Rheology of high-solids biomass slurries for biorenery applications

Jeffrey S. Knutsen and Matthew W. Liberatorea)

Department of Chemical Engineering, Colorado School of Mines, 1613 Illinois Street, Golden, Colorado 80401
(Received 18 November 2008; nal revision received 5 May 2009

Synopsis
Biomass slurries, such as dilute-acid pretreated corn stover PCS , will be a common process stream in bioreneries designed to convert agricultural residues into biofuels such as ethanol. In this work, the advantages and disadvantages of several rheological techniques are evaluated for PCS suspensions. Three ow regimes were evaluated: i shear ow using a vane, ii torsional ow between parallel plates, and iii biaxial extensional ow between plates. The vane provided the simplest methodology and the most reproducible results. Four experiments were conducted using the vane: i transient ow, ii stress ramps, iii creep, and iv oscillatory shear. PCS slurries with fractions of insoluble solids FIS ranging from 5% to 17% by weight exhibited soft-solid characteristics, including an apparent yield stress. Yield stresses were highly dependent on stover concentration, scaling with FIS to the sixth power, and ranged from 0.25000 Pa between 5% and 17% FIS. PCS suspensions were strongly shear thinning, with ow and dynamic viscosities that were highly dependent on FIS. Last, as with many concentrated suspensions, the CoxMerz rule was not followed, although ow and dynamic viscosities were coincident when plotted versus an effective shear rate.

2009 The Society of Rheology. DOI: 10.1122/1.3143878 I. INTRODUCTION Ethanol production from cellulosic biomass has been lauded for many years as a potential renewable, large-scale transportation fuel with numerous benets, including the improvement of air quality, mitigation of global climate change, and improvement of energy security. Although non-grain feed-stock supplies, energy balances, and environmental impacts are generally favorable, economic analyses suggest that current biomassto-ethanol process designs are likely to be prohibitively expensive Cleveland et al. 2006 ; Wyman 2007 . Sugars generated via enzymatic saccharication can be converted into value-added products, including fuel ethanol, in a new process paradigm generally referred to as the biorenery Ragauskas et al. 2006 . However, to be useful, these sugars must be manufactured at a suitably high concentration, and the economics of saccharication must be favorable. Operation of a biorenery at a relatively high-solids loading is one way to meet these requirements. For example, a biomass-to-ethanol design report compiled at the National Renewable Energy Laboratory NREL Aden et al. 2002 calls for an insoluble solids content of over 10% w/w after pretreatment, while

Author to whom correspondence should be addressed; electronic mail: mliberat@mines.edu

