CN101242889A - Porous PTFE materials and articles produced therefrom - Google Patents

Porous PTFE materials and articles produced therefrom Download PDF

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Publication number
CN101242889A
CN101242889A CNA2006800304509A CN200680030450A CN101242889A CN 101242889 A CN101242889 A CN 101242889A CN A2006800304509 A CNA2006800304509 A CN A2006800304509A CN 200680030450 A CN200680030450 A CN 200680030450A CN 101242889 A CN101242889 A CN 101242889A
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goods
bubbling point
film
flux rate
water flux
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J·E·班奇诺
A·R·赫布森
J·J·斯特里德
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Gore Enterprise Holdings Inc
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Gore Enterprise Holdings Inc
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Abstract

Novel porous PTFE membranes are described possessing a unique combination of high strength, low flow resistance, and small pore size. Additionally, unique constructions with superior filtration and venting properties incorporating porous PTFE membranes are described.

Description

Porous PTFE materials and by the goods of its production
Invention field
The present invention relates to combine the porous PTFE film of high air or permeability for liquids and small-bore, and filter material prepared therefrom.
Definition
Term " filter efficiency " used among the application refers under given flow velocity, is filtered the interior particle percentage of specified particle size scope of material or capture medium.
Used term " flows " and refers to that fluid passes through film or filter material in this application.Term " flow velocity " refers to that the volume that flows through in the unit interval, term " flow resistance " refer to the restriction of flowing and being subjected in the process that flows through small-bore film or medium.
The term that uses in this application " permeability " refers to when film or filter material bear different pressure on two side, makes fluid (liquid or gas) transmit ability by the hole of this material.Permeability can characterize by lattice profit (Gurley) value, Fu Leize (Frazier) value or water flux rate (water flux rate).
The term that uses in this application " aperture " refers to the size of perforated membrane mesopore.The aperture can enter pressure by bubbling point, average flow aperture or water and characterize, and will describe in detail hereinafter.
The term that uses in this application " water enters pressure " refers to order about water droplet by the required pressure of film, will further describe in the method for testing that comprises in the text.
Background of invention
Desirable filter membrane has for the enough intensity of target application, and combines high air or permeability for liquids and filtration efficiency.Fall for given transmembrane pressure, high osmosis by film or high fluid ability have shortened filtration time, thereby have reduced cost of energy owing to reduced energy loss.In addition, these characteristics make that littler, more cost-effective system is installed becomes possibility.The improvement of filter efficiency has strengthened catching pollutant.Usually, optimize the decline that any one character in filter efficiency or the permeability is always brought another character.For example, in order to catch smaller particles, described film must have aperture, but smaller aperture due has increased flow resistance usually, thereby has reduced liquid or gas passes through permeability of the membrane.Similarly, be easy to just improve the ability that flows through film, but handle the particle minimizing that causes film to be caught like this, and catch decrease in efficiency than granule by the aperture that increases filter media.
Improvement for the exploitation filter medium concentrates on and finds high osmosis, small-bore and high-intensity desirable combination.Expanded PTFE (ePTFE) film has been obtained very big success in the liquids and gases filtration art.The expanded PTFE film is normally hydrophobic, unless the adjustment of process processing or modification or alternate manner.This class film not only has the heat endurance under high chemical inertness and the extreme temperature, but also has high strength.
Method and the goods prepared therefrom of processing foamed PTFE have been described in No. the 5th, 476,589, the United States Patent (USP) of Bacino.Bacino has described the extremely thin goods that mainly are made of microfibre.This patent can be processed the high strength PTFE goods with unprecedented small particle diameter and high air permeability.These goods make it make in the foaming of vertical and horizontal direction by cross directional stretch PTFE then.Though these materials are compared the strainability with improvement with film before, still there is limitation in they aspect the ever-increasing industrial requirements satisfying.
Be well known in the art the aperture that the expansion ratio of increase PTFE can increase the gained porous, expanded articles usually.Bigger aperture causes the lower flow resistance of passing through film, but as mentioned above, has but reduced filter efficiency, particularly for the filter efficiency of smaller particles.Further stretching often reduces the thickness of film, and the result causes the decline of flow resistance.
Therefore, though carried out countless effort, still need to provide simultaneously the thin and strong filter membrane of small particle diameter and low flow resistance to improve the filtering property of PTFE film.
Summary of the invention
The present invention relates to the novel porous PTFE film that is combined with unique high strength, low flow resistance and small-bore.In addition, the present invention relates to have the high-performance filter material and the ventilating structure of the uniqueness of the strainability that does not also have realization up to now, comprise the structure that those are applicable to ventilatory applications.
The porous PTFE film of making of the present invention can be combined with following character, and for example: the relation of bubbling point-grignard value is equal to or less than equation log (grignard value)=5.13 * 10 -3The line that (bubbling point)-1.26 limit; Surface area is at least 20 meters 2/ gram; The combination of at least 50% light transmittance and at least 50% porosity; Matrix tensile strength (matrix tensile strength) at two orthogonal directions is at least 1.3 * 10 5MPa 2And the various combinations of these peculiar properties.Other film of the present invention shows following character: the relation of grignard value-bubbling point (Gurley number versus bubble point) is equal to or less than equation log (grignard value)=5.13 * 10 -3The line that (bubbling point)-1.58 limit, even be equal to or less than equation log (grignard value)=5.13 * 10 -3The line that (bubbling point)-2.02 limit still shows at least 20 meters simultaneously 2The surface area of/gram.The particular performances that enters the relation measurement in the relation of relation, water flux rate and bubbling point of pressure (water entry pressure) and grignard value and water flux rate and average flow aperture by water also can be used film realization of the present invention.For example, can obtain the film that relation that water enters pressure-grignard value is equal to or higher than the line that equation WEP=3 (grignard value)+2500 limits.In addition, the relation that can make water flux rate-bubbling point is equal to or higher than equation log (water flux rate)=-3.5 * 10 -3The film of the line of (bubbling point)+1.3.In addition, the relation in the water flux rate-average flow aperture film that is equal to or higher than the line that equation log (water flux rate)=16.9 (average flow aperture)-1.85 limits also falls within the scope of the invention.
The goods that can prepare in yet another embodiment of the present invention, the complex that comprises at least one porous PTFE film and at least one other layer.Described at least one other layer can be the form of film, supatex fabric, scrim and/or fabric, specifically depends on the character that end article is required.For example, can form such composite article, the relation of the water flux rate-bubbling point of wherein said complex is equal to or higher than equation log (water flux rate)=-3.5 * 10 -3The line that (bubbling point)+1.3 limit more preferably is equal to or higher than equation log (water flux rate)=-3.5 * 10 -3The line that (bubbling point)+1.6 limit more preferably is equal to or higher than equation log (water flux rate)=-3.5 * 10 -3The line that (bubbling point)+2.0 limit.Perhaps composite construction can comprise the complex of at least one porous PTFE film and at least one other layer, and wherein said complex can be at once by water-wet, and the relation of its water flux rate-bubbling point is equal to or higher than equation log (water flux rate)=-0.01 * 10 -3The line that (bubbling point)+1.3 limit more preferably is equal to or higher than equation log (water flux rate)=-0.01 * 10 -3The line that (bubbling point)+2.48 limit more preferably is equal to or higher than equation log (water flux rate)=-0.01 * 10 -3The line that (bubbling point)+5.0 limit.
In yet another embodiment of the present invention, can according to the present invention make have a following feature can be at once by the goods that contain the porous PTFE film of water-wet: the relation of water flux rate-bubbling point is equal to or higher than equation log (water flux rate)=-0.01 * 10 -3The line that (bubbling point)+1.3 limit more preferably is equal to or higher than equation log (water flux rate)=-0.01 * 10 -3The line that (bubbling point)+2.48 limit most preferably is equal to or higher than equation log (water flux rate)=-0.01 * 10 -3The line that (bubbling point)+5.0 limit.
In yet another embodiment of the present invention, can prepare the goods that contain the porous PTFE film with following character according to description of the invention: oil level (oil rating) is at least 2, more preferably is at least 4, more preferably is at least 5, water enters pressure and surpasses 500kPa, and grignard value is up to 350 seconds.In another embodiment, can prepare this oleophobic property film with following character: water enters pressure and surpasses 1250 kPas, and grignard value is up to 200 seconds.In another embodiment, can prepare this oleophobic property film with following character: water enters pressure and is higher than 2000 kPas, and grignard value is up to 100 seconds.
In yet another embodiment of the present invention, can be by the porous PTFE film preparation goods with following character: light transmittance be at least 50%, and the relation of grignard value-bubbling point is equal to or less than equation log (grignard value)=5.13 * 10 -3The line that (bubbling point)-1.22 limit more preferably is equal to or less than equation log (grignard value)=5.13 * 10 -3The line that (bubbling point)-1.58 limit most preferably is equal to or less than equation log (grignard value)=5.13 * 10 -3The line that (bubbling point)-2.02 limit.
At last, the present invention has also considered to use the filter that combines these unique films and complex (comprising gas permeable material) to filter fluid.
These and other unique characteristic of the present invention have been described in the literary composition.
Description of drawings
Fig. 1 describes according to the grignard value of the porous PTFE film of the embodiment that comprises herein preparation and the figure of bubbling point relation.
