APPARATUS AND METHOD FOR ROLL-TO-ROLL MEMBRANE MANUFACTURE

Abstract

A roll-to-roll process and apparatus is disclosed for treatment of a membrane substrate. The apparatus and process processes the membrane substrate in a forward direction using one or more treatment solutions, and then processes the membrane substrate in a reverse direction using other treatment solutions. The treatment solutions used in the forward and reverse directions are preferably chosen so that the treatment sequence is the same in both directions. In this manner, the membrane substrate can accumulate reaction time by repeated processing in forward and reverse directions. t,?

Claims

1. An apparatus for continuous roll-to-roll processing of a membrane substrate with a first treating solution, a second treating solution, and a third treating solution, the apparatus comprising: a first roll and a second roll, the membrane substrate being windable and unwindable on both the first and second rolls to process the membrane substrate in a forward direction and a reverse direction; the first treating solution for treating the membrane substrate as the membrane substrate is processed in the forward direction but not in the reverse direction; the second treating solution for treating the membrane substrate as the membrane substrate is processed in the reverse direction but not in the forward direction; and the third treating solution for treating the membrane substrate as the membrane substrate is processed in both the forward and the reverse directions.

2. The apparatus according to claim 1, further comprising rollers associated with the first treating solution and the second treating solution, each of the rollers being independently switchable between a treating arrangement and a non-treating arrangement.

3. The apparatus according to claim 1, further comprising treatment baths for holding the first and second treating solutions, each of the treatment baths being independently movable between a treating arrangement and a non-treating arrangement.

4. The apparatus according to claim 1, further comprising treatment baths for holding the first and second treating solutions, and holding tanks in fluid communication with the treatment baths, each of the treating solutions in the treatment baths being independently drainable into a holding tank.

5. The apparatus according to claim 1, further comprising a plurality of treating solutions for treating the membrane substrate as the membrane substrate is processed in the forward direction but not in the reverse direction, and a plurality of treating solution for treating the membrane substrate as the membrane substrate is processed in the reverse direction but not in the forward direction.

6. The apparatus according to claim 1, wherein the first treatment solution, the second treatment solution , and the third treating solutions are arranged in a sequence so that the membrane substrate is treatable with the same sequence of treating solutions when the membrane substrate is processed in both the forward and reverse directions.

7. An apparatus for continuous roll-to-roll processing of a membrane substrate with a plurality of treating solutions, the apparatus comprising: a first roll and a second roll, the membrane substrate being windable and unwindable on both the first and second rolls, the plurality of treating solutions each being changeable between a treating configuration and a non-treating configuration for independently treating the membrane substrate as the membrane substrate is processed in a forward direction or in a reverse direction, wherein the membrane substrate is treatable with a first subset of the plurality of treating solutions and not treatable with a second subset of the plurality of treating solutions when first subset of the plurality of treating solutions is in the treating configuration and the second subset of the plurality of treating solutions is in the non-treating configuration, wherein the membrane substrate is treatable with the second subset of the plurality of treating solutions and not treatable with the first subset of the plurality of treating solutions when the second subset of the plurality of treating solutions is in the treating configuration and the first subset of the plurality of treating solutions is in the non-treating configuration, and wherein the membrane substrate is treatable with a third subset of the plurality of treating solutions when the third subset of the plurality of treating solutions is in the treating configuration.

8. The apparatus according to claim 7, further comprising rollers associated with the first and second subsets of the plurality of treatment baths, each of the rollers being independently switchable between a treating arrangement and a non-treating arrangement.

9. The apparatus according to claim 7, further comprising treatment baths for holding the plurality of treating solutions, each of the treatment baths being independently movable between a treating arrangement and a non-treating arrangement.

10. The apparatus according to claim 7, further comprising treatment baths for holding the plurality of treating solutions, and holding tanks in fluid communication with the treatment baths, each of the treating solutions in the treatment baths being independently drainable into a holding tank.

11. The apparatus according to claim 7, wherein the plurality of treating solutions are arranged in a sequence so that the membrane substrate is treatable with the same sequence of treating solutions when the membrane substrate is processed in both the forward and reverse directions.

12. A method of treating a membrane substrate with a plurality of treating solutions in a roll-to-roll process, the method comprising: processing the membrane substrate in a forward direction by treating the membrane substrate with a first subset of the plurality of treating solutions and not treating the membrane substrate with a second subset of the plurality of treating solutions; processing the membrane substrate in a reverse direction by treating the membrane substrate with the second subset of the plurality of treating solutions and not treating the membrane substrate with the first subset of the plurality of treating solutions; and processing the membrane substrate in forward and reverse directions by treating the membrane substrate with a third subset of the plurality of treating solutions.