2009 by The Society of Rheology, Inc. J. Rheol. 53 4 , 877-892 July/August 2009

0148-6055/2009/53 4 /877/16/$27.00

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a process developed by Iogen Corporation Tolan 2002 accommodates an upper-bound insoluble solids concentration of 15%20% w/w . By minimizing the amount of water entering the process, the resulting sugar concentrations will be higher and capital and operating costs will be lower due to the decreased volume Mohagheghi et al. 1992 . In comparison, processes based on starch have long been run at concentrations as high as 33%37% Thomas and Ingledew 1992 , and optimized cellulose-based designs may eventually reach similarly high concentrations. Lignocellulosic biorenery designs typically rely on an initial pretreatment process, such as dilute-acid hydrolysis, to partially liquefy the raw feedstock by dissolving fractions of lignin and hydrolyzing hemicellulose into ve-carbon sugars Nguyen et al. 1996 . Thus, pretreatment creates biomass slurries rich in cellulose and lignin that can be more readily transported to downstream processes. Unfortunately, high-solids slurries have large viscosities and yield stresses and are notoriously difcult to process. Processing accounts for up to two-thirds of the energy cost per gallon of lignocellulosic fuel Wyman 2007 . Compounding difculties with design and scale up, processing costs are likely to be a very sensitive function of solids concentration. For example, Fan and co-workers 2003 observed that the necessary power requirements for mixing of paper sludges increased sharply with solids concentration; a 4% increase in solids content resulted in a vefold increase in power consumption. Therefore, in pursuit of an optimal biorenery design, understanding and interpretation of the slurries rheological properties is of paramount importance. Recently, investigations of high-solids lignocellulosic slurries have begun Pimenova and Hanley 2003, 2004 ; Dasari and Berson 2007 ; Jrgensen et al. 2007 ; Rosgaard et al. 2007 ; Um and Hanley 2008 ; Viamajala et al. 2009 . Accurate rheological characterization of these slurries is plagued by a number of difculties, especially wall slip and settling of particulates in dilute suspensions. Pimenova and Hanley 2003, 2004 used a helical impeller to infer the rheological properties of corn stover suspensions through a series of relative measurements. Although circumventing many difculties, the helical impeller induced a complex ow that did not allow direct calculation of the shear rate. Rather, relative measurements were made by calibrating the tool with Newtonian and non-Newtonian uid standards. Their work revealed that corn stover suspensions were highly shear thinning with viscosities and yield stresses that were strongly dependent on stover concentration, increasing by orders of magnitude when the concentration of total solids was increased from 5% to 30% w/w Pimenova and Hanley 2003, 2004 . The sensitivity of rheological properties, especially yield stress, to solids concentration is not unique to corn stover. Power-law dependences of the yield stress as a function of concentration e.g., volume fraction or dry solids concentration have been shown for bentonite gels, fermentation broths, and paper pulp Allen and Robinson 1990 ; Bennington et al. 1990 ; Alderman et al. 1991 ; Mohseni and Allen 1995 ; Riley et al. 2000 . The power-law coefcient ranged from about 1 to 3 in these systems. Other systems exhibit yield stresses that vary exponentially with concentration, including titanium dioxide suspensions, wastewater sludges, and corn stover slurries Pimenova and Hanley 2004 ; Mori et al. 2006 ; Nguyen et al. 2006 . At low concentrations, less than 2.3% w/v , a linear correlation between yield stress and solids concentration has also been observed Laera et al. 2007 . In the current work, the concentration scaling of the pretreated corn stover PCS slurries will be an important relationship for designing large-scale bioreneries in the coming years. The focus of the present work is to rheologically characterize model biomass slurries encountered following pretreatment and preceding enzymatic saccharication. This work contrasts the advantages and disadvantages of several ow geometries and establishes an

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accurate, reproducible rheological methodology. Additionally, process design considerations demand a thorough understanding of the variability and scaling of rheological parameters with solids concentration. To this end, the rheology of two different batches of PCS was investigated across a broad range of solids concentrations. II. MATERIALS AND METHODS A. Biomass Slurries of PCS were provided by the NREL Golden, CO . Pretreatment at NREL consisted of mixing corn stover with dilute sulfuric acid in an engineering-scale countercurrent pretreatment reactor system Nguyen et al. 1996 ; Tucker et al. 1998 . Pretreatment hydrolyzes portions of the hemicellulose and dissolves a fraction of the lignin, exposing cellulose bers for subsequent enzymatic hydrolysis. The result is an aqueous suspension, or slurry, of stover particles rich in cellulose and lignin. Optical microscopy indicates that the particles are highly brous in nature, with length scales on the order of microns to millimeters and aspect ratios ranging from 1 to 20. Additionally, about 1020 large particles of stover about 13 mm in diameter are present in a typical 50 mL sample of undiluted PCS. These particles are likely recalcitrant pieces of corn cob or stalk that were not converted during pretreatment. The interstitial uid was Newtonian and consisted mainly of pentose sugars and other residual solutes from pretreatment. The viscosity of the interstitial uid is slightly greater than water = 2.0 0.1 mPa s at 25 C . Suspensions were characterized in terms of their fractions of total, soluble, and insoluble solids. The weight fraction of total solids FTS was measured by evaporating water and other volatile compounds from a sample of suspension. The weight fraction of soluble solids FSS in the liquor was measured by centrifuging a sample of suspension and ltering the supernatant to remove all suspended solids. Volatile liquids in the ltrate were then evaporated, leaving only soluble solids behind. Therefore, FSS is the mass FSS in water, not the mass FSS in the total suspension. The weight fraction of insoluble solids FIS represents the weight fraction of solids that do not dissolve in the suspending liquor at ambient conditions. FIS was estimated by the following mass balance: FIS = FTS FSS . 1 FSS 1

