Encyclopedia of Polymer Science and Technology || Superabsorbent Polymers

Encyclopedia of Polymer Science and TechnologyCopyright c© 2006 John Wiley & Sons, Inc. All rights reserved.

SUPERABSORBENT POLYMERS

Introduction

Superabsorbent polymers are very high molecular mass, cross-linked Polyelec-trolytes (qv) that can absorb or imbibe more than ten times their mass of wateror aqueous solutions. In order to absorb this large quantity of aqueous fluid, thepolymers must be only slightly cross-linked so that the polymer chains can adoptwidely spaced configurations. And in order to remain largely insoluble, while atthe same time being highly expanded, the polymer chains must have very highmolecular mass so that the small number of cross-links connect together all thechains. Cross-linked polyelectrolytes absorb more aqueous liquid than do neutralpolymers as a result of the added osmotic, swelling pressure of the counterionsthat balance the high electric charge of the ionized functional groups spaced alongthe polymer chains (see POLYELECTROLYTES).

Although any high molecular mass, cross-linked polyelectrolyte can functionas a superabsorbent polymer, the commercially available superabsorbent poly-mers are alkali metal salts of poly(acrylic acid) cross-linked with multifunctionalcross-linkers (see ACRYLIC (AND METHACRYLIC) ACID POLYMERS). Most often thecross-links are formed from comonomers that are incorporated into the polymerduring the free-radical-initiated addition polymerization. Common cross-linkersare di- and tri-acrylates or methacrylates. The polymer chains can also be cross-linked after the main polymer chains have been formed. In this case, the cross-linker is multifunctional with groups that can react with the carboxylic acid orcarboxylate groups present along the polymer chains. Examples of this type ofcross-linker are polyols, polyepoxides, polyamines, and the like. Most commonly,the polymers are made by means of free-radical-initiated polymerization of anaqueous solution of the monomers, followed by drying the hydrogel that is formedand grinding the dry polymer to a granular powder.

The principal use of superabsorbent polymers is as a liquid absorbent in dis-posable hygiene products, which include baby diapers, feminine hygiene products,and adult incontinence products. Smaller volume uses include liquid absorbentpads for packaged meats and water-blocking tapes and coatings for electrical andtelecommunication cables.

Physical Properties of Monomers

The monomers useful for making superabsorbent polymers are water-solublemonomers such as those listed in Table 1. Acrylic acid, methacrylic acid,

1

2 SUPERABSORBENT POLYMERS

Table 1. Principal Monomers Used in the Polymerization of Superabsorbent Polymers

2-Acrylamido-N-Isopro- 2-methyl-

Methacrylic pylacryl- propanesulfonicProperty Acrylic acid acid Acrylamide amide Acid

CAS registrynumber

79-10-7 79-41-4 79-06-1 2210-25-5 15214-89-8

Molecularformula

C3H4O2 C4H6O2 C3H5NO C6H11NO C7N13NO4S

Molecularmass, g/mol

72.06 86.10 71.08 113.16 207.21

Melting point,◦C

13.5 16 84.5 62 195

Boiling point,◦C

141(101.3 kPa)

163 136(3.33 kPa)

90 (2 mm) —

Flash point,◦C

50 76 — — 160

Density at20◦C, g/cm3

1.040 1.015 1.122 (30◦C) — —

�Hpolym,kJ/mol

77.5 56.3 81.5 — 92.0

Table 2. Cross-Linkers Used in Superabsorbent Polymers

1,1,1-N,N′- Trimethylol-methylene- Ethylene- propane- Tetra(allyloxy)-

Property bisacrylamide diacrylate triacrylate Triallylamine ethane

CAS registrynumber

110-26-9 2274-11-5 15625-89-5 102-70-5 16646-44-9

Molecularformula

C7H10N2O2 C8H10O4 C15H20O6 C9H15N C14H22O4

Molecularmass, g/mol

154.17 170.16 296.32 137.23 254.33

Boiling point,◦C

— 67 (2 mm) — 150 157 (25 mm)

Density at 20◦C, g/cm3

— 1.094 1.100 0.790 1.001

Flash point,◦C

— 92 >110 30 >110

and 2-acrylamido-2-methylpropanesulfonic acid (1,2) are the principal ionizablemonomers useful for making superabsorbent polymers. Other comonomers suchas acrylamide and N-isopropylacrylamide can also be incorporated into the poly-mer chain. For example, N-isopropylacrylamide imparts temperature sensitivityinto the superabsorbent polymer (3,4). The useful cross-linkers include a varietyof multifunctional monomers, such as those shown in Table 2. They can be di-,tri-, or tetra-functional and can have mixed types of polymerizable groups such asmethacrylate and allyl, as in allylmethacrylate. Mixed types of functional groups

SUPERABSORBENT POLYMERS 3

provide olefins with varying reactivity toward the main monomer. The mixed-functional cross-linkers can be used to control the incorporation of the cross-linksduring the polymerization. For example, the gel point of the polymerization canbe made at lower conversion of monomers by using a cross-linker that is more re-active than the main monomer. Conversely, the gel point can be delayed to higherconversion of monomers by using a less reactive monomer compared to the mainmonomer.