Fig. 2 is porous PTFE film and the water flux rate of composite membrane and the figure of bubbling point relation that describes according to the embodiment preparation that comprises herein.
Fig. 3 is hydrophilic porous PTFE film and the water flux rate of composite membrane and the figure of bubbling point relation that describes according to the embodiment preparation that comprises herein.
Fig. 4 describes to enter the figure of pressure and grignard value relation according to the water of the oleophobic property porous PTFE film of the embodiment that comprises preparation herein.
Fig. 5 describes to enter the figure of pressure and grignard value relation according to the water of the porous PTFE film of the embodiment that comprises preparation herein.
Fig. 6 describes the figure that concerns according to the water flux rate of the porous PTFE film of the embodiment that comprises preparation and average flow aperture herein.
                          Detailed Description Of The Invention
Porous PTFE goods of the present invention provide the combination of wonderful high strength, low flow resistance and small-bore. These goods have been filled up the demand for the high-performance filter medium. The prior art material is compared with material of the present invention, has the problem of high flow resistance or low filter efficiency aspect or has simultaneously the problem of this two aspect. Material of the present invention is compared with the material of prior art, and lower flow resistance and less aperture are provided. Material of the present invention can be used for the liquids and gases filtration application.
Low flow resistance and Gao Shui enter the combination of pressure so that material of the present invention is suitable for ventilative the application, and material will allow gas and steam to pass through in these are used, and refuses simultaneously aqueous water or other liquid passes through.
Can make ePTFE goods of the present invention have oleophobic property by various technology, thereby so that they are suitable for some ventilative application, in these were used, described material had the moving and Gao Shui of upper air current and enters pressure, and can stop that low surface tension liquid such as oil permeate.
Can by various technology make film of the present invention have hydrophily (under the minimum pressure or do not have fully in the situation of pressure can be by water-wet) so that they can be used for relating to the filtration applications that (for example) aqueous fluids filters.
Porous PTFE film of the present invention can be configured to complex filter or composite ventilating hole, and for example, this can be by stacked described film and one or more can finishing other layer that described film provides support or protects. The form of described one or more other layers can be one or more perforated membranes or traditional gas permeable material such as knitted fabric, supatex fabric, scrim, woven fabric etc. According to final instructions for use, can only one or more other layers be set all on the face of film or on two faces at film. According to final instructions for use, one or more other layers can be bonded on the described film or not be bonded on the described film. For example, described film and other layer can be loosely stacking, then is fixed on together around the filter by suitable means, for example by shell, framework, potting compound, adhesive or any other suitable means. Perhaps, by discontinuous laminating adhesive on the surface of one or more other layers, perhaps by any other suitable structure that meets final application requirements, thereby the locational suitable adhesive by at least a portion peripheral can be attached on the film in less several sites one or more other layers. Suitable adhesive includes but not limited to thermoplastic, thermosets of polypropylene, polyester, polyethylene, PFA, PEP and other suitable form etc. The benefit of complex filter and air-vent includes but not limited to: improved the operability of film, so that manufacturing Filter cartridge or air-vent become easier; Improved in some cases filter efficiency; Etc.. In order to make film as complex filter the time, keep its high fluidity matter, usually other layer is selected, flow resistance is minimized. And complex filter and air-vent can be hydrophobicity, oleophobic property or hydrophilic according to their purposes.
Usually expect that according to the description of prior art the degree of PTFE material foaming is higher, the aperture of the PTFE structure that then obtains is larger. But, in situation of the present invention, find under certain conditions unexpectedly, can realize less aperture by the degree that improves foaming. More surprisingly, the increase that reduces to be accompanied by membrane permeability in this aperture. The method obtains the membrane structure that permeability increases the novelty that effective aperture simultaneously reduces. In addition, the film of gained has high strength.
The unique combination of permeability of the membrane of the present invention and aperture character is confirmed by the chart shown in the accompanying drawing. In these charts, permeability characterizes by grignard value or water flux rate. Grignard value reduces (being the air of the given volume time shorten by film under given pressure), Fu Leize value (namely for given pressure drop and sample area, air is by the flow velocity of film) raise and the rising of water flux rate, show that permeability strengthens. The aperture enters pressure (WEP) value by bubbling point (BP), average flow aperture or water and characterizes. Higher foaming point value (making bubble pass through the required pressure of wetting membrane sample) and higher WEP value (ordering about water droplet by the required pressure of film) show less aperture. The present invention provides the method for testing of measuring grignard value, Fu Leize value, water flux rate, WEP, average flow aperture and BP in detail.
Fig. 1-Fig. 6 has shown the feature that goods of the present invention are compared with the goods of prior art.Fig. 1 has described the grignard value and the BP measured value of the film of the present invention and prior art.Equation log (grignard value (second))=2.60 * 10 -3(BP (kPa))-0.54 described among the figure for the straight line of doing greater than 448 kPas bubbling point.The data point of material of the present invention drops on this straight line or the below of this straight line, and the data point of prior art material drops on the top of this straight line.Fig. 2 has described the water flux rate and the BP measured value of the present invention and prior art material.Equation log (the water flux rate (cm per minute/kPa))=-3.5 * 10 -3(BP (kPa))+1.3 the straight line of being done among the figure has been described.The data point of material of the present invention drops on this straight line or the top of this straight line, and the data point of prior art material drops on the below of this straight line.Fig. 3 has described the water flux rate and the BP measured value of the hydrophilic material of the present invention and prior art.Equation log (water flux rate (cm per minute/kPa))=-0.01 (BP (kPa))+1.3 the straight line of being done among the figure has been described.The data point of material of the present invention drops on this straight line or the top of this straight line, and the data point of prior art material drops on the below of this straight line.The water that Fig. 4 has described the oleophobic material of the present invention and prior art enters pressure and grignard value measured value.Entering force value corresponding to the water of the data point of material of the present invention is 500 kPas or higher, and grignard value is 350 seconds or lower.Fig. 5 has described the relation that the water of the present invention and prior art film enters pressure and grignard value.Equation WEP (kPa)=straight line of being done among the figure has been described in 3 (grignard value (second))+2500.The data point of material of the present invention drops on this straight line or the top of this straight line, and the data point of prior art material drops on the below of this straight line.Fig. 6 has described the water flux rate of the present invention and prior art film and the relation in average flow aperture.Equation log (water flux rate (cm per minute/kPa))=16.9 (average flow aperture (microns))-1.85 have described the straight line of being done among the figure.The data point of material of the present invention drops on this straight line or the top of this straight line, and the data point of prior art material drops on the below of this straight line.
In aforesaid equation, the unit of grignard value is second, and the unit of BP be kPa, the unit of water flux rate be cm per minute/kPa, the unit that water enters pressure for kPa, the unit in average flow aperture is micron.Logarithmic equation is used denary logarithm.
In this six width of cloth figure, goods of the present invention are compared with the goods of prior art, show higher permeability for given aperture, show less aperture for given permeability.
The high strength of described film has further improved the filtering property of the excellence of these novel films and composite article.Film of the present invention is the intensity height not only, and they are the highest ePTFE goods of balance matrix tensile strength of producing up to now.Approach the balance that one degree is represented film-strength with the ratio of the matrix tensile strength of film on two orthogonal directions.This ratio of the film of balance is about 2: 1 usually or is littler.In addition, these films have the product of the matrix tensile strength of the maximum of measuring on two orthogonal directions.For example, the product of the matrix tensile strength on two orthogonal directions is greater than 1.3 * 10 5MPa 2, more preferably greater than 1.5 * 10 5MPa 2, more preferably greater than 1.9 * 10 5MPa 2Orthogonal direction includes but not limited to vertical and horizontal.High strength is not valuable especially with filtration application that one or more other layers are used in combination for film.Higher intensity also makes can use thin film.The thicker film identical with others compared, and thin film shows lower flow resistance.High strength also helps thin film-stack on other layer, can also prolong the service life of the filter media of pleating form.In addition, high-strength membrane can need bear in the situation of high pressure or pulse opposing better at filter and breaks.
Yet another wonderful aspect of the present invention is the unprecedented high surface of these novel films, and the measurement of described surface area is as described herein.The surface area of the unit mass of the ePTFE film of prior art is a 10-19 rice 2/ gram.Films more of the present invention can be adjusted to surface area at least up to 20-27 rice 2/ gram.
Compare with the low density form of porous, the non-porous form of PTFE and ePTFE can allow obviously more visible light to pass through.The refractive index of PTFE (percent crystallization in massecuite according to PTFE is generally 1.3-1.4) makes ePTFE material generation diffuse reflection.Usually, the light transmittance of these materials is less than 50%.Another aspect of the present invention can prepare the film with high transparent, and these films have very high porosity.For example, the light transmittance of film of the present invention is at least 50%, and porosity is at least 50%.Porosity can be equal to or greater than 85% greater than the light transmittance of 75% film.This class material is valuable especially in conjunction with transparent or semitransparent property and infiltrative application for needs.
To further describe the present invention with reference to non-limiting example hereinafter described.
Embodiment
The method of testing of using among the embodiment
Thickness measure
Film is placed on the thickness of measuring film between two plates of card good fortune (Kafer) FZ1000/30 thickness calliper (Ka Fu company (KaferMessuhrenfabrik GmbH), film Gen-Shi vinine root, Germany).Use the mean value of measuring for three times.