FIS Eq. 1 estimated in this manner compared well with other methodologies, including repeated washing/centrifugation and membrane dialtration. To assess the effect of concentration on the rheology, the pretreated stover was diluted with de-ionized water to concentrations as low as 5% FIS. Concentrations below 5% were not evaluated, as these suspensions settle appreciably on the experimental time scale, resulting in measurement artifacts. Pretreated stover was also concentrated to as much as 20% FIS by centrifuging and removing supernatant. B. Rheometry All rheological experiments were performed using an AR-G2 rheometer TA Instruments, New Castle, DE operated in controlled-stress or strain rate modes. Torsional and shear ows were investigated using parallel-plate and vane-in-cup geometries, respectively, and biaxial extensional squeeze ow was examined using parallel plates. The presence of large particles in the corn stover suspensions prevented the use of cone-andplate geometry for shear ow experiments.

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Parallel plates used for torsional ow experiments consisted of a 40 mm diameter polished steel upper rotating plate with a larger, stationary, lower plate with Peltier temperature control. A gap height of 4 mm was maintained in torsional ow experiments. In select parallel-plate experiments, coarse-grit adhesive tape 3M, St. Paul, MN was applied to the upper and lower plates to mitigate uid slip. Torsional ow experiments were conducted by controlling the rotational speed of the upper plate and plotting the applied torque as a function of plate displacement. Squeeze ow circumvents many difculties in traditional rheometers by ensuring that the internal deformation of material occurs, especially in the presence of wall slip Sherwood et al. 1991 ; Meeten 2000, 2002, 2004a, 2004b, 2007 ; Chandler et al. 2002 ; Engmann et al. 2005 . In particular, Meeten 2000, 2002 examined the utility of squeeze ow to measure the yield stress of structured uids. He observed that gap heights approached limiting values hL at specic compressive forces and then compared hL to theories using the Herschel-Bulkley relation with no-slip boundary conditions. At hL, the yield stress 0 can be estimated by = FhL
2 3

R3

where F is the force between the plates and R is the plate radius. Thus, a plot of hL versus 2 3 3 R / F should be linear with slope 0. Squeeze ow experiments were conducted by loading PCS preformed into a rough cylinder with an initial height of approximately 6 mm, between smooth 40 mm plates. The rheometer was then programmed to maintain specic compressive forces of 0.1, 10, 30, and 50 N by adjusting the gap height. The gap closure rate was limited, requiring about 30 s for the compressive force to stabilize. Once the compressive force stabilized, the gap continued to slowly close, eventually approaching a limiting value after about 10 min. Two vane geometries were used in shear ow experiments. The cup diameter for both vane geometries was 30 mm and contained Peltier temperature control. The vane diameters were 28 mm for the narrow gap and 15 mm for the wide gap, resulting in gap widths of 1 and 7.5 mm, respectively. The heights of the narrow- and wide-gap vanes were 42 and 38 mm, respectively. After fully immersing the vane in the suspension, the bottom of the vane was 412 mm above the bottom of the cup. The axial force required to press the vane through the slurry was monitored. Although axial forces were substantial for undiluted PCS 17% FIS , reaching 2030 N in some experiments, the vane was easily lowered into dilute suspensions. Axial forces of 0.40.6 N for PCS at a concentration of 10% FIS and 0.1 N or less at 5% FIS were measured the latter force is on the order of the buoyancy force induced by the displaced volume of the vane . To probe the magnitude of end effects, in select experiments with undiluted PCS the vane was retracted 200 300 m to reduce the axial force below 1 N, relieving stresses at the bottom of the cup. To investigate the possibility of slip at the cup wall, a serrated cup was used in select experiments with the narrow-gap vane. However, the presence of a few large stover particles or bers with lengths of 1 to several millimeters would jam the rheometer by lodging between a serration and the vane tip. Therefore, in these experiments the largest particles were removed by sieving through a 500 m sieve. Because large particles were present at a weight fraction of less than 1%, it is not likely that their removal affected the bulk suspension rheology. Several experiments were conducted with the vane, including oscillatory stress/ frequency sweeps in controlled-stress mode and three unidirectional experiments: transient ow, steady-state ow, and stress ramps. Oscillatory stress sweeps were used to