13. The method according to claim 12, further comprising: switching the first subset of the plurality of treating solutions from treating arrangements to non-treating arrangements, and switching the second subset of the plurality of treating solutions from non-treating arrangements to treating arrangements.

14. The method according to claim 12, further comprising: moving rollers associated with the first subset of the plurality of treating solutions between treating arrangements and non-treating arrangements; and moving rollers associated with the second subset of the plurality of treating solutions between treating arrangements and non-treating arrangements.

15. The method according to claim 12, wherein: moving treatment baths containing the first subset of the plurality of treating solutions between treating arrangements and non-treating arrangements; and moving treatment baths containing the second subset of the plurality of treating solutions between treating arrangements and non-treating arrangements.

16. The method according to claim 12, wherein: transferring the first subset of the plurality of treating solutions between treatment baths and corresponding holding tanks; and transferring the second subset of the plurality of treating solutions between treatment baths and corresponding holding tanks.

17. The method according to claim 12, wherein the membrane substrate is exposed to the first subset of the plurality of treating solutions in a first sequence, and the membrane substrate is exposed to the second subset of the plurality of treating solutions in a second sequence, and wherein the first sequence and the second sequence are the same.

18. The method according to claim 12, wherein the method comprises processing the membrane substrate in a forward direction by treating the membrane substrate with the first and the third subsets of the plurality of treating solutions.

19. The method according to claim 12, wherein the method comprises processing the membrane substrate in a reverse direction by treating the membrane substrate with the second and the third subsets of the plurality of treating solutions.

20. An apparatus for continuous roll-to-roll processing of a membrane substrate with at least one treating solution, the apparatus comprising: a first roll and a second roll, the membrane substrate being windable and unwindable on both the first and second rolls; the at least one treating solution for treating the membrane substrate as the membrane substrate is processed in a forward direction, in a reverse direction, or in both the forward and the reverse direction.

21. A method of treating a membrane substrate with a treating solution in a roll-to-roll process, the method comprising: processing the membrane substrate in a forward direction by treating the membrane substrate with the treating solution while unwinding the membrane substrate from a first roll to a second roll; rewinding the treated membrane substrate from the second roll back to the first roll; and processing the treated membrane substrate in a forward direction by treating the treated membrane substrate with the treating solution while unwinding the treated membrane substrate from the first roll to the second roll.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Embodiments of the present disclosure will now be described, by way of example only, with reference to the attached Figures.

[0017] FIG. 1 illustrates one configuration of an example of an apparatus according to the present disclosure.

[0018] FIG. 2 illustrates another configuration of the apparatus illustrated in FIG. 1.

[0019] FIG. 3 illustrates one configuration of another example of an apparatus according to the present disclosure.

[0020] FIG. 4 illustrates another configuration of the apparatus illustrated in FIG. 3.

DETAILED DESCRIPTION OF THE INVENTION

[0021] FIG. 1 illustrates roll-to-roll processing apparatus 10. The apparatus 10 is an example of an immersion dip treatment apparatus. The apparatus 10 includes a first roll 12, and a second roll 14. A membrane substrate 16 is wound from the first roll to the second roll, passing around rollers 18A-F that are immersable in treating solutions 20A-F.

[0022] Rollers 18A-F are moveable between treating arrangements and non-treating arrangements, though it would be understood that each roller is independently movable and the configurations illustrated in FIGS. 1 and 2 are not the only possible configurations of the apparatus 10.

[0023] In one example, as illustrated in FIG. 1, rollers 18A, 18C, and 18D are positioned in treating arrangements to expose the membrane substrate 16 to the treating solutions 20A, 20C and 20D. The rollers 18B, 18E and 18F are positioned in non-treating arrangements, which allow the membrane substrate to be processed without being treated by the treating solutions 20B, 20E and 20F.

[0024] Once the membrane substrate has been treated in the forward direct using the configuration illustrated in FIG. 1, thereby exposing the membrane substrate to the treating solutions 20A, 20C and 20D, the membrane substrate is treated in the reverse direction by unwinding the membrane substrate from the second roller 14 onto the first roller 12, as illustrated in FIG. 2. In this manner, the membrane substrate is exposed to the treating solutions 20E, 20C and 20B, in that order. In the configuration illustrated in FIG. 2, roller 18F remains in the non-treating arrangement.