Manufacture of Monomer

The principal monomer used in the manufacture of superabsorbent polymers isacrylic acid. Acrylic acid is made by the oxidation of propene in two steps (5). First,propene is oxidized to acrolein, and then the acrolein is further oxidized to acrylicacid. Different mixed metal oxide catalysts are used for each step to optimizethe yield and selectivity of the oxidation reactions. Technical-grade acrylic acidis isolated from the steam-quenched reaction gas by means of solvent extractionand distillation, and is used principally in the further preparation of acrylateesters. The technical-grade acrylic acid is further purified by distillation or bycrystallization from the melt to afford the polymerization-grade monomer.

Properties of Polymers

The principal useful feature of superabsorbent polymers is their ability to absorbaqueous liquids and expand or swell in size. The swollen polymer—a cross-linkedpolymer solution—holds tightly to the liquid and prevents the liquid from beingeasily squeezed from the expanded structure. The two principal properties of thepolymer that define their usefulness are the swelling ratio and the elastic modulusof the swollen polymer.

Swelling Ratio. The swelling characteristic of superabsorbent polymershas been described in several ways. A volumetric swelling ratio is equal to the vol-ume of solvent absorbed per unit volume of the polymer. The gravimetric swellingratio, or specific absorbency, is equal to the mass of solvent absorbed per unit massof unswollen polymer. The gravimetric ratio is most commonly used in the mea-sure of swelling in commercial practice. These volumetric and gravimetric ratioscan be easily interconverted by multiplication with the ratio of densities of thesolvent and polymer. The molecular theories of swelling and elasticity of cross-linked polymer networks use the volume fraction of polymer in the gel phase asa measure of swelling extent. The reciprocal of the volume fraction, equal to theratio of gel volume to polymer volume, is an alternative volumetric swelling ratio.The theory (6) yields equation 1 for the swelling ratio qm in terms of the essentialstructural and polymer synthesis parameters of the system.

q5/3m = (1/2 − χ )2Mc

V1ρ0υ2/320 (1 − 3Mc/Mn)

(1)

Assuming a randomly cross-linked, four-functional network, and includingthe ionic effects in an “apparent χ”, the swelling ratio depends on the molecular


Fig. 1. Effect of neutralization on specific absorbency.

mass of polymer chain between cross-links Mc, on the backbone molecular massMn, the molar volume V1 of the solvent, and the density ρ0 of the unswollenpolymer. The volume fraction of monomer υ20 during polymerization influencesthe maximum swelling ratio through the term υ20

2/3.Commercialized superabsorbent polymers are salts of weak polyacids; hence,

their swelling varies with the pH of the swelling liquid or the ionization extentof the polymer, as shown in Figure 1. For superabsorbents made from strongacid monomer such as 2-acrylamido-2-methyl-1-propanesulfonic acid, the swellingextent does not depend on the pH of the swelling liquid (7).

The swelling ratio of any superabsorbent polymer depends directly on thecross-link density imposed during synthesis. The actual cross-link density oftendiffers from the stoichiometry of reagents employed on account of inefficient in-corporation of cross-linker, poor reactivity of cross-linker relative to acrylic acid,and the functionality (number of reactive olefinic groups) of the cross-linkermolecule.

The swelling ratio is limited by the elastic stress caused by the stretchingpolymer chains, and by any other mechanical or osmotic stresses that act on thepolymer phase. Lower swelling, or deswelling, in salt solutions (8–10) or underuniform hydrostatic pressure (11,12) is well known. In an important paper byHorkay and Zrinyi (13), the application of stress through mechanical compressionresulted in equivalent deswelling compared to an equal magnitude osmotic stressapplied by means of a surrounding polymer solution. The implication is that allequal magnitude stresses cause equal magnitude deswelling of a given superab-sorbent polymer. A scaling theory analysis (14) of the effect of stress on swellingyields equation 2 for superabsorbent swelling ratio as a function of the applied


pressure, where QP is the swelling at pressure P, Q0 is the swelling at atmosphericpressure, and G is the elastic modulus of the swollen gel.

