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Polymers As Advanced Materials for Desiccant Applications: 1987

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Polymers As Advanced Materials for Desiccant Applications: 1987 5ERI/PR·255·3308 Polymers as Advanced Materials for Desiccant Applications: 1987 A. W. Czanderna December 1988 Prepared under Task No. 58307151 Solar Energy Research Institute A Division of Midwest Research Institute 1617 Cole Boulevard Golden, Colorado 80401-3393 Prepared for the U.S. Department of Energy Contract No. DE-AC02-83CH10093 NOTICE This report was prepared as an account of work sponsored by an agency of the United States government. Neither the United States government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, com­ pleteness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process. or service by trade name, trademark, manufacturer, or otherwise does not necessarily con­ stitute or imply its endorsement, recommendation, or favoring by the United States government or any agency thereof. The views and opinions of authors expressed herein do not necessarily state or reflect those of the United States government or any agency thereof. PR-3308 LIST OF FIGURES 3-1 Block Diagram Showing the Principal Components of a Quartz Crystal Microbalance Apparatus..................................... 13 3-2 Schematic of Vacuum System for QCM Apparatus....................... 14 5-1 Water Vapor Sorption Isotherm for PSSASS at 22.1°C••••••••••••••••• 24 5-2 Water Vapor Sorption Isotherm for SPSS at 22.1°C••••••••••••••••••• 25 5-3 Water Vapor Sorption Isotherm for PACM at 22.1°C••••••••••••••••••• 25 5-4 Water Vapor Sorption Isotherm for PAAAS at 22.loC.................. 26 5-5 Water Vapor Sorption Isotherm for PMAASS at 22.1°C••••••••••••••••• 26 5-6 Water Vapor Sorption Isotherm for PVAVSSS at 22.1°e•••••••••••••••• 27 5-7 Water Vapor Sorption Isotherm for PAASS at 22.1°C•••••••••••••••••• 27 5-8 Water Vapor Sorption Isotherm for CSSS at 22.1°e••••••••••••••••••• 28 5-9 Water Vapor Sorption Isotherm for Me at 22.1°C••••••••••••••••••••• 28 5-10 Water Vapor Sorption Isotherm for PVP at 22.1°e•••••••••••••• ~ ••••• 29 5-11 Water Vapor Sorption Isotherm for PAA at 22.1°e•••••••••••••••••••• 29 5-12 Water Vapor Sorption Isotherm for PEO at 22.1°C•••••••••••••••••••• 30 5-13 Water Vapor Sorption Isotherm for PEG at 22.1°C•••••••••••••••••••• 30 5-14 Water Vapor·Sorption Isotherm for PVSPS at 22.1°C•••••••••••••••••• 31 5-15 Water Vapor Sorption Isotherm for PFSA at 22.1°C••••••••••••••••••• 31 5-16 Water Vapor Sorption Isotherm for PHMA at 22.1 oC ••••••••••••••••••• 32 5-17 Water Vapor Sorption Isotherm for PVSASS at 22.1°C••••••••••••••••• 32 5-18 Water Vapor Sorption Isotherm for PSMQ at 22.1°e••••••••••••••••••• 33 5-19 Water Vapor Sorption Isotherm for AMBH at 22.1°C••••••••••••••••••• 33 5-20 Water Vapor Sorption Isotherm for CA at 22.1°C••••••••••••••••••••• 34 5-21 Water Vapor Sorption Isotherm for PBM at 22.1oC.................... 34 ix PR-3308 LIST OF FIGURES (Concluded) 5-22 Water Vapor Adsorption by PMAASS and PSSASS at 70%, 40%, and 9.5% R.B. after Pressure Increases from 60%, 30%, and 5% R.H., respectively....................................................... 35 5-23 Water Vapor Desorption by PAAAS, PVAVSSS and CSSS at 70%, 50%, and 5% R.H. after Pressure Decreases from 80% 60%, and 60% R.H. respectively••••• ~ •••••••••••••••••••••••••••••••••••• ~............ 35 5-24 Water Vapor Sorption Isotherms for SPSS at 22.1°C (Three Cycles)..................................................... 36 5-25 Water Vapor Sorption Isotherms for PAAAS at 22.1°C (Three Cycles)..................................................... 36 5-26 Water Vapor Sorption Isotherms for CSSS at 22.1°C (Three Cycles)..................................................... 37 5-27 Water Vapor Desorption Isotherms for SPSS at 22.1°C (Three Cycles)..................................................... 37 5-28 Water Vapor Desorption Isotherms for PAAAS at 22.1°C (Three Cycles)..................................................... 38 5-29 Water Vapor Desorption Isotherms for CSSS at 22.1°C (Three Cycles) ••• e·................................................ 38 5-30 Water Vapor Sorption Isotherms for PEO at 22.1 oC (Four Cycles) •••••••••.••••••••••.••••••••••••.•••••.••••.