[0025] In some examples, the treating solutions 20A and 20E have the same chemical compositions, and the treating solutions 20B and 20D have the same chemical compositions. In such situations, the membrane substrate 16 is treated with the same sequence of treating solutions in both FIGS. 1 and 2. For example, when treating solutions 20A and 20E are ethanol solutions, when treating solutions 20B and 20D are basic solutions, and when treating solution 20C is an acidic solution, the membrane substrate is treated with, in order: ethanol, acid, then base, in both the forward processing direction of FIG. 1 and the reverse processing direction of FIG. 2.

[0026] The membrane substrate 16 is treated with treating solution 20C for a total time calculated on the distance the membrane substrate is contacting the treating solution 20C, divided by the linear velocity of the membrane substrate (feet per minute), multiplied by the number of times the membrane substrate is processed in either the forward or reverse directions.

[0027] In one specific example, the membrane substrate 16 is treated using the protocol shown in Table 1, where solutions 20A and 20E have the same chemical composition, and where solutions 20B and 20D have the same chemical compositions:

TABLE-US-00001 TABLE 1 Processing 18A 18B 18C 18D 18E 18F direction position position position position position position Forward Treating Not Treating Treating Not Not treating treating treating Reverse Not Treating Treating Not Treating Not treating Treating treating Forward Treating Not Treating Treating Not Not treating treating treating Reverse Not Treating Treating Not Treating Not treating treating treating Forward Treating Not Treating Treating Not Treating treating treating

[0028] Using the protocol in Table 1, the membrane substrate 16 is treated with treating solution 20C five times. At a linear rate of 2 feet per minute, and a reaction distance of 120 feet, the membrane substrate 16 is treated for a total of 120/2*5=300 minutes, or 5 hours. In order to achieve the same 300 minute reaction time using only a single-pass roll-to-roll process, it would be necessary to treat the membrane substrate at a linear velocity of 0.4 feet per minute if the distance was kept at 120 feet, or it would be necessary to increase the distance to 600 feet if the linear velocity was kept at 2 feet per minute.

[0029] The apparatus 10 may have additional rollers and treating solutions. For example, the apparatus may include a roller and treating solution between roller/treating solution 18E/20E and roller/treating solution 18F/20F. This additional treating solution may be a buffer solution to bring the porous membrane to a desired pH.

[0030] In an exemplary process, a polyacrylonitrile membrane, which has pores of 0.01 microns and a molecular weight cut off about 20,000 to 50,000 Daltons, is treated with acid to generate a hydrophilic membrane. The polyacrylonitrile membrane is treated using the protocol shown in Table 1, where: treating solution 20A is a solvent-exchange solution, treating solution 20B is a basic solution, treating solution 20C is an acidic solution, treating solution 20D is a basic solution, treating solution 20E is a solvent-exchange solution, and treating solution 20F is a humectant solution.

[0031] A solvent-exchange solution, such as ethanol solution, removes water from the membrane by exchanging the water for ethanol. A humectant solution, for example a solution of about 20% glycerol in water, enables a porous membrane to be dried while maintaining stability of the membrane morphology.

[0032] At a linear rate of 2 feet per minute, in a reaction tank that provides for 120 feet of reaction distance, and five processing directions, the polyacrylonitrile membrane is treated with acid for a total of 5 hours, is rinsed with a basic solution after every acid treatment, and is rinsed in a humectant solution after the final acid treatment.

[0033] The acid bath may be heated, for example to a temperature of up to 41? C. Heating the acid bath increases the reaction rate and allows the total reaction time to be decreased, for example by increasing the linear velocity of the membrane, decreasing the reaction distance, or reducing the number of times the membrane is processed. Raising the temperature from 21? C. to 31? C. doubles the reaction rate, and allows the linear velocity to be increased from 2 feet per minute to 4 feet per minute, thereby doubling the amount of hydrophilic membrane produced per unit time. Raising the temperature from 31? C. to 41? C. double the reaction rate again, and allows the linear velocity to be increased to 8 feet per minute, again doubling the amount of hydrophilic membrane produced per unit time.

[0034] The linear velocity of any processing step may independently differ from the linear velocity of other processing steps. Changing the linear velocity of a processing step changes the reaction time of the treating solutions used in that processing step. For example, a method may include a first processing step at a first linear velocity for treating the membrane substrate with a first subset of the treating solutions. The membrane substrate may then be treated in a second processing step at a second linear velocity for treating the membrane substrate with a second subset of the treating solutions. The second linear velocity may be reduced in comparison to the first linear velocity if it is desirable to increase the reaction time of the membrane substrate in the second subset of treating solutions.