Density measure
Sample to the square-section of 15.24 centimetres of die-cut formation 2.54 cm x is measured, determine their quality (using MT assay balance (Mettler-Toledo analytical balance), model AG204) and thickness (using card good fortune (Kafer) FZ1000/30 calliper).Use these data, by the following formula bulk density:
ρ = m w * l * t
Wherein: ρ=density (gram per centimeter 3); M=quality (gram); The w=width (centimetre); L=length (centimetre); T=thickness (centimetre).Use the mean value of measuring for three times.
The calculating of the measurement of tensile fracture load and matrix tensile strength (MTS)
Use is equipped with the INSTRON1122 stretching testing machine of plane anchor clamps and 0.445kN load cell and measures tensile fracture load.Gauge length is 5.08 centimetres, and crosshead speed is 50.8 cm per minute.Sample size is 15.24 centimetres of 2.54 cm x.Measure for vertical MTS, the dimension that sample is bigger is along the machine direction orientation or along " thin slice (down web) " direction orientation.Measure for horizontal MTS, the dimension that sample is bigger is orientated perpendicular to machine direction, is also referred to as the direction of vertical thin slice.Use the weight of MT assay balance (Mettler Toledo Scale, model AG204) each sample of weighing, use card good fortune (Kafer) FZ1000/30 thickness calliper to measure sample thickness then.Then each sample is tested on tester for elongation respectively.Measure three different parts of each sample.Use the mean value of three maximum loads (being the peak value of power) measured value.Use following equation to calculate vertical and horizontal MTS:
The density of MTS=(maximum load/sectional area) * (bulk density of PTFE)/perforated membrane),
Wherein the volume density of PTFE is got 2.2 gram per centimeters 3
Steel ball bursting (ball burst) ionization meter
W.L.Gore ﹠amp; Associates, Inc. have developed method of testing and relevant sample erection unit, use Cha Telun testboard (Chatillon Test Stand).This thermometrically materials such as fabric (Woven fabric, knitted fabric, supatex fabric etc.), porous or nonporous plastic film, film, sheet, with and the bursting strength of other material of duplexer and flat type.
Be installed between two annular clamping plate but sample tightened with not elongating, have a diameter and be 7.62 centimetres opening.Have diameter and be 2.54 centimetres the metal bar at spherical polished steel tip with Z direction (with X-Y plane direction quadrature) to the center of sample imposed load.The other end of metal bar links to each other with suitable Cha Telun dynamometer in being installed in Cha Telun testing of materials platform (model TCD-200).Speed imposed load with 25.4 cm per minute begins to be damaged up to sample.The damage of sample (tear, break etc.) may taken place by any position in folder zone.The mean value of three measurement results of the maximum, force that applies before sample damages is as test result.
Test is carried out under the temperature and humidity condition in environmental chamber, generally carries out under the relative humidity of 21-24 ℃ temperature and 35-55%.Steel ball bursting data can be represented with the variation of the quality of unit are sample with the steel ball bursting strength; The quality of unit are sample can be determined by the product of sample rate and thickness of sample.
Ge Li measures
Lattice empty profit air-flow has moved thermometrically 100 centimetres 3Air is depressed by 6.45 centimetres in 12.4 cm of water 2The time (second) that sample is required.Use the sharp densometers of lattice (model 4340, automation densometer) to measure sample.Grignard value is carried out Fu Leize value test less than about 2 seconds goods, because this test provides more reliable measured value to the sign of high osmosis sample.Use the mean value of measuring for three times.
Fu Leize measures
Fu Leize permeability reading is to be under the situation of 12.7 millimeters of water at the pressure reduction of striding test specimens, the speed that per unit sample area per minute air flows, and unit is a foot 3/ (foot 2Second).Measure air permeability by the following method: specimen is clipped in the annular fixing member of band sealing flange, this fixture provides 17.2 cm diameters (232 centimetres of areas 2) annular opening.The upstream side of sample fixture is connected with the flowmeter with source of dry compressed air.The downstream of sample fixture is opened wide to atmosphere.Measurement is by the flow velocity of sample, and as the Fu Leize value record.Use the mean value of measuring for three times.Can the Fu Leize Value Data be converted to grignard value by following equation: grignard value=3.126/ Fu Leize value, wherein grignard value is unit representation with the second.
The water flux rate is measured
Use following steps to calculate the water flux rate of passing through film.Described film dangled stride across tester (47 millimeters on Sterifil support, catalog number (Cat.No.): XX11 J4750, micropore (Millipore)) or cut to suitable dimension coverage test plate.At first use 100% isopropyl alcohol complete wetting film.In tester, fill up deionized water (room temperature).Apply 33.87 kPas pressure in the both sides of film; Measure 400 centimetres 3Deionized water flows through the required time of film.Calculate the water flux rate according to following equation then:
The water flux rate [cm per minute/kPa]=water flow velocity [centimetre 3/ minute]/sample area [centimetre 2]/test pressure [kPa].
It should be noted that for hydrophilic film this film does not need to use in advance isopropyl alcohol wetting.Use above-mentioned identical step to measure the water flux rate of passing through complex filter.Use the mean value of measuring for three times.
Water enters pressure measxurement
It is to measure the method for testing of water intrusion by film that water enters pressure.(series number: 8240+92+2949 is by the BF Pi Ken company (MA USA) makes for BF.Perkins, Chicopee) of Massachusetts, United States Qi Kepi to use Mullen  tester.Specimen is clipped in the middle of the test fixture that the square Plexiglass sheet of 10.16 centimetres of a pair of each length of sides by 1.27 cm thicks makes.The fixture of below can pressurize to sample in cross section under the effect of water.A slice pH test paper is placed on the sample top as the indicator that shows that water enters.Pressure with little increment pressurizes to sample then, up to the color change of observing the pH test paper.Penetrate pressure accordingly or enter pressure and be called water and enter pressure.Use the mean value of measuring for three times.
Bubbling point is measured
General guide according to ASTM F31 6-03 uses Capillary Flow porometer (Capillary FlowPorometer) (model C FP 1500AEXL, (the PorousMaterials Inc. of porous material company from New York Ithaca U.S., Ithaca, NY)) measurement bubbling point and average flow aperture.Sample film is placed in the sample room, is the Si Weike silicone fluid (SilWick Silicone Fluid) (can buy from porous material company (Porous Materials Inc.)) of 19.1 dynes per centimeter with surface tension) wetting.It is 2.54 centimetres that the bottom folder of sample room has diameter, thickness is 3.175 millimeters porous metals dish plug-in unit (Mo Te (Mott Metallurgical), Farmington, CT, 40 microns porous metals dish), the top folder of sample room has the hole of 3.175 mm dias.Use Kapp literary composition (Capwin) software version 6.62.1, following parameter is set according to the regulation of following table.The value in expression bubbling point and average flow aperture is the mean value of twice measurement.
Parameter Set point Parameter Set point
Peak Flow Rate (cc/m) 200000 Minimum equilibration time (mineqtime) (second) 30
Foaming flow velocity (bublflow) (cc/m) 100 Pressure-swing (presslew) (cts) 10
F/PT (old foaming time) 40 Flow revolution (flowslew) (cts) 50
Minimum foaming pressure (minbppres) (PSI) 0 eqiter 3
Zero-time (zerotime second) 1 aveiter 20
v2incr(cts) 10 Maximum differential pressure (maxpdif) (PSI) 0.1
preginc(cts) 1 Maximum stream flow poor (maxfdif) (centimetre 3/ rice) 50
Pulse daley 2 Initiation pressure (sartp) (PSI) 1
Maximum pressure (maxpre) (PSI) 500 Beginning flow (sartf) (centimetre 3/ rice) 500
Pulse width 0.2
Light transmittance is measured
Use radiometer (model IC 1700, international Optical Co., Ltd (International Light), Newburyport, Massachusetts) to measure the amount of the light that sees through the ePTFE membrane sample.The pipe (outer dia of its diameter and optical receiving sensor is roughly the same, and model SED 033) of a black is clipped on the optical sensor, stretches out about 13.3 centimetres from the receiving plane of sensor.Light source (50 watts of Xi Erwei Niamey reflectors (Sylvania Reflector), 120 volts of bulbs) is directly installed on the opposite of optical receiver from the about 28.6 centimetres distance of the receiving plane of optical sensor.Calibration radiation meter in the following manner: the result who obtains when a cap is placed on an end of the pipe that stretches out from optical sensor is set at zero point, remove cap, and opening light source, the result who obtains when any obstacle not being set between light source and optical sensor is set at 100% point.Behind the calibration radiation meter, the ePTFE film is installed in the embroidery frame frame of 25.4 cm diameters, and remains between light source and the optical sensor, about 7.6 centimetres apart from light source.The printing opacity percentage that record IC 1700 radiometers show.Use the mean value of measuring for three times.