QP = Q0

(1 + P

G

)− 0.44

(2)

The application of superabsorbents in absorbent composites such as diaperspresents several kinds of stresses on the polymer (15). The effects of hydrostaticcompression from swelling in polymer solutions, salt partitioning between geland unabsorbed liquid, restriction by the network of wettable fibers, competitionfor liquid by the small capillaries between fibers, and interparticle friction be-tween the polymer particles and the fibers have recently been determined (16).The swelling reduction caused by restriction due to the fiber network was foundto be about equal to that from partitioning of salts between liquid and gel phases.Swelling reduction due to capillary tension in the pores and the reduction due touncross-linked polyelectrolyte partitioning into the liquid phase were each aboutone-third that of the salt-partitioning effect.

The swelling extent of all superabsorbent polymers is very sensitive to thesalt concentration of the swelling liquid (9), as a direct result of their polyelec-trolyte nature. The swelling extent decreases with increasing concentration of ionsin solution. Divalent ions, such as calcium or magnesium, decrease the swellingof superabsorbent polymers much more than monovalent ions (per mole of ions)(17). The additional effect is so large that it has been erroneously believed that thedivalent ions behave like cross-linkers. Measurements of both the swelling extentand elastic modulus of the swollen gels have disproved that notion (18). The gels,swollen in solutions of divalent ions, had equivalent modulus to the gels swollento the same volume fraction polymer in monovalent salt solution. However, manyhigher valence ions, such as ferric or chromic, add to the cross-link density of gelsswollen in their solutions.

Modulus of Elasticity. When a swollen superabsorbent polymer parti-cle is subjected to mechanical stress, it strains and changes shape. The elasticmodulus of the material is the ratio of the applied stress to the resulting strain.For swollen superabsorbent polymers, the magnitude of the elastic shear modu-lus principally depends on the cross-link density established during synthesis ofthe polymer and on the extent of swelling during measurement of the modulus.Polymer swelling lowers the cross-link density by increasing the volume in whichthe cross-links reside.

The elastic modulus of the swollen superabsorbent polymer is important forseveral reasons. The powdered polymer is typically used in a physical blend withfibers such as cellulose and thermoplastic binder fibers. The resulting structureis called the absorbent core. The absorbent core relies on pore spaces betweenthe fibers and polymer particles to provide liquid transport volume for the overallstructure. When the swollen superabsorbent particles have low modulus, they areeasily deformed by body pressures and can fill in the interfiber and interparticlepores. This prevents liquid flow and wicking of liquid into the drier portions of thecore. Higher modulus limits the deformation of the particles and helps maintainthe pore space.


The elastic modulus also influences the swelling kinetics of the superab-sorbent polymer in the blend (19). For a cross-linked polymer, different shapedparticles have different swelling kinetics. This results from the coupling betweenthe diffusion of water into the polymer network through the surfaces of the par-ticles, and the relaxation of the cross-linked polymer chains in the presence ofthe swelling agent. Of the simple shapes, spherical particles have the fastest ki-netics whereas flat disks have the slowest kinetics. Spherical particles that aredeformed into a disk-like shape swell more slowly, and therefore the more de-formable swollen particles (lower elastic modulus) will be slower than similarsized particles with higher modulus that are less deformable.

The elastic modulus is controlled by the polymer network structure and syn-thesis conditions. The number of cross-links added per mole of main monomerhelps define the molecular mass between cross-links. The molecular mass of thebackbone polymer chain (obtained if no cross-linker was used) affects the effec-tiveness of the cross-links in forming a fully connected network with no solublefraction and minimum content of dangling chains. The polymer volume fractionduring cross-linking υ20 defines the extent of entanglement of the network chains,and therefore influences the elastic modulus. From the molecular theory of net-works, the shear modulus is given in terms of polymerization parameters accord-ing to equation 3

G = ρ0RT2Mc

(1 − 3Mc

Mn

)υ

2/320 υ

1/32 (3)

wherein the parameters have the same meanings as given above for the equationof the swelling ratio. The extent of swelling during measurement is expressedthrough the volume fraction of polymer in the gel υ2. The gas constant R and thetemperature T also affect the magnitude of the modulus. By comparing equations1 and 3, the swelling capacity and the elastic modulus are inversely related to thesame structural parameters. This relationship is shown in Figure 2.

