TECHNICAL BULLETIN A Brief Discussion of Gel Background Over the past decade the use of gel materials to seal HEPA filters to housings, holding frames and grids has gained in popularity. Gel materials are soft, resulting in filter installations that are easier to seal and require lower clamping pressure than typical foam gasket systems. Silicone gel originally was the only suitable material available for this application. Since then polyurethane gel systems have gained in popularity because of their lower outgassing characteristics and lower cost. Thermoplastic hydrocarbon based gels are also available but have not yet gained acceptance in the HEPA filter marketplace. By nature, gel systems are lightly crosslinked thermoset elastomers. The systems are highly plasticized by materials that may or may not be chemically bonded to the polymer backbone. The delicate nature of these lightly cross-linked systems is the primary reason that gel materials are unforgiving in processing and final characteristics may vary. Silicone Gel vs. Polyurethane Gel The two systems perform the same task with respect to HEPA filter sealing. They provide a compliant, air tight seal between the filter frame and the air delivery system. The physical properties in terms of softness, surface tack, and elasticity are generally similar. Beyond that the similarities end. Silicone gels are well known, produced by three major corporations, and find their way into a variety of electrical, electronic (encapsulation), vibration dampening and sealing applications. HEPA filter sealing is just one small market for these gels. Drawbacks of silicone gel include outgassing (detrimental to microelectronic, disk drive and optical applications), high cost, and possible cure inhibition when applied directly to incompatible substrates. Advantages of silicone include, higher use temperature and generally good chemical resistance. Polyurethane gels have become well known and understood over the past www.camfil.com 15 years. The products suitable for the HEPA filtration market are made primarily by one or two small domestic (USA) manufacturers. Other manufacturers of polyurethane gel are regionally known world-wide and the chemistry and techniques are accessible to many in the polyurethane industry. Polyurethane gels have gained acceptance into other markets including footwear, toys and novelty items, however the gel systems used for these items are generally not considered suitable for cleanroom use. Drawbacks of polyurethane gel include high moisture sensitivity of the unreacted components resulting in a limited raw material shelf-life, and incompatibility with certain substrates that may result in cure inhibition. The advantages of polyurethane gel include, lower outgassing, less ability to adsorb onto surfaces and remain there causing changes to surface energy and wet-ability, lower cost, low toxicity, and fairly good chemical resistance. The bottom line is that both Silicone and Polyurethane gels will perform the basic job of sealing HEPA filters to the air delivery system. The specific choice of gel and the filter industry move toward polyurethane gel is dictated by the needs of the end user. Gel Concerns Over the years a number of concerns have arisen involving both Silicone and Polyurethane gel. Only concerns of the end user, not those of the filter manufacturer will be mentioned below. Concerns of gel in finished product include: • • • • Exudation of liquid components (blooming, wet surface, gel dripping) Reversion (from gel back to liquid state) UV degradation Chemical degradation, Chemical compatibility Migration of liquid test aerosols into and through the gel Migration of unreacted components out of the gel • • • • • Tearing, cutting Clumping, clinging Surface tack variability Skin formation Variability of final gel properties Outgassing Insufficient Penetration of Knife Edge into Gel Color shift These concerns may be assigned to five basic categories: 1. Normal gel behavior, normal characteristic. 2. Improper design of gel or choice of gel for application. 3. Improper handling and processing of gel by filter manufacturer. 4. Improper handling, use, or design by filter installer or end user. 5. Invalid or inconsequential concern. Normal Gel Behavior, Normal Characteristics This category exists because many users of gel are simply not familiar with the normal properties and characteristics of gel systems. Most people lack the experience to recognize the difference between normal gel and a gel system that is failing. In some cases this has led to misdiagnosis of root causes for problems encountered in the clean- room and ineffective, misguided and wasteful corrective action. Improper Design of Gel, or Improper Choice of Gel for Application This category exists because many users of gel are simply not familiar with the gel systems available, have little understanding of end user needs and application, have little experience in using gels, or are driven by other factors (cost, speed of cure etc.) above all other factors. Resulting issues of concern include: Exudation, Reversion, UV degradation, chemical degradation, poor chemical compatibility, tearing, skin formation, unacceptable outgassing. Numerous CLEAN AIR SOLUTIONS TECHNICAL BULLETIN A Brief Discussion of Gel examples over recent years can be cited where an improper gel was chosen for a particular application. When the wrong gel is used for HEPA filter applications the problems that result in the industry are usually widespread and may affect many end users. Improper Handling and Processing of Gel by the Filter Manufacturer This category exists because many users of gel simply do not have the expertise, equipment or internal controls and maintenance to avoid processing problems. As mentioned earlier, gel chemistry is fragile and unforgiving. While some variability in the physical properties of the end product should be expected and tolerated, gel systems should not fail due to processing problems. Problems related to manufacturing processing problems include exudation, unacceptably large variability of final gel properties, cure inhibition (wet spots), and gel dripping. These are usually related to using gel that is not stored properly, is past its shelf life, is not metered and/or mixed properly, or is applied to an incompatible or contaminated substrate. Numerous examples over recent years can also be cited where the filter manufacturer experienced problems due to process control issues. The subsequent problems that result in the industry are usually isolated to a single or small batch of filters, but related problems may also be found sporadically among filters over many batches and over a widespread number of customers and sites if no corrective action (or ineffective corrective action) is taken and the process remains out of control. Improper Handling, Use or Design by End User This category exists because many end users of gel simply do not understand how the gel system should work and how filters and systems containing gel should be handled. Problems include insufficient penetration of the knife edge into the gel, cutting of the gel, tearing, clumping, clinging, UV degradation, reversion, and chemical incompatibility with the process. Some of these issues can be avoided by simply designing the sealing interface properly or unpacking, installing and removing filters properly. Other times the combination of gel selection and end-user handling and use result in issues. Care www.camfil.com should be taken in design stages that the knife edge is centered in the gel channel and sufficiently penetrates the gel surface when the gel surface is 1/16 inches (1.5 mm) to 3/16 inches (4.8 mm) below the top of the gel channel. It is never recommended to fill a gel channel completely since this causes manufacturing problems and can cause the gel to bulge out of the channel when the knife edge is inserted. Theoretical design interface may allow the knife edge to “bottom out” in the gel channel, but in reality, the filter should not be clamped so tightly that the knife edge cuts completely through the gel. Exceeding the elastic limits of the gel will result in splitting and cutting of the gel. Below the elastic limits, the gel will “snap back” and return to nearly its original state when the filter is removed. Since gel is tacky and since the disperse phase of the gel is mobile within the gel system the margins along a cut in the gel have a tendency to stick back together. This is sometimes (incorrectly) referred to as “self-healing.” Once the gel is cut or fractured, it may stick back together and form a seal, but it will not reform chemical bonds. Therefore the gel will not “self-heal” any more than a rubber band that has snapped or a tire that is punctured will heal itself. Some individuals have tried to blame problems with gel on either improper gel selection or improper installation or design when the real problem has been improper handling or processing of the gel by the filter manufacturer. An illustration of this was a recent case where an end user was told that the gel used in their product could not be installed in a vertical application or it would run out of the track due to gravity. This is nonsense. The fact is that gel is a cross-linked thermoset system, incapable of flowing. Most gel filters are, in fact, shipped with the gel in a vertical position. Many tens of thousands of gel seal filters are installed today in air handlers with vertical banks. The same gel that is used for ceiling grids and horizontal applications may be used in vertical applications. If the gel flows out of the channel there is something has gone wrong with the gel and the cause needs to be identified. Invalid or Inconsequential Issues This category exists in part, because of the problems and issues cited above, some end users have become hypersensitive to problems and rightfully so, when critical downstream processes are at stake. There is normal variation in gel