Surface area is measured
Use Courtelle (Coulter) SA3100 gas absorption analyzer ((the Beckman Coulter Inc. of Beckman Courtelle company of California Fu Ledun, Fullerton, CA)) according to Brunouer-Amy spy-Taylor (Brunauer-Emmett-Teller) (BET) method measure the surface area of per unit mass ePTFE film (unit be meter 2/ gram).Downcut sample from the center of ePTFE film thin slice, be placed in the sample QC (parameter 8201151).The quality of ePTFE sample is about the 0.1-0.2 gram.This pipe is put into Courtelle (Coulter) SA-Prep surface degassing instrument (Surface Area Outgasser) (model SA-PREP, P/N 5102014, (the Beckman Coulter Inc. of Beckman Courtelle company from California Fu Ledun, Fullerton, CA) in, at 110 ℃ with helium purge 2 hours.Then sample cell is taken out from the SA-Prep degassing instrument, weigh.Then sample cell is put into SA3100 gas absorption analyzer, according to instrument explanation the carrying out measurement of BET surface area, used helium to calculate free space then, use nitrogen as adsorbed gas.Each sample record one-shot measurement result.
Porosity is calculated
Represent porosity with percentage, the coefficient of the coefficient (as indicated above) of the averag density by from 1, deducting goods and the bulk density of PTFE, and then multiply by 100% and determine porosity.Calculate for this, the bulk density of PTFE is got 2.2 gram per centimeters 3
Oleophobic spare measurement/oil level
Use AATCC method of testing 118-1997 to measure the oil level.That lower rank in two ranks that the oil level of described film obtains when being two sides of test membrane.This value is high more, illustrates that the oleophobic property of film is good more.
Wettability is measured
In order to characterize the hydrophilicrty of sample, measure wettability.Described sample is fixed in the frame that stretches tight of 10.16 centimetres of diameters, keeps the state of tightening.Single water droplet is from just dropping on sample in the position of 5 cm heights above the sample.The measurement water droplet penetrates the time of sample hole.Use the rank of following standard rating wettability:
The 0=water droplet penetrated sample in 5 seconds
The 1=water droplet is surpassing 5 seconds, is penetrating sample in less than 60 seconds time
The 2=water droplet did not penetrate sample later on yet at 60 seconds.
Hydrophobic material such as porous ePTFE material have less hole, and the wettability rank is 2 usually.The wettability rank is that 0 or 1 material thinks can be wetting at once.
Embodiment 1
With PTFE fine polymer powder the end ((DaikinIndustries of Da Ken industrial group of New York Orangeburg, Ltd., Orangeburg, NY)) with lsopar K ((the Exxon Mobil Corp. of the Exxon Mobil Corporation of Virginia, USA Fairfax, Fairfax, VA)) mix according to the ratio of 0.196 gram/gram fine powder.The lubricated powder of compacting forms bead in cylinder, places about 12 hours in being set at 70 ℃ baking oven.Bead through compacting and heating is carried out plunger type extrude, produce wide about 15.2 centimetres, thick about 0.73 millimeter band.Produce independently band of three volumes, these bands are stacked together between pressure roller, to thickness be 0.76 millimeter.With described band cross directional stretch to 56 centimetre (being that ratio is 3.7: 1), limit then, dry in being set at 270 ℃ baking oven then.Dry zone longitudinal dilatation between two the roller limits (bank of roll) that are set on 340 ℃ the heating plate.The i.e. expansion ratio of speed ratio between the second roller limit and the first roller limit is 8: 1.Band lateral expansion to ratio under about 320 ℃ temperature with longitudinal dilatation is 34: 1 then, limits then, and heating is about 24 seconds in being set at 320 ℃ baking oven.The method condition of this embodiment and the size of intermediate are shown in Table 1.This method produces high intensity, porous film.
Table 1
Method condition ﹠ intermediate size Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
Lubricant content (gram/gram resin) 0.196 0.196 0.202 0.196 0.202
Bead conditioning-the time (hour) 12 12 12 12 12
Bead conditioning-temperature set-point (℃) 70 70 70 70 70
Bandwidth (centimetre) 15.2 15.2 15.2 15.2 15.2
Tape thickness (millimeter) 0.73 0.73 0.73 0.73 0.73
The number of plies of band 3 3 3 1 3
Tape thickness (millimeter) through calendering 0.76 0.76 0.76 0.25 0.76
The cross directional stretch ratio 3.7∶1 3.7∶1 3.7∶1 3.7∶1 3.7∶1
The baking temperature set point (℃) 270 270 250 270 250
The expansion temperature set point (℃) 340 340 345 345 345
The longitudinal dilatation ratio 8∶1 13∶1 15∶1 15∶1 20∶1
The expansion temperature set point (℃) 320 320 360 360 360
The lateral expansion ratio 34∶1 32∶1 30∶1 30∶1 22∶1
The heat treated temperature set-point (℃) 320 320 390 380 390
The heat treated time (second) 24 24 20 24 20
Measure various character by aforesaid method then and characterize this film.The film character of Zhi Bei sample is shown in Table 2 in this embodiment.The grignard value of the sample of this embodiment and BP data are shown among Fig. 1.The water flux rate and the BP data of the sample of this embodiment are shown among Fig. 2.The water of the sample of this embodiment enters pressure and the grignard value data are shown among Fig. 5.The water flux rate of the sample of this embodiment and average flow aperture data are shown among Fig. 6.
Table 2
Film character Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4 Embodiment 5
Density (gram per centimeter 3) 0.357 0.339 0.348 0.294 0.358
Thickness (millimeter) 0.020 0.013 0.010 0.0025 0.0076
Vertical MTS (MPa) 217 312 471 414 584
Horizontal MTS (MPa) 214 249 289 460 229
Product (the MPa of vertical and horizontal MTS 2) 46,570 77,568 136,042 190,562 133,539
Steel ball bursting strength (newton) 21.3 18.0 45.4 16.5 35.1
Grignard value (second) 11.1 7.6 12.5 2.1 7.3
Bubbling point (kPa) 647 564 877 605 764
The water flux rate (cm per minute/kPa) 0.23 0.33 0.12 0.61 0.25
Average flow aperture (micron) 0.056 0.065 0.05545 0.0765 0.0642
Water enter pressure (kPa) 3111 2939 ≥4136
Surface area (rice 2/ gram) 17.2 18.4 27.4 23.5
Embodiment 2
With PTFE fine polymer powder the end ((DaikinIndustries of Da Ken industrial group of New York Orangeburg, Ltd., Orangeburg, NY)) with lsopar K ((the Exxon Mobil Corp. of the Exxon Mobil Corporation of Virginia, USA Fairfax, Fairfax, VA)) mix according to the ratio of 0.196 gram/gram fine powder.The lubricated powder of compacting forms bead in cylinder, places about 12 hours in being set at 70 ℃ baking oven.Bead through compacting and heating is carried out plunger type extrude, produce wide about 15.2 centimetres, thick about 0.73 millimeter band.Produce independently band of three volumes, these bands are stacked together between pressure roller, to thickness be 0.76 millimeter.With described band cross directional stretch to 56 centimetre (being that ratio is 3.7: 1), limit then, dry in 270 ℃ baking oven then.Longitudinal dilatation between two roller limits of dry zone in being set at 340 ℃ the thermal treatment zone.The i.e. expansion ratio of speed ratio between the second roller limit and the first roller limit is 13: 1.Band lateral expansion to ratio under about 320 ℃ temperature with longitudinal dilatation is 32: 1 then, limits then, about 24 seconds of 320 ℃ of heating.The method condition of this embodiment and the size of intermediate are shown in Table 1.This method produces high intensity, porous film.
Measure various character by aforesaid method then and characterize this film.The film character of Zhi Bei sample is shown in Table 2 in this embodiment.The grignard value of the sample of this embodiment and BP data are shown among Fig. 1.The water flux rate and the BP data of the sample of this embodiment are shown among Fig. 2.The water of the sample of this embodiment enters pressure and the grignard value data are shown among Fig. 5.The water flux rate of the sample of this embodiment and average flow aperture data are shown among Fig. 6.
Embodiment 3
Will (Exxon Mobil Corporation of Virginia, USA Fairfax (Exxon Mobil Corp., Fairfax, VA)) be according to the ratio mixing of 0.202 gram/gram fine powder as the end of the PTFE fine polymer powder described in the United States Patent (USP) 6541589 and lsopar K.The lubricated powder of compacting forms bead in cylinder, places about 12 hours in being set at 70 ℃ baking oven.Bead through compacting and heating is carried out plunger type extrude, produce wide about 15.2 centimetres, thick about 0.73 millimeter band.Produce independently band of three volumes, these bands are stacked together between pressure roller, to thickness be 0.76 millimeter.With described band cross directional stretch to 56 centimetre (being that ratio is 3.7: 1), limit, then then 250 ℃ of dryings.Dry zone longitudinal dilatation between two roller limits that are set on 345 ℃ the heating plate.Speed ratio between the second roller limit and the first roller limit is 15: 1.Band lateral expansion to ratio under about 360 ℃ temperature with longitudinal dilatation is 30: 1 then, limits then, and heating is about 20 seconds in being set at 390 ℃ baking oven.This method produces high intensity, porous film.The method condition of this embodiment and the size of intermediate are shown in Table 1.
Measure various character by aforesaid method then and characterize this film.The film character of Zhi Bei sample is shown in Table 2 in this embodiment.Notice that water enters pressure and is at least 4136 kPas, this is because the tester higher value of energy measurement not.The grignard value of the sample of this embodiment and BP data are shown among Fig. 1.The water flux rate and the BP data of the sample of this embodiment are shown among Fig. 2.The water flux rate of the sample of this embodiment and average flow aperture data are shown among Fig. 6.