Swelling Kinetics. A first-order relaxation process in which the polymerchains relax and diffuse into the aqueous solution controls the swelling rate, whichis given by equation 4:

Rate of swelling = dQdt

= k(Qmax − Q(t)) (4)

wherein Qmax and Q(t) are the swelling ratios at equilibrium and at any time t,under the conditions of the experiment. The first-order rate (or relaxation) co-efficient k depends on the diffusion coefficient of the polymer chains and on theparticle radius. Integration over the total swelling time yields equation 5.

Q(t) = Qmax(1 − e− kt) (5)

The rate coefficient k depends on the elastic subchain length (between cross-links), decreasing with increasing chain length between cross-links (ie, lowercross-link density). The rate coefficient also decreases with increasing particle ra-dius. Increasing the temperature hastens the thermal fluctuations of the chains,


Fig. 2. Relationship of gel shear modulus to the specific absorbency. Polymers wereswollen in 0.9% NaCl solution. To convert kPa to dyn/cm2, multiply by 104.

and hence increases the rate coefficient. The rate coefficients for the weak poly-electrolyte superabsorbent polymers vary with the pH (extent of neutralization)and the salt concentration as well. At higher pH, the chains adopt a stiffer con-formation; hence, the rate coefficient increases with pH. Addition of monovalentsalts has the reverse effect on conformation; hence, the rate coefficient decreaseswith increasing salt concentration.

Polymerization

Superabsorbent polyacrylates are prepared by means of free-radical-initiatedcopolymerization of acrylic acid and its salts with a cross-linker (20,21). Twoprincipal processes are used: bulk, aqueous solution polymerization and sus-pension polymerization of aqueous monomer droplets in a hydrocarbon liquidcontinuous phase (22) (see BULK AND SOLUTION POLYMERIZATIONS REACTORS; HET-EROPHASE POLYMERIZATION). In either process, the monomers are dissolved in wa-ter at concentrations of 20–40 wt% and the polymerization is initiated by freeradicals in the aqueous phase (23). The free radical initiators, (qv) used includethermally decomposable initiators, reduction–oxidation systems, and photochem-ical initiators and combinations. Redox systems include persulfate/bisulfite, per-sulfate/thiosulfate, persulfate/ascorbate, and hydrogen peroxide/ascorbate. Ther-mal initiators include persulfates, 2,2′-azobis(2-amidinopropane)- dihydrochlo-ride, and 2,2′-azobis(4-cyanopentanoic acid). Combinations of initiators are usefulfor polymerizations taking place over a temperature range.

The copolymerization is conducted either at low pH with the acid-formmonomers, which are neutralized after polymerization, or at roughly neutralpH with partially neutralized carboxylate salts. Sodium hydroxide and sodium


carbonate typically are the neutralizing agents. The cross-linkers vary in func-tionality, from difunctional acrylate esters and methylenebisacrylamide, to tri-functional compounds, such as 1,1,1-trimethylol-propanetriacrylate and trially-lamine, and to tetrafunctional compounds, such as tetra(allyloxy)ethane.

In the case of acrylic and methacrylic acids, the reactivity of the monomer to-ward polymerization is a complex function of the pH (extent of neutralization) andmonomer concentration. The reactivity of ionized monomer being lower than theneutral carboxylic acid, polymerization proceeds more slowly as pH is increased(24–26). A minimum in the polymerization rate occurs at pH of 7 (27–29). AbovepH of 7, the rate increases again because of electrostatic screening due to increasedionic strength.

An emerging method of influencing the modulus of the polymerized gels is topolymerize the gels in the presence of nanoparticles such as hydrotalcite or atta-pulgite clay (30,31). Nanoparticles have improved some mechanical properties ofpolymer composites in unswollen systems. Although the hydrogel properties areinfluenced by the presence of the intercalated, inorganic particles, it is yet un-clear whether the materials have enhanced performance, especially improved re-sistance to deswelling under pressure, compared to conventional superabsorbentsin absorbent products such as diapers.

Processing of Polymers

Gel Size Reduction. After polymerization, the gel intermediate must bedried. However, prior to drying, the size of the gel pieces must be reduced in orderto increase surface area and speed drying. In some commercial processes, thegel size reduction is done in the polymerization vessel by means of high torqueagitators or screws. In other processes, gel is sized in a separate unit operation ofgel extrusion and cutting or mincing. Final gel particles are in the diameter rangeof 0.5–3 cm.