properties that are acceptable. Batch to batch the hardness, surface tack, color of the gel may vary somewhat. It is important for all segments from supplier, processor, manufacturer, installer through end user to be knowledgeable and aware of what is acceptable and what constitutes a problem for a given application. The use of gel systems specifically recommended for HEPA filtration applications is the first step toward achieving this goal. Color change, particularly a color shift clear to light amber or from blue toward green, yellow or clear, by itself, is also normally considered of little consequence as long as all other properties of the gel remain acceptable. The pigments used to color gel are normally organic, non-metal containing pigments and are not necessarily color fast and usually not chemically bound to the gel. The (un-pigmented) gel material itself, over time tends to shift from a water clear color toward a yellow clear color. This is a normal characteristic of many elastomer systems. With pigmented gels, Camfil, in conjunction with the Gel Supplier, has controlled the level of blue pigment in the gel in order to avoid noticeable color shift over time during normal use. Recent issues of Gel compatibility with Aseptic Cleanroom Chemicals and Process Camfil, over the past year has become aware of a number of situations where gel failure has occurred in cleanrooms. While most of the information regarding these incidents has been “word of mouth,” Camfil does have specific knowledge regarding cases where gel in some filters repeatedly exhibited the accumulation of a wet oily substance. Working with suppliers, end users, independent experts and laboratories we have done a significant amount of work to try to establish the facts surrounding these incidents. In cases where we have detailed information and based on extensive laboratory testing, the circumstances and experimental evidence does not support an early theory that antimicrobial agents, specifically Spor-Klenz, or sodium hypochlorite (bleach) solutions are singularly to blame for the problem. Experimental evidence under very severe CLEAN AIR SOLUTIONS TECHNICAL BULLETIN A Brief Discussion of Gel conditions does suggest that sequential use of Spor-Klenz and bleach can lead to reactions that can occur in the gel and can cause the liquid content of the gel to increase. Since normal conditions are much less severe, we can only say that these agents used in combination may worsen or accelerate but not by themselves cause gel failure. Evidence also suggests that prolonged exposure to acids (e.g. hydrochloric acid (HCl) and acetic acid, can be detrimental to gel systems and can contribute to problems of gel dripping. The current thinking is that a combination of factors is usually to blame when a gel problem, especially gel dripping, is observed. The quality of the gel materials, the extent of the curing reaction, the characteristics of the gel system and the control of the component mixing are all factors that are also important and can influence the likelihood and extent of a problem with the gel. The temperature of the use environment and the application of excessive amounts of liquid oil aerosols (PAO, DOP, DEHS, Mineral Oil, etc.) can also worsen or accelerate a gel dripping problem. It has been demonstrated that with a driving force present it is possible that liquid aerosol used to test the filters (PAO) accumulated above the gel can theoretically migrate through the gel and then along with unreacted components of the gel, accumulated downstream often at the corner miter joints of the filter especially if these joints are not well sealed. Tests indicate that these oil aerosols when applied in vast excess may cause a small amount of swelling to the gel or can extract components of the gel but do not chemically react to the gel. Camfil conducted cursory tests to determine the compatibility of various filter construction materials including gel, with Spor-Klenz. Polyurethane Potting compounds, Filter Media, Gasket Material, Silicone Potting Compound, Silicone Gel and Polyurethane Gel substrates were all directly exposed to both concentrated Spor-Klenz and to a 1% Spor-Klenz solution (recommended solution for disinfection of surfaces.) In this study the Spore-Klenz solutions were directly applied to the substrate surface using a dropper. The pool of liquid Spore-Klenz was allowed to sit on the surface at room temperature overnight until it evaporated the next day. After 24 hours, no change www.camfil.com to any substrate, including both gels, was observed for both the concentrated and dilute Spore- Klenz solutions. Another test was conducted where polyurethane gel was directly exposed to concentrated vapors of an acidified hypochlorite bleach solution at room temperature. After one month of exposure some “skinning” and loss of surface tack were noted on the polyurethane gel sample. The skin was a frosty white color and was very thin. There was a slight decrease in the