Embodiment 4
Will (Exxon Mobil Corporation of Virginia, USA Fairfax (Exxon Mobil Corp., Fairfax, VA)) be according to the ratio mixing of 0.196 gram/gram fine powder as the end of the PTFE fine polymer powder described in the United States Patent (USP) 6541589 and lsopar K.The lubricated powder of compacting forms bead in cylinder, places about 12 hours in being set at 70 ℃ baking oven.Bead through compacting and heating is carried out plunger type extrude, produce wide about 15.2 centimetres, thick about 0.73 millimeter band.The band that to extrude is rolling between pressure roller then, to thickness be 0.254 millimeter.With described band cross directional stretch to 56 centimetre (being that ratio is 3.7: 1), limit, then then 270 ℃ of dryings.Dry zone longitudinal dilatation between two roller limits that are set on 345 ℃ the heating plate.Speed ratio between the second roller limit and the first roller limit is 15: 1.Band lateral expansion to ratio under about 360 ℃ temperature with longitudinal dilatation is 30: 1 then, limits then, and heating is about 24 seconds in being set at 380 ℃ baking oven.This method produces high intensity, porous film.The method condition of this embodiment and the size of intermediate are shown in Table 1.
Measure various character by aforesaid method then and characterize this film.The film character of Zhi Bei sample is shown in Table 2 in this embodiment.Recording light transmittance is 90%.The grignard value of the sample of this embodiment and BP data are shown among Fig. 1.The water flux rate and the BP data of the sample of this embodiment are shown among Fig. 2.The water flux rate of the sample of this embodiment and average flow aperture data are shown among Fig. 6.
Embodiment 5
Will (Exxon Mobil Corporation of Virginia, USA Fairfax (Exxon Mobil Corp., Fairfax, VA)) be according to the ratio mixing of 0.202 gram/gram fine powder as the end of the PTFE fine polymer powder described in the United States Patent (USP) 6541589 and lsopar K.The lubricated powder of compacting forms bead in cylinder, places about 12 hours in being set at 70 ℃ baking oven.Bead through compacting and heating is carried out plunger type extrude, produce wide about 15.2 centimetres, thick about 0.73 millimeter band.Produce independently band of three volumes, these bands are stacked together between pressure roller, to thickness be 0.76 millimeter.With described band cross directional stretch to 56 centimetre (being that ratio is 3.7: 1), limit, then then 250 ℃ of dryings.Longitudinal dilatation between two roller limits of dry zone in being set at 345 ℃ the thermal treatment zone.Speed ratio between the second roller limit and the first roller limit is 20: 1.Band lateral expansion to ratio under about 360 ℃ temperature with longitudinal dilatation is 22: 1 then, limits then, about 20 seconds of 390 ℃ of heating.This method produces high intensity, porous film.The method condition of this embodiment and the size of intermediate are shown in Table 1.
Measure various character by aforesaid method then and characterize this film.The film character of Zhi Bei sample is shown in Table 2 in this embodiment.The grignard value of the sample of this embodiment and BP data are shown among Fig. 1.The water flux rate and the BP data of the sample of this embodiment are shown among Fig. 2.The water flux rate of the sample of this embodiment and average flow aperture data are shown among Fig. 6.
Embodiment 6
According to the following step the film of embodiment 1 is handled and to be made its possess hydrophilic property.In the frame that stretches tight with described membrane sample stuck-at-0.16 cm diameter, keep the state of tightening.1% polyvinyl alcohol (catalog number (Cat.No.) 363170, sigma-A Deruiqi company (Sigma-Aldrich Co)) is dissolved in 50/50 mixture of isopropyl alcohol/deionized water, makes a kind of solution.With the described frame submergence 1 minute in this solution of stretching tight, washed again 1 minute with deionized water then.Then the described frame that stretches tight is being contained 2% glutaraldehyde (catalog number (Cat.No.) 340855, sigma-A Deruiqi company (Sigma-Aldrich Co)), submergence 1 minute in the deionized water solution of 1% hydrochloric acid (catalog number (Cat.No.) 435570, sigma-A Deruiqi company (Sigma-Aldrich Co)).Solution temperature is remained on 50 ℃.Spent deionised water then 1 minute.At last, sample is dry in being set at 150 ℃ baking oven.Behind the sample finish-drying, it is taken out from baking oven.The gained sample can be at once by water-wet, and its wettability rank shows as 0.In this embodiment the bubbling point of Zhi Bei hydrophilic film and water flux rate value be respectively 697 kPas and 0.03 cm per minute/kPa.The water flux rate and the BP data of this embodiment sample are shown among Fig. 3.
Embodiment 7
According to the following step the film of embodiment 2 is handled and to be made its possess hydrophilic property.In the frame that stretches tight with described membrane sample stuck-at-0.16 cm diameter, keep the state of tightening.1% polyvinyl alcohol (catalog number (Cat.No.) 363170, sigma-A Deruiqi company (Sigma-Aldrich Co)) is dissolved in 50/50 mixture of isopropyl alcohol/deionized water, makes a kind of solution.With the described frame submergence 1 minute in this solution of stretching tight, washed again 1 minute with deionized water then.Then the described frame that stretches tight is being contained 2% glutaraldehyde (catalog number (Cat.No.) 340855, sigma-A Deruiqi company (Sigma-Aldrich Co)), submergence 1 minute in the deionized water solution of 1% hydrochloric acid (catalog number (Cat.No.) 435570, sigma-A Deruiqi company (Sigma-Aldrich Co)).Solution temperature is remained on 50 ℃.Spent deionised water then 1 minute.At last, sample is dry in being set at 150 ℃ baking oven.Behind the sample finish-drying, it is taken out from baking oven.The gained sample can be at once by water-wet, and its wettability rank shows as 0.In this embodiment the bubbling point of Zhi Bei hydrophilic film and water flux rate value be respectively 672 kPas and 0.05 cm per minute/kPa.The water flux rate and the BP data of this embodiment sample are shown among Fig. 3.
Embodiment 8
According to the following step the film of embodiment 4 is handled and to be made its possess hydrophilic property.In the frame that stretches tight with described membrane sample stuck-at-0.16 cm diameter, keep the state of tightening.1% polyvinyl alcohol (catalog number (Cat.No.) 363170, sigma-A Deruiqi company (Sigma-Aldrich Co)) is dissolved in 50/50 mixture of isopropyl alcohol/deionized water, makes a kind of solution.With the described frame submergence 1 minute in this solution of stretching tight, washed again 1 minute with deionized water then.Then the described frame that stretches tight is being contained 2% glutaraldehyde (catalog number (Cat.No.) 340855, sigma-A Deruiqi company (Sigma-Aldrich Co)), submergence 1 minute in the deionized water solution of 1% hydrochloric acid (catalog number (Cat.No.) 435570, sigma-A Deruiqi company (Sigma-Aldrich Co)).Solution temperature is remained on 50 ℃.Spent deionised water then 1 minute.At last, sample is dry in being set at 150 ℃ baking oven.Behind the sample finish-drying, it is taken out from baking oven.The gained sample can be at once by water-wet, and its wettability rank shows as 0.In this embodiment the bubbling point of Zhi Bei hydrophilic film and water flux rate value be respectively 760 kPas and 0.1 cm per minute/kPa.The water flux rate and the BP data of this embodiment sample are shown among Fig. 3.
Embodiment 9
With PTFE fine polymer powder the end ((DaikinIndustries of Da Ken industrial group of New York Orangeburg, Ltd., Orangeburg, NY)) with lsopar K ((the Exxon Mobil Corp. of the Exxon Mobil Corporation of Virginia, USA Fairfax, Fairfax, VA)) mix according to the ratio of 0.196 gram/gram fine powder.The lubricated powder of compacting forms bead in cylinder, places about 12 hours in being set at 70 ℃ baking oven.Bead through compacting and heating is carried out plunger type extrude, produce wide about 15.2 centimetres, thick about 0.73 millimeter band.Produce independently band of three volumes, these bands are stacked together between pressure roller, to thickness be 0.76 millimeter.With described band cross directional stretch to 56 centimetre (being that ratio is 3.7: 1), limit then, dry in being set at 270 ℃ baking oven then.Dry zone longitudinal dilatation between two roller limits that are set on 340 ℃ the heating plate.Expansion ratio with the ratio calculation between the speed on two roller limits is 25: 1.Band lateral expansion to ratio under about 360 ℃ temperature with longitudinal dilatation is 20: 1 then, limits then, and heating is about 60 seconds in being set at 390 ℃ baking oven.This method produces high intensity, porous film.
Described film has following character: thickness is 0.0051 millimeter, and density is 0.334 gram per centimeter 3, vertically matrix tensile strength is 546 MPas, laterally matrix tensile strength is 276 MPas, the steel ball bursting strength is 22.7 Ns, and the Fu Leize value is 2.8, and bubbling point is 317 kPas, the water flux rate be 1.72 cm per minute/kPa, the average flow aperture is 0.101 micron, surface area is 24.8 meters 2/ gram.The water flux rate and the BP data of this film are shown among Fig. 2.The water flux rate of this film and average flow aperture data are shown among Fig. 6.