Drying. The water used as solvent in the polymerization is removed fromthe polymerized gel by evaporation in continuous operation, hot-air convectiondryers or in contact dryers such as steam-heated drum dryers. In hot-air convec-tion dryers, the rate of moisture removal depends on the heating gas temperature,humidity and flow rate, and the diffusion characteristics of water from the gel.Drying occurs in three general stages. For high water content in the gel, the dryingrate is constant, as the rate is limited by heat transfer into the gel. At low watercontents, the drying is limited by diffusion of water through the gel, and the dryingrate falls as water is further depleted. In the intermediate or transition regime,some of the polymer is still in the constant-rate regime while other portions haveentered the diffusion-controlled regime.

On rotating drum dryers, the drying energy is conductively transferred fromthe hot metal drum to the gel (32). The hydrogel must be applied to the drum in asufficiently thin layer, accounting for the available heat transfer and drum size, sothat it is thoroughly dry in about three quarters of a revolution of the drum roll,whereupon it is scraped from the drum with flaking knives. In order to spreadthe gel layer effectively onto the drum, the hydrogel must be soft enough to bedeformable in the dryer nip.


Grinding and Sieving. Grinding or milling the very coarse dryer product,followed by sieving sets the particle size distribution of the dried superabsorbentpolymer. The common polyacrylate superabsorbent polymers have a particle sizedistribution ranging from about 200 to 800 µm. Two-stage milling is frequentlyused in combination with sieving and recycle of the oversize particles in order toprepare a relatively narrow size distribution of the final granular powder. Knifemills, attrition mills, roll crushers, and the like are used in the first stage to providea coarse but narrower particle size distribution feed for the second grinding stage.In the second stage, the final average particle size is attained. Sieving off boththe coarse tail and the fine tail of the size distribution typically narrows the finalsize distribution further. The coarse tail is recycled to the grinder, and the fine tailmay be used for other purposes or recycled back to the polymerization reactor.

Surface Cross-linking. Since small particles of hygroscopic polymer ab-sorb water very fast, they can quickly form a thin, sticky layer of gel at the par-ticle surface and then clump together or “gel block”. The resulting interparticleadhesion causes the formation of large, sticky agglomerates with low interparticleporosity and drastically slower swelling rate. One remedy is to add a solution ofmultivalent cations to the surface of the dry particles, forming an ionically cross-linked surface layer (33). Alternatively, the particle surface can be coated withand reacted at elevated temperature with polyols, polyepoxides, linear or cyclicdiesters or polyamines, as examples, forming a covalently cross-linked surfaceshell (34–36). This shell of higher cross-link density is less swellable, less sticky,more rigid than the untreated polymer surface, and prevents gel blocking. Thisimproves the permeability of the particle bed toward liquids.

A third method to produce these so-called structured particles is to first forma particle with higher cross-link density and then lower the cross-link densityin the center of the particle. Cross-linked polymers made in the presence of ox-idizing agents such as sodium or potassium chlorate have shown improvementsin absorbency under load and swelling capacity after a high temperature heatingstep (37) wherein a portion of the polymer chains in the particle center are cleavedthrough the action of the oxidizers.

Economic Aspects

Cross-linked, partially neutralized poly(sodium acrylate) represents the over-whelming majority of the superabsorbents manufactured in the world today. Theglobal manufacturing capacity for these superabsorbent polymers in 2001 wasestimated to be about 1.187 million metric tons per year. This quantity is splitwith 380 kt/year in Europe, 427 kt/year in the United States of America, and 380kt/year in Asia. Total global usage of superabsorbent polymers in 2001 amountedto about 1093 kt, or just over 92% of the global manufacturing capability (38).

In 2001, there were six principal global manufacturers of superabsorbentpolymers. BASF Aktiengesellschaft had about 305 kt/year of manufacturing ca-pacity, followed by Degussa (Stockhausen division) with about 245 kt/year, NipponShokubai Kagaku Kogyo with about 230 kt/year, The Dow Chemical Companywith about 120 kt/year, SanDia (Sanyo and Mitsubishi joint venture) with about95 kt/year, and Sumitomo Chemical with about 60 kt/year. Several more small


manufacturers together made up another 132 kt/year of manufacturing capa-bility. Included in this group of smaller companies are those who make slightlydifferent superabsorbent polymers such as cross-linked, partially neutralizedpoly(potassium acrylate) and cross-linked, slightly ionized polyacrylamide, whichare used mainly in the agricultural and horticultural industries.

Superabsorbent polymers are used mainly in disposable, personal care hy-giene products. About 81% of total tonnage (885 kt/year) is used in infant diapersand child-training pants. Another 14% of the total (157 kt/year) is used in adultincontinence products, and about 2% (22 kt/year) is used in feminine menstrualpads and napkins. The remaining 3% of total tonnage (32.8 kt/year) is used inother applications such as construction materials, cable-wrapping tapes, agricul-ture, and horticulture.

