the cavity ring down spectroscopic unit along with the carrier gas for analysis and measurement of permeability.
6. The method as claimed in claim 5, wherein the permeability is ranging from about 1000 g/m2/day to about 10"6g/m2/day.
7. The method as claimed in claim 5, wherein the carrier gas is selected from a group comprising nitrogen (N2),oxygen (02), compressed air, carbon dioxide (C02), carbon-monoxide (CO), nitrogen dioxide (N02), nitrous oxide (N20), methane (CH4), acetylene (C2H2), hydrogen fluoride (HF) and hydrogen chloride (HC1).
8. The method as claimed in claim 5, wherein the gas is selected from a group comprising water vapor, oxygen, carbon dioxide, acetylene, carbon monoxide, nitrogen dioxide, nitrous oxide, methane, hydrogen fluoride and hydrogen chloride.
9. The method as claimed in claim 5, wherein the gas is preferably water vapor.