According to the following step this film is handled and to be made its possess hydrophilic property.In the frame that stretches tight with described membrane sample stuck-at-0.16 cm diameter, keep the state of tightening.1% polyvinyl alcohol (catalog number (Cat.No.) 363170, sigma-A Deruiqi company (Sigma-Aldrich Co)) is dissolved in 50/50 mixture of isopropyl alcohol/deionized water, makes a kind of solution.With the described frame submergence 1 minute in this solution of stretching tight, washed again 1 minute with deionized water then.Then the described frame that stretches tight is being contained 2% glutaraldehyde (catalog number (Cat.No.) 340855, sigma-A Deruiqi company (Sigma-Aldrich Co)), submergence 1 minute in the deionized water solution of 1% hydrochloric acid (catalog number (Cat.No.) 435570, sigma-A Deruiqi company (Sigma-Aldrich Co)).Solution temperature is remained on 50 ℃.Spent deionised water then 1 minute.At last, sample is dry in being set at 150 ℃ baking oven.When sample drying, it is taken out from baking oven.The gained sample can be at once by water-wet, and its wettability rank shows as 0.In this embodiment the bubbling point of Zhi Bei hydrophilic film and water flux rate value be respectively 312 kPas and 0.42 cm per minute/kPa.The water flux rate and the BP data of the treated film of this embodiment are shown among Fig. 3.
Embodiment 10
By the hydrophilic film with embodiment 7 be clipped in two other the layer between and this hydrophilic film is built into the composite hydrophilic filter.
These exterior layers are that the Fu Leize value is 40 the ePTFE film that has carried out hydrophilicity-imparting treatment subsequently.These two layers are as cover layer (promptly covering the layer at least a portion surface of described film); They have high fluid permeability, and the composite hydrophilic filter of the assembling of gained has and the essentially identical permeability of the hydrophilic film of embodiment 7 like this.Use following steps to make skin or covering layer film possess hydrophilic property.Each covering layer film is fixed in the frame that stretches tight of 10.16 centimetres of diameters, keeps the state of tightening.1% polyvinyl alcohol (catalog number (Cat.No.) 363170, sigma-A Deruiqi company (Sigma-Aldrich Co)) is dissolved in 50/50 mixture of isopropyl alcohol/deionized water, makes a kind of solution.With the described frame submergence 1 minute in this solution of stretching tight, washed again 1 minute with deionized water then.Then the described frame that stretches tight is being contained 2% glutaraldehyde (catalog number (Cat.No.) 340855, sigma-A Deruiqi company (Sigma-Aldrich Co)) submergence is 1 minute and in the deionized water solution of 1% hydrochloric acid (catalog number (Cat.No.) 435570, sigma-A Deruiqi company (Sigma-Aldrich Co)).Solution temperature is remained on 50 ℃.Spent deionised water then 1 minute.At last, each cover layer is dry in being set at 150 ℃ baking oven.When sample drying, it is taken out from baking oven.
At this moment, be arranged between two hydrophily coverlays with stacked but not bonding structure by hydrophilic film and assembled the composite hydrophilic filter embodiment 7.Therefore, described complex filter is to be made of three layers that pile up that loosen successively.The marginal portion of this complex is according to the requirement sealing of test fixture.The bubbling point of described hydrophily complex and water flux rate value be respectively 678 kPas and 0.06 cm per minute/kPa.Described complex can be at once by water-wet, and its wettability rank shows as 0.The water flux rate and the BP data of the sample of this embodiment are shown among Fig. 3.The data point of noting described composite article is very approaching with the data point of the film (embodiment 7) that is used to make up this complex.The similarity of described film and described goods proves that the good character of described film can remain in the final composite article.
Embodiment 11
By the hydrophilic film with embodiment 8 be clipped in two other the layer between and this hydrophilic film is built into the composite hydrophilic filter.These two exterior layers or cover layer are according to making with embodiment 10 described identical methods.
Be arranged between two hydrophily coverlays with stacked but not bonding structure by hydrophilic film and assembled the composite hydrophilic filter embodiment 8.Therefore, described complex filter is to be made of three layers that pile up that loosen successively.The marginal portion of this complex is according to the requirement sealing of test fixture.In this embodiment the bubbling point of Zhi Bei hydrophily complex and water flux rate value be respectively 705 kPas and 0.09 cm per minute/kPa.Described complex can be at once by water-wet, and its wettability rank shows as 0.The water flux rate and the BP data of the sample of this embodiment are shown among Fig. 3.The data point of noting described composite article is very approaching with the data point of the film (embodiment 8) that is used to make up this complex.The similarity of described film and described complex proves that the good character of described film can remain in the final composite article.
Embodiment 12
By the hydrophilic film with embodiment 9 be clipped in two other the layer between and this hydrophilic film is built into the composite hydrophilic filter.These two exterior layers or cover layer are according to making with embodiment 10 described identical methods.
At this moment, be arranged between two hydrophily coverlays with stacked but not bonding structure by hydrophilic film and assembled the composite hydrophilic filter embodiment 9.In test process, suitably the marginal portion of described complex is clamped, to test.Therefore, described complex filter is to be made of three layers that pile up that loosen successively.The marginal portion of described complex is according to the requirement sealing of test fixture.Described complex can be at once by water-wet, and its wettability rank shows as 0.The water flux rate and the BP data of the sample of this embodiment are shown among Fig. 3.The data point of noting described composite article is very approaching with the data point of the film (embodiment 9) that is used to make up this complex.The similarity of described film and described complex proves that the good character of described film can remain in the final composite article.
Embodiment 13
Embodiment 1 described film to the embodiment of the invention 1 according to No. the 5116650th, United States Patent (USP) is handled, and makes it have oleophobic property.The oil level of gained film is 3.The water of the oleophobic property film for preparing among this embodiment enters pressure and grignard value is respectively 2447 kPas and 34 seconds.The water of the sample of this embodiment enters pressure and the grignard value data are shown among Fig. 4.
Embodiment 14
Embodiment 1 described film to the embodiment of the invention 2 according to No. the 5116650th, United States Patent (USP) is handled, and makes it have oleophobic property.The oil level of gained film is 3.The water of the oleophobic property film for preparing among this embodiment enters pressure and grignard value is respectively 2530 kPas and 22 seconds.The water of the sample of this embodiment enters pressure and the grignard value data are shown among Fig. 4.
Embodiment 15
Be clipped between two other layers by film and use this film to make up complex filter embodiment 2.These two exterior layers or cover layer are that the Fu Leize value is 40 ePTFE film.These two layers are as cover layer; They have high fluid permeability, and the complex filter of gained has and the essentially identical permeability of the film of embodiment 2 like this.
Be arranged between two coverlays with stacked but not bonding structure by film and assembled complex filter embodiment 2.Therefore, described complex filter is to be made of three layers that pile up that loosen successively.The marginal portion of described complex is according to the requirement sealing of test fixture.The bubbling point of described complex filter and water flux rate value be respectively 556 kPas and 0.37 cm per minute/kPa.The water flux rate and the BP data of the sample of this embodiment are shown among Fig. 2.The data point of noting described complex is very approaching with the data point of the film (embodiment 2) that is used to make up this complex.The similarity of described film and described complex proves that the good character of described film can remain in the final composite article.
Embodiment 16
Be clipped between two other layers by film and use this film to make up complex filter embodiment 4.This two layers of outer layer is that the Fu Leize value is 40 ePTFE film.These two layers are as cover layer; They have high fluid permeability, and the complex filter of gained has and the essentially identical permeability of the film of embodiment 4 like this.
Be arranged between two coverlays with stacked but not bonding structure by film and assembled complex filter embodiment 4.Therefore, described complex filter is to be made of three layers that pile up that loosen successively.The marginal portion of described complex is according to the requirement sealing of test fixture.The bubbling point of described complex filter and water flux rate value be respectively 575 kPas and 0.66 cm per minute/kPa.The water flux rate and the BP data of the sample of this embodiment are shown among Fig. 2.The data point of noting described composite article is very approaching with the data point of the film (embodiment 4) that is used to make up this complex.The similarity of described film and described complex proves that the good character of described film can remain in the final composite article.
Embodiment 17
(Exxon Mobil Corporation of Virginia, USA Fairfax (Exxon Mobil Corp., Fairfax, VA)) is according to the ratio mixing of 0.196 gram/gram fine powder with the described PTFE fine polymer powder of No. the 6541589th, United States Patent (USP) end and lsopar K.The lubricated powder of compacting forms bead in cylinder, places about 12 hours in being set at 70 ℃ baking oven.Bead through compacting and heating is carried out plunger type extrude, produce wide about 15.2 centimetres, thick about 0.73 millimeter band.The band that to extrude is rolling between pressure roller then, to thickness be 0.19 millimeter.Then with described band cross directional stretch to 56 centimetre (being that ratio is 3.7: 1), then 250 ℃ of dryings.Dry zone longitudinal dilatation between two roller limits that are set on 340 ℃ the heating plate.Speed ratio between the second roller limit and the first roller limit is 20: 1.Band lateral expansion to ratio under about 360 ℃ temperature with longitudinal dilatation is 20: 1 then, limits then, and heating is about 180 seconds in being set at 400 ℃ baking oven.