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identify linear viscoelastic regions LVRs and were especially useful in determining the presence and magnitude of a yield stress, dened both by the crossover of G and G and the maximum value of the elastic stress G 0 . Details are described by Walls et al. 2003 . Transient ow TF experiments were conducted by rotating the vane at a slow steady rate and plotting the applied torque as a function of vane displacement. These experiments were conducted using both the narrow- and wide-gap vanes and with smooth and serrated cups. After each experiment, the stover was removed from the cup, remixed by hand using a laboratory spatula, and re-loaded. Steady-state ow experiments were conducted by controlling the rotational speed of the vane at several rates and monitoring the applied torque over time. If the applied stress torque became relatively steady, based on several criteria, the steady value was used as a data point in the steady-state ow experiment. Stress ramp experiments were conducted using the narrow-gap vane by steadily increasing the applied torque and monitoring the rotational speed of the vane. Note that the rst two ow experiments, based on controlled-strain rate, were generally more reliable, as the inhomogeneous stover suspensions unpredictably jammed the rheometer in controlled-stress mode. Jamming effects are mitigated in controlled-strain rate experiments because the rheometer quickly increases the applied stress to maintain a steady rate of strain. Thus, jamming appears as small obvious stress peaks that are readily discounted in the data analysis. However, in controlled-stress mode, even small jams that only slightly exceed the applied stress will completely halt the deformation of sample. All experiments were completed at 25 C. Error bars represent one standard deviation of at least three replicate runs unless otherwise noted. III. RESULTS AND DISCUSSION A. Torsional ows Controlled-strain ow experiments using the smooth parallel-plate geometry typically resulted in torque versus displacement curves that rapidly approached a steady value as the upper plate was rotated. However, bulk deformation of the stover was not observed during these experiments, and it appeared likely that the tool was simply slipping over the suspension. Additionally, loading of the suspensions in this geometry was difcult, as the stover must be preformed into a 40 mm diameter cylinder with a height approximately equal to the desired gap height, typically 4 mm. Initial experiments revealed that the initial height of the formed stover cylinder signicantly affected the ow curves. A cylinder height taller than the desired gap would be compressed upon loading, resulting in a normal force between the plates and relatively high torque curves. To test whether meaningful results could be gained from smooth plates, a set of experiments was conducted by changing the normal force between the plates, as shown in Fig. 1 a . In each experiment, the applied torque reached a steady value after small displacements of the upper plate. Higher values were observed for higher applied normal forces. When the steady torque values are plotted against applied normal force Fig. 1 b , the data appear linear, with an intercept at the origin. This result suggests that the upper plate is indeed slipping, with a coefcient of dynamic friction f that is proportional to the slope of the data, as shown in Fig. 1 b . The coefcient of dynamic friction f = FS / FN is the ratio of the shear or tangential force FS, acting between two sliding surfaces, to the applied normal or compressive force FN. It is typically a constant for two given surfaces; consequently, the shear force is proportional to the normal force. f can be estimated using two rotating circular surfaces by integrating a differential torque balance across their radii. The resulting equation shown in Fig. 1 b relates f to the plate radius r, the torque required to turn the plate M, and the applied normal force Matthews 2002 . A value of

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200000 40 N (b) 180000 160000 Steady Torque - M (N-m) 140000 120000 100000 80000 60000 40000 20000 0 0.02 0.04 0.06 0.08 0.10 0 10 20 30 40 50 Plate Displacement (revolutions) Normal Force - F N (N)