penetration (softness) of the gel probably due to the formation of the skin. No liquefaction or reversion was observed. The underlying gel was unaffected, only the gel surface showed the changes noted. In another study silicone gel was partially immersed in an acidified sodium hypochlorite solution for 24 hours at room temperature. Observations following exposure indicated that the gel matrix itself was unchanged, however the bleach solution effectively removed the blue pigment from the gel sample and the sample shifted in color from blue to clear. Camfil has a program of continual study and characterization of gels in an effort to further develop industry knowledge. In summary, the issue of gel dripping seems to be caused by a combination of multiple factors including the original choice of gel, the quality of the components, the reliability of the mixing process and the exposure of the gel to oxidizing chemicals or other detrimental environmental stressors. A significant excess exposure to oil or elevated temperature may exacerbate the problem. Recent Investigation of Gel Compatibility with PAO (polyalpha olefin) In other studies with gel, Camfil and others were able to document a reduction in the plasticizer level of polyurethane gel when it was immersed in PAO at room temperature. The test conducted was a very severe test since PAO would never be expected to be present in such large quantities where gel filters are installed. Polyurethane gel plasticizer was able to migrate out of the gel into the PAO, and PAO was not able to migrate into the gel in sufficient quantities to replace the plasticizer, resulting in shrinkage (reduced bulk volume) of the polyurethane gel. This is strictly a physical reaction having to do with diffusion of liquid materials into and out of the gel. There was no noticeable indication of any chemical reaction occurring between silicone gel or polyurethane gel and PAO. Independent investigation by multiple researchers indicates slight swelling of silicone gel when exposed to PAO. In a study conducted by Camfil we quantitatively measured on average 5.5% swelling of silicone gel after immersion in PAO for 7 days at room temperature and about 9.5% swelling after 55 days of immersion. The gel specimens appeared normal and we were unable to visually detect swelling of immersed samples of silicone gels in PAO. We did notice that one type of silicone gel containing a blue pigment became clear when immersed in PAO, and the PAO took on a blue tint. Obviously, the pigment was extracted from the silicone gel and into the PAO. In either case, these effects may be of only academic interest, since the quantity of PAO present as a result of normal HEPA filter integrity testing, in relation to the quantity of gel present in the system is extremely small, and in actual field installation the physical effect of PAO on gel should be unnoticeable. Migration of Gel Discrete Phase Recently Camfil and a researcher from a large pharmaceutical company conducted similar experiments where small plugs of gel were placed on filter paper at a controlled temperature and the resulting diffusion or migration of unreacted components of the gel out onto the filter paper was measured over time. A “bullseye” ring formed around the gel and grew in size over time. The rate of migration was measured and found to vary based on type of gel, manufacturer and grade. For a particular type of gel, the results were reproducible and were and characteristic of the gel. In general we also were able to qualitatively relate the rate of migration directly with the quantity of extractable material in the gel (determined by Soxhlet extraction) and inversely with increased physical properties of the gel. The Effect of Knife Edge Insertion into Gel Recently Camfil conducted a series of controlled experiments where various types of knife edges were inserted into different types of gel. The knife edges used were: CLEAN AIR SOLUTIONS TECHNICAL BULLETIN A Brief Discussion of Gel 1. 2. 3. Dull edged extruded anodized aluminum Dull edged 11 gauge stainless steel Sharp 90° edged 11 gauge stainless steel In each case the knife edges were inserted into cured gel by a depth of 7/16 inches (11 mm) and the knife edge was never allowed to approach the bottom of the gel channel closer than about 1/8 inches (3mm). We found that certain gels have extremely low toughness and tensile strength and cut or split in reaction to the stress of knife edge insertion regardless of the type of knife edge. We found that other gels cut and split to some degree depending upon the type of knife. In some cases cuts and splits took only minutes to appear and in other cases it took days or weeks. Still other types of gels are extremely tough and resist cutting or splitting even when the knife edge was left inserted for up to 5 months. Upon removal of the knife edge, some gels tended to release from all knife edges easily. Some adhered more to the stainless steel than the anodized aluminum and still