Analytical and Test Methods

Swelling Capacity. Several methods have been used to measure the spe-cific absorbency (mass of liquid absorbed per unit mass of superabsorbent poly-mer), swelling ratio, or swelling capacity (39). In the most common technique (40),a small quantity of superabsorbent polymer is placed in a porous, heat-sealablebag, which is then immersed in the desired aqueous liquid. The polymer is al-lowed to absorb liquid for a time long enough to reach maximum or equilibriumswelling, which is usually from 30 to 90 min. Then the porous bag and its contentsare centrifuged under standard conditions to remove the unabsorbed liquid fromthe pore spaces between the swollen particles. The liquid absorbed is determinedby gravimetry.

Elastic Modulus. The elastic shear modulus of swollen superabsorbentpolymer is commonly measured by means of oscillatory rheometry, using any ofa variety of commercially available instruments (41). The sample to be analyzedis screened to the desired particle size cut such that the swollen particle size issmaller than the gap between the measuring plates. The sample is swollen in thedesired liquid, usually 0.9 wt% NaCl solution or synthetic urine. Excess liquid isremoved from the swollen hydrogel by blotting to minimize interparticle slippage.The hydrogel typically is placed onto the lower circular plate. An upper conicalplate is positioned at the proper sample gap, which is packed with the gel. Anoscillating torque is applied at a known frequency to the upper plate, and theresulting angular displacement of the cone is determined. The shear modulus ofthe hydrogel is calculated from the ratio of the applied stress to the resultingstrain (42).

Particle Size Distribution. The particle size distribution is determinedby sieving. The Rotap sieving, similar to the ASTM method used for polymerpowders (43) is typically used. The method consists of placing a known quan-tity of the powder in a stack of sieves that are shaken horizontally while be-ing hit at the top with a hammer (44). Alternatively, vibrating sieve sets maybe used. The mass of polymer on each sieve is measured gravimetrically. Fromthis data, the size distribution may be plotted and the mass-median particle sizecalculated.


Bulk Density and Flowability. The polymer bulk density (45) and poly-mer flowability (46) affect conveying pipe and hopper design in the polymer-manufacturing plants and dosing machine settings on diaper-manufacturinglines. Flowability is typically evaluated by timing the flow of a 100-g granularsample from a funnel into a cylinder of known volume. The bulk density, takenfrom the same procedure, is the mass/volume ratio of polymer in the cylinder.

Swelling Kinetics Methods. Swelling kinetics for superabsorbent poly-mers may be measured by a viscometric method (47), based on the dependence ofsuspension viscosity on the volume fraction of the suspended particles. However,the swelling rate is most often measured by determining the specific absorbencyas a function of time, for example, by means of the centrifuge capacity analysis.An absorption rate may also be obtained from data of swelling vs time using thedemand absorbency method (48).

A simple, single-point measurement of kinetics has been used in the patentart (49–51), and its characteristics have been described (52). The method, referredto as the “vortex time” analysis, is based upon the earlier exponential kineticequation, rearranged to obtain equation 6 for a characteristic swelling time interms of the values of Q, Qmax, and the rate coefficient k. When the relative swellingof the sample Q/Qmax is known or is held constant, then tv is simply related to therate coefficient.

tv = − 1k

ln(

1 − QQ max

)(6)

In the original method (49), 2 g of polymer sample is mixed with 50 mL of thedesired test fluid, which is stirred by means of a magnetic stirring bar in a smallbeaker. As the fluid absorption proceeds, the viscosity of the suspension increasesuntil the stirring vortex disappears at time tv. The volume fraction of swollenpolymer in the suspension when the vortex disappears was estimated to be equalto 0.52 (52). For the most accurate and comparable results across samples withdifferent swelling capacities, the mass of polymer added must be adjusted basedon the value of the specific absorbency. As the specific absorbency increases, lesspolymer is used in the test so that each sample reaches the same relative swellingextent at time tv (53).