M N m = 3930 70 FN N

20 N 80000 60000 40000 5N 20000 0 0.00

f =

3M 1 = 0.295 0.005 2 FN r

FIG. 1. Experiments with smooth 40 mm parallel plates using undiluted PCS 17% FIS . a Torque versus plate displacement for normal forces of 5, 20, and 40 N bottom to top . b Steady torque as a function of normal force. The line is a least-squares regression of the data with an intercept at the origin. The rotational speed was about 1 rph.

f 0.3 was observed in these experiments. For comparison, the coefcient of dynamic friction between PCS and the steel rotating plate is slightly higher than the published value for wood-on-wood f = 0.2 and roughly half the published value for steel-on-steel f = 0.57 Serway 1995 . Controlled-strain experiments conducted with roughened parallel plates Fig. 2 produced markedly different results than the smooth plates. In these experiments, the applied torque grew rapidly after the initial deformation, plateaued, and then decreased as the plate continued to rotate. Early researchers have suggested that elastic deformation occurs prior to yielding e.g., Dzuy and Boger 1983 , although Meeten 2008 recently indicated that a viscous component is likely present in this region. As will be shown through
3000 5000

(2)

(a)

(b)

2500

4000

Shear Stress (Pa)

Yield Stress (Pa)

(1) (3)

2000

3000

1500

2000

1000

500

1000

0 0 0.2 0.4 0.6 Revolutions 0.8 1

0 0 1 2 3 4 Normal Force (N) 5 6

FIG. 2. a Shear stress versus displacement of 40 mm parallel plates covered with rough adhesive tape for undiluted PCS 17% FIS . The strain rate was controlled at 0.01 s1, and the initial normal force was 2.5 N. Two example curves are shown. Photographs show PCS 1 just after loading, 2 upon yielding, and 3 after fracture and subsequent ejection from between the plates. b Apparent yield stress as a function of initial normal force upon loading. The solid line is a power-law trend to guide the eyes.

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7000 6000 5000 Gap (m) 4000 3000 2000 1000 0 0 10 20 30 Normal Force (N) 40 50 6000

883

(a)

(b)
0 = 320 Pa

5000
0 = 2500 Pa 0 = 9800 Pa 0 = 6500 Pa

4000 hL (m)

3000

2000

1000

0 0 5 10 3 R /F (m/Pa) 15 20

FIG. 3. a Limiting gap height as a function of normal compressive force between 40 mm parallel plates. Photographs show the extraction of interstitial uid from PCS due to compression initially 17% FIS . b Gap 2 height plotted against 3 R3 / F. For a yield stress uid without slip at the interface, the data in b would follow the linear trend with slope 0. Deviations from linearity are possibly due to radial ltration of the interstitial uid, with predicted values of 0 increasing as shown.

oscillatory experiments, viscous energy dissipation indeed occurs at small pre-yield strains. Nonetheless, in these experiments the maximum shear stress is considered an apparent yield stress. Upon yielding, the subsequent decrease in shear stress coincided with the fracture and eventual ejection of suspension from between the plates, and therefore no further information is generated. The apparent yield stress did not change signicantly with deformation rate across three decades, from = 0.01 to 1 s1. However, as with the smooth parallel plates, the normal force upon loading did affect the yield stress, as shown in Fig. 2 b . By qualitatively judging the contact between the roughened parallel plates and the initial stover cylinder, useful initial normal forces were typically between 1 and 3 N. Initial forces below about 1 N resulted in insufcient contact between the stover and the upper plate, and the plate simply slipped over the surface of the suspension, resulting in minimal bulk deformation. Initial normal forces above about 3 N resulted in gross biaxial deformation squeezing and excretion of interstitial uid from the suspension e.g., see inset photographs in Fig. 3 a . The latter phenomenon known as radial ltration results in undesired increases in solids concentration and measurement artifacts, especially when the interstitial uid viscosity is low Meeten 2007 . B. Squeeze ows The gap height measured in several squeeze ow experiments decreased from about 6 to roughly 3.5 mm when the compressive force was stepped from 0.1 to 50 N, as shown in Fig. 3 a . The linear behavior predicted by Eq. 2 was not observed, however, when 2 the limiting gap height was plotted versus 3 R3 / F, as shown in Fig. 3 b . If the theory did hold, data points would follow the shallowest line from right to left as compression proceeded, and 0 320 Pa would be maintained throughout the duration of the experiment. However, radial ltration, the excretion of interstitial uid from between the plates as the compressive force increases, results in non-uniform solids concentrations across the plate radius that increase as the experiment progresses Meeten 2007 . As an approximation, it was assumed that only interstitial uid was squeezed radially from beneath the periphery of the upper plate, as shown by photographs in Fig. 3 a . By this