••••••••• 39 5-31 Block Diagram of Arrangement of a Combined QCM and SM Apparatus •••• 39 x PR-3308 SUMMARY The scientific objective of this task is to determine how the desired sorption performance of advanced desiccant materials can be predicted by understanding the role of their surface phenomena and the materials modifications. The technological objective is to identify a next-generation, low-cost material with which solar energy or heat from another low-cost energy source can be used for regenerating the water vapor sorption activity of the desiccant. This research is concerned with solid materials used as desiccants for desic­ cant cooling systems (DCS) that process water vapor in an atmosphere to pro­ duce cooling. The purpose of the Advanced Desiccant Materials (ADM) project during 1987 was to evaluate the sorption performance of polymeric materials for their potential application in solid commercial desiccant cooling systems (CDCS). An ADM can advance solar buildings technology not only by lowering the cost of CDCS to compete with conventional air-conditioning but also by eliminating the need for adding peak-load generating capacity by electric utilities. Background information is presented that includes an introduction to DCS and the role of the desiccant as a system component. The purpose, background, rationale, and long-term technical approach for studying advanced desiccant materials are reported including using polymers as ADM and the key research issues concerning polymers. The experimental method for measuring water vapor sorption by desiccants is described for a quartz crystal microbalance (QCM). Improvements needed for the experimental measurements are cited based on limi­ tations actually encountered in 1987 in using the QCM. The water vapor sorption performance criteria are identified for narrowing the potential ADM to a few candidate ADM. The sorption performance includes the sorption capacity from 5% to 80% relative humidity, isotherm shape, rate of adsorption and desorption, and cyclic stability of the ADM in water vapor. These criteria are in addition to the key materials parameters for ranking potential ADM, which are also listed from a previous report. The procedures used for preparing 23 polymers for studies with the QCM are discussed in gen­ eral and given specifically for 5 different types of polymers. Measurements are presented for the sorption performance of 23 potential com­ mercially available polymeric ADM materials with the QCM. The data include sorption isotherms, the rate of adsorption and desorption at each pressure increment or decrement, cyclic stability, and qualitative evaluation of the permeation rate. The criteria cited above were then applied to narrow the 23 potential ADM to 9 candidate ADM. The candidate polymers ~re polystyrenesul­ fonic acid sodium salt, sodium polystyrene sulfonate, polyacrylamide-carboxyl modified, polyacrylic acid ammonium salt, poly(methacrylic acid) sodium salt, poly(n-vinylacetamide, vinyl sulfonate} sodium sal t , polycrylic acid sodium salt, cellulose sulfate sodium salt, and methyl cellulose. The remaining polymers studied or considered for study that are of no further interest are also listed. Additi~nal commercially available polymers identified in a 1987 update of the original 1985 literature search are listed. Future activities for the project are addressed. The priority need for modi­ fying existing polymers and/or "molecularly engineering" the preparation of polymers to serve as an ideal desiccant are highlighted. v PR-3308 A five-page summary of the project, which has been prepared for an industrial peer review panel, is included in Appendix E. The reader may find it helpful to read Appendix E before plunging into the detail of the entire report. Vi PR-3308 CONTENTS 1.0 Introduction••••••••••••••••••••••••••••••••••••••••••••••••••••••• 1 1.1 Objectives and Previous Reports •••••••••••••••••••••••••••••• 1 1.2 Desiccant Cooling Systems •••••••••••••••••••••••••••••••••••• 1 1.3 Purpose of Advanced Desiccant Materials Research••••••••••••• 2 1.4 Relationship of Desiccant Materials to Desiccant Cooling Systems •.••••....•.••••.•.•....•..•.••.••••.•••.•..•.•....•• 3 1.5 Background for Studies of Advanced Desiccant Materials ••••••• 3 1.6 Polymers as Advanced Desiccant Materials ••••••••••••••••••••• 6 1.7 Goals/Specific Objectives•••••••••••••••••••••••••••••••••••• 7 1.8 Technical Approach for Studying Advanced Desiccant Materials.................................................... 7 2.0 Criteria for Identifying Potential and Candidate Advanced Desiccant Materials•••••••••••••••••••••••••••••••••••••••••••••••• 10 2.1 Criteria Used for Ranking Potential Candidate Ma terials ...•.••.•....•...•...•......•••••.•••.•....•.•..•..• 10 2.2 Performance Criteria for Advanced Desiccant Materials •••••••• 10 3.0 Experimental Measurement of Water Vapor Sorption by Desiccants ••••• 12 3.1 Ihtroduction••••••••••••••••••••••••••••••••••••••••••••••••• 12 3.2 QCM Apparatus •••••••••••••••••••••••••••••••••••••••••••••••• 15 3.3 Procedures Used for Determining Isotherms and Rates of Mas s Change.................................................. 15 4.0 Selection and Preparation
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