This method produces high intensity, porous film.Described film has following character: thickness is 0.0025 millimeter, and density is 0.180 gram per centimeter 3, vertically matrix tensile strength is 609 MPas, laterally matrix tensile strength is 220 MPas, the steel ball bursting strength is 3.6 Ns, and the Fu Leize value is 6.1, and bubbling point is 337 kPas, the water flux rate be 2.49 cm per minute/kPa, the average flow aperture is 0.085 micron, light transmittance is 92%.The water flux rate of this film and average flow aperture data are shown among Fig. 6.
Use this film to make up complex filter by this film being clipped between two other layers.These exterior layers are that the Fu Leize value is 40 ePTFE film.These two layers are as cover layer; They have high fluid permeability, and the complex filter of gained has the essentially identical permeability of film for preparing before with this embodiment like this.
By being arranged between two coverlays with stacked but not bonding structure, this film assembled complex filter.Therefore, described complex filter is to be made of three layers that pile up that loosen successively.The marginal portion of described complex is according to the requirement sealing of test fixture.The bubbling point of described complex filter and water flux rate value be respectively 374 kPas and 1.92 cm per minute/kPa.The water flux rate and the BP data of the film of this embodiment and composite article are shown among Fig. 2.The data point of noting described composite article is very approaching with the data point of the film that is used to make up this complex.The similarity of described film and described complex proves that the good character of the film of this embodiment preparation can remain in the final composite article.
Though disclosed the present invention in conjunction with some embodiment and detailed description, but it will be apparent for a person skilled in the art that, can make amendment or change these details without departing from the spirit of the invention, these modifications or change be also thought within the scope of the claims.

Claims (87)

1. goods, it comprises the porous PTFE film, and the relation of the grignard value-bubbling point of described film is equal to or less than equation log (grignard value)=5.13 * 10 -3The line that (bubbling point)-1.26 limit, surface area is at least 20 meters 2/ gram.
2. goods as claimed in claim 1 is characterized in that, described porous PTFE film comprises expanded PTFE.
3. goods as claimed in claim 1 is characterized in that, the ratio of the matrix tensile strength on two orthogonal directions is 2: 1 or littler.
4. goods as claimed in claim 1 is characterized in that, the product of described matrix tensile strength on two orthogonal directions is greater than 1.3 * 10 5MPa 2
5. goods as claimed in claim 1 is characterized in that, the product of described matrix tensile strength on two orthogonal directions is greater than 1.5 * 10 5MPa 2
6. goods as claimed in claim 1 is characterized in that, the product of described matrix tensile strength on two orthogonal directions is greater than 1.9 * 10 5MPa 2
7. goods as claimed in claim 1 is characterized in that the light transmittance of described PTFE film is greater than 50%.
8. goods as claimed in claim 1 is characterized in that, the relation of described grignard value-bubbling point is equal to or less than equation log (grignard value)=5.13 * 10 -3The line that (bubbling point)-1.58 limit.
9. goods as claimed in claim 1 is characterized in that, the relation of described grignard value-bubbling point is equal to or less than equation log (grignard value)=5.13 * 10 -3The line that (bubbling point)-2.02 limit.
10. goods, it comprises the porous PTFE film, and the light transmittance of described film is at least 50%, porosity is at least 50%.
11. goods as claimed in claim 10 is characterized in that, described porous PTFE film comprises expanded PTFE.
12. goods as claimed in claim 10 is characterized in that, the light transmittance of described porous PTFE film is at least 85%, and porosity is at least 75%.
13. goods, it comprises the porous PTFE film, and the surface area of described film is at least 20 meters 2/ gram.
14. goods as claimed in claim 13 is characterized in that, described porous PTFE film comprises expanded PTFE.
15. goods as claimed in claim 13 is characterized in that, the surface area of described porous PTFE film is at least 27 meters 2/ gram.
16. goods, it comprises the porous PTFE film, and the bubbling point of described film is at least 448 kPas, and the relation of grignard value-bubbling point is equal to or less than equation log (grignard value)=2.60 * 10 -3The line that (bubbling point)-0.54 limits.
17. the article of claim 16 is characterized in that, described porous PTFE film comprises expanded PTFE.
18. the article of claim 16 is characterized in that, the relation of described grignard value-bubbling point is equal to or less than equation log (grignard value)=2.60 * 10 -3The line that (bubbling point)-0.59 limits.
19. the article of claim 16 is characterized in that, the relation of described grignard value-bubbling point is equal to or less than equation log (grignard value)=2.60 * 10 -3The line that (bubbling point)-1.12 limit.
20. a porous PTFE film, the product of its matrix tensile strength on two orthogonal directions is at least 1.3 * 10 5MPa 2
21. goods as claimed in claim 20 is characterized in that, described porous PTFE film comprises expanded PTFE.
22. goods as claimed in claim 20 is characterized in that, the product of described matrix tensile strength on two orthogonal directions is greater than 1.5 * 10 5MPa 2
23. goods as claimed in claim 20 is characterized in that, the product of described matrix tensile strength on two orthogonal directions is greater than 1.9 * 10 5MPa 2
24. goods, it comprises the porous PTFE film, and the relation of the grignard value-bubbling point of described film is equal to or less than equation log (grignard value)=5.13 * 10 -3The line that (bubbling point)-1.26 limit, the product of the matrix tensile strength on two orthogonal directions is at least 1.3 * 10 5MPa 2
25. goods as claimed in claim 24 is characterized in that, described porous PTFE film comprises expanded PTFE.
26. goods as claimed in claim 24 is characterized in that, the product of described matrix tensile strength on two orthogonal directions is greater than 1.5 * 10 5
27. goods as claimed in claim 24 is characterized in that, the product of described matrix tensile strength on two orthogonal directions is greater than 1.9 * 10 5
28. goods as claimed in claim 24 is characterized in that, the relation of described grignard value-bubbling point is equal to or less than equation log (grignard value)=5.13 * 10 -3The line that (bubbling point)-1.58 limit.
29. goods as claimed in claim 24 is characterized in that, the relation of described grignard value-bubbling point is equal to or less than equation log (grignard value)=5.13 * 10 -3The line that (bubbling point)-2.02 limit.
30. goods, it comprises the porous PTFE film, and the relation that the water of described film enters pressure-grignard value is equal to or higher than the line that equation WEP=3 (grignard value)+2500 limits.
31. goods as claimed in claim 30 is characterized in that, described porous PTFE film comprises expanded PTFE.
32. goods as claimed in claim 30 is characterized in that, the relation that described water enters pressure-grignard value is equal to or higher than the line that equation WEP=3 (grignard value)+2900 limits.
33. goods as claimed in claim 30 is characterized in that, the relation that described water enters pressure-grignard value is equal to or higher than the line that equation WEP=3 (grignard value)+3100 limits.
34. goods as claimed in claim 30 is characterized in that, the relation of described grignard value-bubbling point is equal to or less than equation log (grignard value)=5.13 * 10 -3The line that (bubbling point)-1.26 limit.
35. goods as claimed in claim 30 is characterized in that, described grignard value is 1-50 second.
36. goods as claimed in claim 30 is characterized in that, described grignard value is 5-50 second.
37. goods, it comprises the porous PTFE film, and the relation of the water flux rate-bubbling point of described film is equal to or higher than equation log (water flux rate)=-3.5 * 10 -3The line that (bubbling point)+1.3 limit.
38. goods as claimed in claim 37 is characterized in that, described porous PTFE film comprises expanded PTFE.
39. goods as claimed in claim 37 is characterized in that, the relation of described water flux rate-bubbling point is equal to or higher than equation log (water flux rate)=-3.5 * 10 -3The line that (bubbling point)+1.6 limit.
40. goods as claimed in claim 37 is characterized in that, the relation of water flux rate-bubbling point is equal to or higher than equation log (water flux rate)=-3.5 * 10 -3The line that (bubbling point)+2.0 limit.
41. goods, it comprises the porous PTFE film, and the relation in the water flux rate-average flow aperture of described film is equal to or higher than the line that equation log (water flux rate)=16.9 (average flow aperture)-1.85 limits.
42. goods as claimed in claim 41 is characterized in that, described porous PTFE film comprises expanded PTFE.
43. goods as claimed in claim 41 is characterized in that, the relation in water flux rate-average flow aperture is equal to or higher than the line that equation log (water flux rate)=16.9 (average flow aperture)-1.6 limits.
44. goods as claimed in claim 41 is characterized in that, the relation in water flux rate-average flow aperture is equal to or higher than the line that equation log (water flux rate)=16.9 (average flow aperture)-1.05 limits.
45. goods, it comprises the complex by at least one porous PTFE film and at least one other layer, and the relation of the water flux rate-bubbling point of described complex is equal to or higher than equation log (water flux rate)=-3.5 * 10 -3The line that (bubbling point)+1.3 limit.
46. goods as claimed in claim 45 is characterized in that, described porous PTFE film comprises expanded PTFE.
47. goods as claimed in claim 45 is characterized in that, the relation of water flux rate-bubbling point is equal to or higher than equation log (water flux rate)=-3.5 * 10 -3The line that (bubbling point)+1.6 limit.
48. goods as claimed in claim 45 is characterized in that, the relation of water flux rate-bubbling point is equal to or higher than equation log (water flux rate)=-3.5 * 10 -3The line that (bubbling point)+2.0 limit.
49. goods as claimed in claim 45 is characterized in that, described at least one other layer is selected from supatex fabric, scrim and fabric.