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3500 3000 2500 Shear Stress (Pa) 2000 1500 1000 500 0 0 0.25 0.5 0.75 1 Vane Displacement (Revolutions) 2 5 3 6 4 0 = 2500500 Pa

1 2

FIG. 4. Typical results using undiluted PCS 17% FIS showing shear stress changing with vane displacement. Yield points for each experiment are identied with circles. Numbering as follows: narrow-gap vane at 1: 0.0007 rpm; 2: 0.007 rpm two example curves shown ; 3: 0.07 rpm; 4: 0.7 rpm; 5: wide-gap vane at 0.7 rpm, and 6: narrow-gap vane using a serrated cup at = 0.07 rpm.

approximation, FIS will increase by a predictable amount as interstitial uid is removed, resulting in a concomitant increase in the yield stress, and strong deviations from the predicted linear behavior in Fig. 3 b . For example, the reduction in gap height from 5400 to 3300 m results in a predicted increase in FIS from 17% to nearly 28% when a volume of uid V = 2 r2 h is removed. Thus, yield stresses predicted by Eq. 2 can be correlated with FIS, as shown in Fig. 9.

C. Shear ows In general, the most successful measurements were made by inducing shear ows with the vane geometry. Typical stress-displacement ow curves Fig. 4 are similar to the roughened parallel-plate experiments, exhibiting a rapid increase in the shear stress at small deformations, reaching a plateau upon yielding, and then decreasing with additional strain, behavior that agrees qualitatively with prior investigations e.g., Dzuy and Boger 1983 . Yield stresses measured in controlled-strain experiments were found to be independent of vane rotational speeds from 0.0007 to 0.7 rpm, equivalent to shear rates of 0.001 1 s1, averaged between the vane periphery and the cup wall. The independence of yield stress on rotational speed agrees with the ndings of several other investigators, who examined rotational speeds across similar ranges Dzuy and Boger 1983, 1985 ; Alderman et al. 1991 ; Leongpoi and Allen 1992 ; Nguyen and Boger 1992 ; Liddel and Boger 1996 ; Meeten 2000 . An important consideration is the possibility of slip occurring at the inner surface of the cup. The degree of slip was assessed qualitatively by using the narrow-gap vane with the serrated cup and by using the wide-gap vane with the smooth cup. Twenty-eight vertical serrations 2 mm deep mitigate slip in the former geometry, and wall shear

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0.1 5% FIS 0.01 Shear Rate (s )
-1

885

17% FIS

10% FIS 0.001

0.0001

0.00001 0.001

0.01

0.1

1 10 100 Shear Stress (Pa)

1000

10000

FIG. 5. Shear rate versus shear stress as measured in stress ramp experiments using the narrow-gap vane. Shear stresses were increased at rates of 100, 0.7, and 0.07 Pa/min for 17%, 10%, and 5% FIS suspensions of PCS, respectively.