[0035] The apparatus 10 may be used in alternate configurations than those illustrated in FIGS. 1 and 2. For example, in an exemplary method the rollers 18A and 18C, are first positioned in treating arrangements to expose the membrane substrate 16 to the treating solutions 20A and 20C. Once the membrane 16 has been treated in a forward direction, the roller configuration is changed to expose the membrane substrate 16 to the treating solution 20C. After processing in one or more forward and/or reverse directions in order to expose the membrane 16 to the desired total reaction time for treating solution 20C, the roller configuration is changed to expose the membrane substrate 16 to one or more other treating solutions.

[0036] An exemplary protocol for such a method is illustrated in Table 2. In this protocol, membrane 16 is exposed to treating solution 20C five times and is exposed to treating solutions 20D and 20F after the final exposure to treating solution 20C. In such an exemplary protocol, treating solutions 20B and 20E may be omitted.

[0037] Using such a protocol, and if treating solution 20A is an ethanol solution, treating solution 20C is an acidic solution, treating solution 20D is a basic solution, and treating solution 20F is a glycol solution, the membrane is treated first with ethanol to remove water from the membrane, then treated five times with acid. The acidic membrane is then neutralized by treating it with the basic solution, and then treated with the glycol solution. The protocol may include treating the membrane with a buffer solution between the basic solution and the glycol solution.

TABLE-US-00002 TABLE 2 Processing 18A 18C 18D 18F direction position position position position Forward Treating Treating Not Not treating treating Reverse Not Treating Not Not treating treating treating Forward Not Treating Not Not treating treating treating Reverse Not Treating Not Not treating treating treating Forward Not Treating Treating Treating treating

[0038] If a protocol resulted in the method finishing with the membrane travelling in a reverse processing direction, the apparatus may include roller 18B instead of roller 18D, and roller 18F may be positioned after roller 18B. In such a manner, the membrane 16 could be exposed to treating solutions 20C, 20B and 20F, in that order, in the final reverse processing step.

[0039] FIGS. 3 and 4 illustrate two configurations of an alternative apparatus 110 for a treating a membrane substrate. The components of apparatus 110 are the same as those discussed above with respect to apparatus 10 and, accordingly, have parallel reference numbers and are not discussed in detail. In contrast to apparatus 10, apparatus 110 includes movable treatment baths 120A-F, but stationary rollers 118A-F. FIG. 3 illustrates treatment baths 120A, 120C and 120D in treating arrangements, and treatment baths 120B, 120E and 120F in non-treating arrangements. FIG. 4 illustrates treatment baths 120B, 120C and 120E in treating arrangements, and treatment baths 120A, 120D and 120F in non-treating arrangements. Apparatus 110 is capable of treating the membrane substrate according to the protocols shown in Tables 1 and 2.

[0040] As illustrated above, the sequence of treatments may be the same when considered in the forward direction as when considered in the reverse direction. For example, the membrane substrate may be treated in a forward processing direction with solutions in the order A, B, C then D, and treated in the reverse processing direction with solutions in the same order A, B, C then D. Since the membrane substrate is being transferred between the first roll and the second roll, the solutions may be physically set up in the order: [first roll]-A, B, C, D, D, C, B, A-[second roll], where a prime indicates the subset of the treating solutions used in the forward processing direction, and double prime indicates the subset of the treating solutions used in the reverse processing direction. Treating solutions without a prime or double prime are shared in both the forward and reverse processing directions. It is beneficial to share a treating solution in both the forward and reverse processing so as to avoid duplication of the treating solution.

[0041] In view of the above, it should be understood that the chemical compositions of the treating solutions used to treat the membrane substrate may be the same regardless of the processing direction. That is, processing in the forward direction may include treating the membrane with the same solution, or with a separate solution of the same chemical composition that is used when processing in the reverse direction. For example, treating solutions A and A have the same chemical composition.

[0042] Other orders may be used to treat the membrane substrate with treating solutions A, B, C then D in both the forward and reverse processing directions. For example: [first roll]-A, D, B, C, B, D, A-[second roll]; [first roll]-A, D, C, B, C, D, A-[second roll]; [first roll]-D, C, B, A, B, C, D-[second roll]; or [first roll]-D, C, A, B, C, D, A-[second roll] all result in the membrane substrate being treated with treating solutions in the order A, B, C then D in both the forward and reverse directions.