Absorbency under Load. The absorbency under load is a commonly usedmeasure of the performance of superabsorbent polymers in absorbent productssuch as diapers. It is not so much a property of the superabsorbent polymer, butrather a swelling phenomenon of a compressed, packed bed of polymer particles.The test system consists of a short plastic cylinder with a fine mesh screen fixedover one end. A quantity of dry polymer particles is placed on the screen andcovered with a loose-fitting plastic disk as a piston. A standard weight is placedon the plastic piston, and then the polymer is put into contact with a saline so-lution through the fine mesh screen. As the polymer absorbs liquid, the swellingparticles fill the cylindrical cell and push up the piston. The gravimetric swellingratio achieved in a standard time is determined. The test is thought to mimic thebehavior of the polymer as it swells within the absorbent core, under compression


applied by the baby’s body. The test has been modeled in terms of the polymerproperties and some characteristics of the particle bed (54).

Gel Bed Permeability. The liquid permeability of composites of cellu-lose fiber and superabsorbent polymer is critical to the proper performance ofabsorbent hygiene products such as infant diapers. The permeability of swollenbeds of superabsorbent particles is used as a measure of the contribution of thepolymer toward the permeability of the composites. The permeability of particlebeds is described as a function of both the specific surface of the pores and theporosity of the bed, according to the Carman-Kozeny equation (55). For dynami-cally swelling systems, the specific surface and porosity change with time becausethe volume of the particles and their elastic modulus changes during swelling.Compression of the bed complicates the situation.

Several patents describe superabsorbent polymers that provide for bettergel bed permeability (56–58). An early technique to measure gel bed permeabilityhas been described by Amiya (59). In this method, the superabsorbent particlesare swollen freely to equilibrium in saline solution within a glass buret. Thenthe liquid flow rate through the gel bed is used as a measure of permeability. Asimilar method, but with the swelling in saline done under compression is alsodescribed, and the permeability is calculated from the flow rate and bed geometry(60). Methods to measure the porosity of a gel bed under compression (61) or thegel bed resiliency or compressibility (62) have also been described.

Uses

The unique attributes of superabsorbents make them useful in many different ap-plications. The liquid absorption and retention ability makes them useful in dis-posable hygienic products. These include infant diapers, feminine hygiene pads,and adult incontinence products. Other absorbent products suitable for superab-sorbent polymers are paper towels, surgical sponges, meat trays, disposable matsfor outside doorways, household pet litter, bandages, and wound dressings. Be-cause the gels can slowly release water vapor to the atmosphere, they can be usedin humidity-controlling products or as soil conditioners. Superabsorbent polymerscan also release water-soluble substances from within the network structure intosurrounding solutions; hence, pharmaceuticals or fertilizers may be controllablyreleased from within the gels. The rubbery nature of the swollen gels can controlthe consistency of cosmetics or concrete and yield a soft and dry feel to hot or coldpacks for sore muscles. The combination of swelling and soft rubber propertiesimparts sealing properties to products that may come into contact with water oraqueous solutions, such as underground wires and cables. In the following para-graphs, additional details will be given of how the properties of superabsorbentpolymers affect their utility in specific products.

Disposable Infant Diapers. A basic disposable diaper consists of an ab-sorbent core sandwiched between a liquid permeable top-sheet and an imperme-able back-sheet (63). The top-sheet, next to the baby’s skin, allows urine to flowthrough it into the core. The back-sheet, made of impermeable plastic, helps keepthe baby’s clothing dry. The core takes in the liquid, distributes it within the core,and holds the liquid under compression from the baby.


In a diaper, the polymer is mixed with 0.5–10 times its mass of cellulosepulp fluff (processed wood fiber) to make up the core (64–66). Cores containingsuperabsorbents are thinner because a smaller volume of dry superabsorbentpolymer can absorb the same volume of aqueous liquid as a larger volume offluff.

In addition to the specific absorbency of the superabsorbent polymer, the ab-sorption rate of the diaper must be optimized to the urination rate of the baby.When the core absorbs too slowly relative to the urination rate, the liquid over-flows the core and leaks from the diaper. The absorption rate of the composite isinfluenced by the absorption rate of the superabsorbent polymer. Fast swellingof the polymer can contain the liquid quickly. However, in some diaper designs,fast swelling may cause the diaper to leak if the porosity and permeability of thecomposite is reduced too rapidly.

Adult Incontinence. Adult incontinence products include belted or fitteddisposable garments and light incontinence pads, which are similar to femininenapkins. Similar design considerations are used as in baby diapers. In adults theliquid volume is larger and the urination rate is faster than in infants; therefore,polymers with larger specific absorbency and faster swelling rate are desired forthis application (67). The market for these products is growing with the agingpopulation.