50. goods as claimed in claim 45 is characterized in that, described at least one other layer comprises at least one other layer on each side that is positioned at described at least one film.
51. goods as claimed in claim 45 is characterized in that, described at least one other layer comprises at least one perforated membrane.
52. goods as claimed in claim 51 is characterized in that, described at least one perforated membrane comprises ePTFE.
53. goods as claimed in claim 50 is characterized in that, described at least one other layer that is positioned on each side comprises ePTFE.
54. goods as claimed in claim 45 is characterized in that, are the filter form.
55. goods as claimed in claim 45 is characterized in that, are the air-vent form.
56. goods as claimed in claim 54 is characterized in that, are the Filter cartridge form.
57. goods, it comprises the complex of being made up of at least one porous PTFE film and at least one other layer, described complex can also be at once by water-wet, and the relation of the water flux rate-bubbling point of described complex is equal to or higher than the line that equation log (water flux rate)=-0.01 (bubbling point)+1.3 limit.
58. goods as claimed in claim 57 is characterized in that, described porous PTFE film comprises expanded PTFE.
59. goods as claimed in claim 57 is characterized in that, the relation of water flux rate-bubbling point is equal to or higher than the line that equation log (water flux rate)=-0.01 (bubbling point)+2.48 limit.
60. goods as claimed in claim 57 is characterized in that, the relation of water flux rate-bubbling point is equal to or higher than the line that equation log (water flux rate)=-0.01 (bubbling point)+5.0 limit.
61. goods as claimed in claim 57 is characterized in that, described at least one other layer is selected from supatex fabric, scrim and fabric.
62. goods as claimed in claim 57 is characterized in that, described at least one other layer comprises at least one other layer on each side that is positioned at described at least one film.
63. goods as claimed in claim 57 is characterized in that, described at least one other layer comprises at least one perforated membrane.
64., it is characterized in that described at least one perforated membrane comprises ePTFE as the described goods of claim 63.
65. goods as claimed in claim 62 is characterized in that, described at least one other layer that is positioned on each side comprises ePTFE.
66. goods as claimed in claim 57 is characterized in that, are the filter form.
67. goods as claimed in claim 57 is characterized in that, are the air-vent form.
68. as the described goods of claim 66, it is characterized in that, be the Filter cartridge form.
69. goods, it comprises can be at once by the porous PTFE film of water-wet, and the relation of the water flux rate-bubbling point of described film is equal to or higher than the line that equation log (water flux rate)=-0.01 (bubbling point)+1.3 limit.
70., it is characterized in that described porous PTFE film comprises expanded PTFE as the described goods of claim 69.
71., it is characterized in that the relation of water flux rate-bubbling point is equal to or less than the line that equation log (water flux rate)=-0.01 (bubbling point)+2.48 limit as the described goods of claim 69.
72., it is characterized in that the relation of water flux rate-bubbling point is equal to or less than the line that equation log (water flux rate)=-0.01 (bubbling point)+5.0 limit as the described goods of claim 69.
73. goods, it comprises at least one porous PTFE film, and the oil level of described film is at least 2, and the water of described goods enters pressure greater than 500 kPas, and grignard value is up to 350 seconds.
74., it is characterized in that the oil level of described goods is at least 3 as the described goods of claim 73.
75., it is characterized in that the oil level of described goods is at least 5 as the described goods of claim 73.
76., it is characterized in that the water of described goods enters pressure greater than 1250 kPas as the described goods of claim 73, grignard value is up to 200 seconds.
77., it is characterized in that the water of described goods enters pressure greater than 2000 kPas as the described goods of claim 73, grignard value is up to 100 seconds.
78., it is characterized in that described porous PTFE film comprises expanded PTFE as the described goods of claim 73.
79. goods, it comprises the porous PTFE film, and the relation of the grignard value-bubbling point of described film is equal to or less than equation log (grignard value)=5.13 * 10 -3The line that (bubbling point)-1.22 limit, light transmittance is at least 50%.
80., it is characterized in that described porous PTFE film comprises expanded PTFE as the described goods of claim 79.
81., it is characterized in that the relation of described grignard value-bubbling point is equal to or less than equation log (grignard value)=5.13 * 10 as the described goods of claim 79 -3The line that (bubbling point)-1.58 limit.
82., it is characterized in that the relation of described grignard value-bubbling point is equal to or less than equation log (grignard value)=5.13 * 10 as the described goods of claim 79 -3The line that (bubbling point)-2.02 limit.
83. a method of filtering fluid, it comprises:
The filter that comprises the porous PTFE film is provided, and the relation of the water flux rate-bubbling point of described film is equal to or higher than equation log (water flux rate)=-3.5 * 10 -3The line that (bubbling point)+1.3 limit;
Make the fluid that contains particle by described filter;
Thereby from described fluid, filter described particle.
84. a method of filtering fluid, it comprises:
The filter that comprises the porous PTFE film is provided, and the relation in the water flux rate-average flow aperture of described film is equal to or higher than the line that equation log (water flux rate)=16.9 (average flow aperture)-1.85 limits;
Make the fluid that contains pollutant by described filter;
Thereby from described fluid, filter described particle.
85. a method of filtering fluid, it comprises:
The filter that comprises the complex that is made of at least one porous PTFE film and at least one other layer is provided, and the relation of the water flux rate-bubbling point of described complex is equal to or higher than equation log (water flux rate)=-3.5 * 10 -3The line that (bubbling point)+1.3 limit;
Make the fluid that contains particle by described filter;
Thereby from described fluid, filter described particle.
86. a method of filtering fluid, it comprises:
Provide that comprise can be at once by the filter of the porous PTFE film of water-wet, the relation of the water flux rate-bubbling point of described film is equal to or higher than the line that equation log (water flux rate)=-0.01 (bubbling point)+1.3 limit;
Make the fluid that contains particle by described filter;
Thereby from described fluid, filter described particle.
87., it is characterized in that described filter comprises the hydrophily complex as the described method of claim 85.
CNA2006800304509A 2005-07-18 2006-06-21 Porous PTFE materials and articles produced therefrom Pending CN101242889A (en)

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US11/184,706 2005-07-18
US11/334,243 2006-01-18

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Cited By (7)

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Publication number Priority date Publication date Assignee Title
CN101850201A (en) * 2009-03-23 2010-10-06 通用电气公司 Layered filtration membrane and manufacture method thereof
CN102233691A (en) * 2010-04-29 2011-11-09 通用电气公司 Improved porous membrane
CN102395419A (en) * 2009-03-17 2012-03-28 日本奥亚特克斯股份有限公司 Water vapor-permeable diaphragm material
CN102939328A (en) * 2010-06-15 2013-02-20 日东电工株式会社 Polytetrafluoroethylene porous membrane with small elongation anisotropy and process for production thereof
CN103037722A (en) * 2010-05-06 2013-04-10 戈尔企业控股股份有限公司 Contamination resistant air permeable fabric laminate and garments made therefrom
CN103458934A (en) * 2011-04-01 2013-12-18 W.L.戈尔及同仁股份有限公司 Durable high strength polymer composite suitable for implant and articles produced therefrom
CN106471821A (en) * 2014-07-07 2017-03-01 W.L.戈尔及同仁股份有限公司 For protecting equipment and the method for microelectromechanical systems

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102395419A (en) * 2009-03-17 2012-03-28 日本奥亚特克斯股份有限公司 Water vapor-permeable diaphragm material
CN102395419B (en) * 2009-03-17 2014-06-11 日本奥亚特克斯股份有限公司 Water vapor-permeable diaphragm material
CN101850201B (en) * 2009-03-23 2015-09-02 Bha阿尔泰尔有限责任公司 Layered filtration membrane and manufacture method thereof
CN101850201A (en) * 2009-03-23 2010-10-06 通用电气公司 Layered filtration membrane and manufacture method thereof
CN102233691A (en) * 2010-04-29 2011-11-09 通用电气公司 Improved porous membrane
CN103037722A (en) * 2010-05-06 2013-04-10 戈尔企业控股股份有限公司 Contamination resistant air permeable fabric laminate and garments made therefrom
CN103037722B (en) * 2010-05-06 2015-10-21 W.L.戈尔及同仁股份有限公司 Resistant to pollution, to can pass through air fabric laminate and the clothes obtained by it
CN102939328A (en) * 2010-06-15 2013-02-20 日东电工株式会社 Polytetrafluoroethylene porous membrane with small elongation anisotropy and process for production thereof
CN103458934A (en) * 2011-04-01 2013-12-18 W.L.戈尔及同仁股份有限公司 Durable high strength polymer composite suitable for implant and articles produced therefrom
CN103458934B (en) * 2011-04-01 2017-02-15 W.L.戈尔及同仁股份有限公司 Durable high strength polymer composite suitable for implant and articles produced therefrom
CN106471821A (en) * 2014-07-07 2017-03-01 W.L.戈尔及同仁股份有限公司 For protecting equipment and the method for microelectromechanical systems
EP3167623A1 (en) * 2014-07-07 2017-05-17 W. L. Gore & Associates, Inc. Apparatus and method for protecting a micro-electro-mechanical system
EP3167623B1 (en) * 2014-07-07 2023-08-30 W. L. Gore & Associates, Inc. Apparatus and method for protecting a micro-electro-mechanical system

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