[0043] Apparatuses according to the present disclosure may use any methods, techniques, or components known in the art for treating the membrane substrate with a treating solution. Various method, techniques, or components may be used to process the membrane substrate without treatment by one or more of the treating solutions.

[0044] Depending on the roll-to-roll process being used to treat the membrane substrate, processing the membrane substrate without being treated by one or more of the treating solutions may be achieved by separating the membrane substrate from one or more of the treating solutions, or by not applying one or more of the treating solutions to the membrane substrate. The membrane substrate may be separated from a treating solution, or may not have a treating solution applied, by changing the membrane substrate from a treating arrangement to a non-treating arrangement.

[0045] For example, the apparatus may include one or more immersion dip treatment baths containing the treating solutions. In such an apparatus, a roller may be at least partially immersed in the treating solution so that the membrane substrate contacting the roller is exposed to the treating solution. Non-treating arrangements may include a roller that is completely removed from the treating solution so that the membrane substrate contacting the roller is not exposed to the treating solution. The membrane substrate may be separated from the treating solutions using rollers that are independently moveable between treating arrangements and non-treating arrangements, such as illustrated in FIGS. 1 and 2. Alternatively, the membrane substrate may be separated from the treating solutions using treatment baths that are independently moveable between treating arrangements and non-treating arrangements, such as illustrated in FIGS. 3 and 4.

[0046] In another alternative, the membrane substrate may be separated from the treating solutions using treating solutions that are drainable into corresponding holding tanks. In such an alternative, when a treatment solution is contained in a treating bath, the membrane substrate is in a treating arrangement. When a treatment solution is drained in a holding tank, the membrane substrate is in a non-treating arrangement.

[0047] In yet another alternative, the apparatus may include one or more coating rollers to apply the treating solution to the membrane substrate. In such an apparatus, a non-treating arrangement may include a coating roller that is separated from the membrane substrate, a coating roller that is separated from the treating solution, a pickup roller that is separated from the coating roller or from the treating solution, a metering blade that removes substantially all of the treating solution from the coating roller or from the pickup roller, or any combination thereof.

[0048] In still another alternative, the apparatus may include a spray treatment to apply the treating solution to the membrane substrate. In such an apparatus, a non-treating arrangement may include a sprayer that is turned off

[0049] An apparatus according to the present disclosure may additionally include one or more dryers for drying the membrane after the membrane has been treated with one of the treating solutions. For example, the apparatus may include a dryer for drying the membrane after the membrane has been treated with ethanol. Such a dryer may remove substantially all of the ethanol before the membrane is treated with, for example, an acidic solution. Removing a treating solution before the membrane is treated with a subsequent treating solution may enhance the effects of the subsequent treating solution, or may reduce the amount of chemicals used in the subsequent treating solution.

[0050] Alternatively, or additionally, the apparatus may include a dryer for drying the membrane after the membrane has been treated with the humectant solution. Such a dryer may remove substantially all of the humectant before the membrane is wound up, for example for storage or filter assembly. A dried porous membrane may be stored without degradation for longer periods of time than wet porous membrane.

[0051] A dryer which may be used in the apparatus is sized and shaped to accommodate entry of the membrane along its width, and includes an under-skirt movable between an open and a closed position, and rollers that are moveable between a drying position and a non-drying position. In the drying position, the rollers position the membrane within the length of the dryer and the under-skirt is in the closed position, creating a tunnel through with the membrane passes as it is dried by the dryer. In the non-drying position, the membrane is outside the dryer.

[0052] An alternative dryer which may be used in the apparatus is sized and shaped to accommodate entry of the membrane along its width. The membrane travels through the dryer, and the dryer is turned on if the membrane is to be dried and it turned off if it is not necessary for the membrane to be dried.

[0053] In the preceding description, for purposes of explanation, numerous details are set forth in order to provide a thorough understanding of the embodiments. However, it will be apparent to one skilled in the art that these specific details are not required. Accordingly, what has been described is merely illustrative of the application of the described embodiments and numerous modifications and variations are possible in light of the above teachings.

[0054] Since the above description provides example embodiments, it will be appreciated that modifications and variations can be effected to the particular embodiments by those of skill in the art. Accordingly, the scope of the claims should not be limited by the particular embodiments set forth herein, but should be construed in a manner consistent with the specification as a whole.

[0055] This written description uses examples to disclose the invention, including the preferred embodiments, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. The patentable scope of the invention is defined by the claims, and may include other examples that occur to those skilled in the art. Such other examples are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.