Feminine Hygiene. The first personal-hygiene product commercializedwith superabsorbent polymer was a feminine napkin in Japan. Perhaps the biggestchallenge in using superabsorbent polymer in these products is the huge differencein properties between urine and menstrual fluid. Menstrual fluid is a complex,viscous mixture of water, salts, proteins, and cells. The cells are far too large tobe absorbed into the superabsorbent polymer, and the proteins make the fluidvery viscous and thereby slow the diffuse of liquid into the polymer. In other bloodabsorption applications, such as in surgery and surgical appliances, the polymerscan be chemically modified to prevent undesired blood clotting (68). Incorporatingsimilar additives into superabsorbent polymers may improve their performancein feminine hygiene products.

Agricultural and Horticultural Applications. Superabsorbents in agri-culture and horticulture are used as a mulch, to help the soil retain moisture(69,70). To provide this function, the polymers optimally are mixed into soil ata concentration of about 0.1 wt%. The resulting mixture retains moisture longerthan untreated soil and helps maintain optimum germination conditions. Super-absorbent polymer helps improve porosity in clay soils, as the polymer particlesexpand and contract during the moisture cycles. However, in wet and soggy soilswith low oxygen content, superabsorbent polymers can prolong the unfavorablesoil conditions. Salt-tolerant superabsorbent polymers may be more useful thanthe common polyacrylates for this application. An excellent review of superab-sorbents in soil has been published (71).

Construction Materials. Superabsorbent polymers are used to controlliquid water in a variety of construction-related products. Joint-sealing compos-ites are made by blending superabsorbents into chloroprene rubber (72) or intopoly(ethylene-co-vinyl acetate) (73). These composites are used like mortar in theconcrete block walls of the structure. Gaps left during construction are subse-quently filled as the superabsorbent swells in any water, and subsequent leaks


are prevented. A water-blocking construction backfill has also been developed fromcement, water-absorbing polymer, and an asphalt emulsion (74).

The swelling property of superabsorbents also protects communication ca-bles from water damage (75,76). Water-blocking tapes are wrapped around fiber-optic communication cables and power transmission cables to stop intrusion ofwater into the cables if the water-resistant coverings are cut or broken (77). Theswelling polymer seals the damaged area and slows water penetration furtheralong the cable.

Food Packaging. Superabsorbent polymer can also absorb juice or waterfrom raw chicken, shellfish and other meats, or from frozen foods as they thaw, re-ducing sogginess of the product (78). Chilled superabsorbent polymer gels can alsobe used as a dry-cooling medium to keep perishable foods cold (79). The humidity-controlling property of superabsorbent polymer can also be used to maintain aconstant humidity in vegetable and fruit storage and prevent water spotting onfruits (80).

Sensors. Superabsorbent polymers can be used in sensor systems byvirtue of their swellability and rubbery nature, which are controllable by changesin water content, pH, and ionic strength. Because a small voltage may be inducedin a soft hydrogel by applying mechanical stress to the gel, a pressure-sensitiveswitch is possible (81). The potential that develops between the stressed and un-stressed parts of the gel generates a signal that can light a photo diode. The in-tensity of the light emitted by the diode depends on the magnitude of the appliedstress. The application of a voltage across a polyelectrolyte gel conversely causes avolume change in the gel. This may be used to perform work in applications suchas robotic fingers (82) or artificial muscle (83).

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GENERAL REFERENCES

F. L. Buchholz and N. A. Peppas, eds., Superabsorbent Polymers, Science and Technology(ACS Symposium Series 574), American Chemical Society, Washington, D.C., 1994.F. L. Buchholz and A. T. Graham, eds., Modern Superabsorbent Polymer Technology, Wiley-VCH, New York, 1998.J. P. Cohen Addad, Physical Properties of Polymeric Gels, John Wiley & Sons, Inc., NewYork, 1996.D. DeRossi, K. Kajiwara, Y. Osada, and A. Yamauchi, eds., Polymer Gels, Fundamentalsand Biomedical Applications, Plenum Press, New York, 1991.L. Brannon-Peppas and R. Harland, Absorbent Polymer Technology, Elsevier Science Pub-lishing Co., New York, 1990.P. K. Chatterjee, ed., Absorbency, Elsevier Science Publishing Co., New York, 1985.K. Dusek, ed., Responsive Gels: Volume Transitions 1 (Advances in Polymer Science, Vol.109), Springer-Verlag, Berlin, 1993.K. Dusek, ed., Responsive Gels: Volume Transitions 2 (Advances in Polymer Science Vol.110), Springer-Verlag, Berlin, 1993.

FREDRIC L. BUCHHOLZ

The Dow Chemical Company

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Encyclopedia of Polymer Science and Technology || Superabsorbent Polymers