other gels stuck tenuously to all materials. Additional certain gels tended to tear upon knife edge removal resulting in avulsion to the gel with associated gel residue remaining on the knife edge surface. Basically, some cutting and splitting of the gel is normal depending upon the system design and the type of gel used. Conclusions about the gel cannot be made based solely upon field observations regarding the presence or absence of cuts, splits or avulsions in the gel after filter removal from the system. We were able to determine what the normal characteristics of the gel are during and after knife edge insertion. Quality Assurance In addition to the certificate of compliance provided by the raw material supplier, HEPA filter manufacturers who use gels in their products are must have a robust and comprehensive quality assurance process in place that ensures the quality of each lot of component materials received and the quality of the mixed components being applied to the filters. The program must ensure that both the materials and the process being used are acceptable to give a good, consistent quality end product. Proper mixing and curing of the gel must be verified prior to every production run (at least daily). Cured retain samples should be maintained for an extended period of time. www.camfil.com Conclusion Legal Disclaimer By nature, gel systems, whether silicone based or polyurethane based, offer many advantages and many challenges to end users and filter manufacturers. The use of gel to achieve filter seals is a welldeveloped and effective technology when done correctly. Due to the fragile nature of the chemistry (lightly cross-linked system) the proper choice of materials and very good process control in manufacturing of filters is required in order to achieve consistent quality. Because of our depth of knowledge, experience, quality systems, process control systems, and availability of technical resources, Camfil has established the qualifications needed to successfully implement this technology while avoiding widespread field problems. In many cases, our experiments and observations have been duplicated by independent parties interested in the subject and we have been able to likewise duplicate a number of experiments conducted by others. Because of their many advantages, Camfil continues to offer high quality silicone gel seal systems primarily targeted for life science applications and polyurethane gel systems primarily targeted to microelectronic, aerospace, optical and surface coating applications. The information, recommendations or advice contained herein is given in good faith; supplier makes no warranty or guarantee, express or implied, (1) that the results described herein will be obtained under enduse conditions, or (2) as to the effectiveness or safety of any design incorporating supplier’s materials, products, services recommendations or advice. Nothing in this document or any other document shall alter, vary supersede or operate as a waiver of any of the supplier’s standard conditions of sale. Each user bears the full responsibility for making its own determination as to the suitability of supplier’s materials, products, services, recommendations or advice for its own particular purpose. Each user must identify and perform tests and analysis sufficient to assure it that its finished parts will be safe and suitable for use under enduse conditions. Because the actual use of products by the user is beyond the control of Supplier, such use is within the exclusive responsibility of the user and supplier cannot be held responsible for any loss incurred through incorrect of faulty use of the products. Further, no statement contained herein concerning a possible or suggested use of any material, product, service or design is intended or should be construed to grant any license under any patent or other intellectual property right of supplier or any of its subsidiaries or affiliated companies, or as a recommendation for the use of such material, product, and service or design in the infringement of any patent or other intellectual property right. The information contained in this document is truthful and factual to the extent that the facts are known at this time. The information is provided in good faith to help in understanding the issues discussed. Specific references to actual companies or individuals have not been made and assumptions shall be avoided. Similarities to actual events may not be used as evidence that a particular company, event, material or individual was involved in the cases cited above. This document may contain proprietary and confidential information and is to be treated as such by Camfil. and by the reader. Reproduction and distribution of this document by any means is prohibited without the express written permission of Camfil. Steve Devine B.S. Engineering Chemistry M.S. Polymer Science and Engineering Vice President of Research and Development Camfil Revised 11/29/12 CLEAN AIR SOLUTIONS