stresses in the latter are low enough that slip is not likely to occur. Flow curves 5 and 6 in Fig. 4 measured using these geometries suggest that slip is minimal, as their respective yield stresses are within experimental uncertainty. After reaching maxima at the yield point, shear stresses in Fig. 4 decline with strain, eventually approaching relatively steady values that are nearly independent of shear rate. After pre-straining the samples, the results of steady-state ow experiments across three decades of shear rates from 0.01 10 s1 are shown in Fig. 8. These data show the shear-thinning nature of these suspensions, as well as the strong dependency of viscosity on FIS. Due to the relative independence of the steady-state shear stress with changes in shear rate, power-law coefcients in Fig. 8 were all very close to 1 i.e., three-order increases in shear rate consistently resulted in three-order decreases in the apparent viscosity . Additionally, viscosities at each shear rate exhibit a nearly exponential increase with FIS; viscosities were 1001000 times smaller when 17% FIS suspensions were diluted to 5%. Yield stresses were also measured by way of stress ramp experiments, in which the applied torque was ramped up at a continuous rate. Stress ramps were performed as described by Meeten 2002 by plotting the shear rate versus shear stress on logarithmic axes. Two nearly linear regions were observed, and the yield stress was dened by the intersection of lines tting each region Fig. 5 . The utility of creep experiments to measure yield stress was also investigated. In these experiments, an initial shear stress at the low end of the viscoelastic region was selected, based on oscillatory stress sweeps, and then increased sequentially in successive steps. Prior to yielding, little variation in the stover compliance is observed, and the rate of strain decreases to nearly zero over time Fig. 6 . The small but measurable amount of plastic deformation at low stresses corroborates the ndings of Meeten 2008 . He observed that stress was dissipated in step-strain experiments with dry foams at strains well below the yield point, suggesting pre-yield energy dissipation. Once the yield stress of PCS is exceeded, compliance is highly dependent on the applied stress, and the suspen-

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0.010 0.009 0.008 0.007 Compliance (1/Pa) 0.006 0.005 0.004 0.003 0.002 0.001 0.000 0 1 2 3 1500 Pa

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50 45 40 35 Compliance (1/Pa) 30 25 20 15 10 500 Pa; 100 Pa; 10 Pa 4 5 6 Time (min) 7 8 9 10 5 0 0 1 2 3 4 5 6 Time (min) 7 8 9 10 0.25 Pa; 0.1 Pa; 0.01 Pa 1 Pa

(a)

(b)

0.5 Pa

1000 Pa

FIG. 6. Compliance over time in creep experiments using the narrow-gap vane and smooth cup for a 17% and b 5% FIS suspensions of PCS. The yield stress is between 500 and 1000 Pa in a and between 0.25 and 0.5 Pa in b .

sion continues to strain indenitely. Yield stresses for 17% and 5% FIS suspensions were found to be between 500 and 1000 Pa and 0.25 and 0.5 Pa, respectively. Creep experiments required long experimental times and provided only a bounding estimate of the yield stress. Therefore, the utility of creep experiments was found to be limited, and additional experiments were not pursued. D. Oscillatory experiments Oscillatory stress ramps Fig. 7 exhibit traits indicative of soft-solid behavior, common to both raw and diluted PCS suspensions. The presence of a LVR at low oscillatory stresses is observed, with G roughly one order of magnitude larger than G , suggesting

100000 (2) LVR G'

1000

1000 Oscillatory Stress = Elastic Stress (1) 100 1 10 100 1000 Oscillatory Stress (Pa)

10

1 10000

FIG. 7. Oscillatory stress sweep of PCS 17% FIS using the narrow-gap vane geometry. Yield stresses are dened by 1 the crossover of G and G and by 2 the maximum value of the elastic stress. At low oscillatory stresses, the elastic stress equals the oscillatory stress, indicated by the diagonal line. A LVR was observed at oscillatory stresses below about 25 Pa. The oscillatory frequency was 1 Hz.

Elastic Stress (Pa)

10000 G' G" (Pa)

G"

100

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10000000 1000000 100000 ; | *| (Pa-s) 10000 1000 100 10 Osc FIS 17% Flow FIS 17% Osc FIS 10% Flow FIS 10% Osc FIS 5% Flow FIS 5%

887

1000000

100000

Flow Osc: 1% Strain Osc: 3% Strain Osc: 10% Strain

; | *| (Pa-s)

10000

= 920& 1.1

Flow:

1000

* = 910& 0.9
100

SAOS 10% Strain:

1 (a) 0.1 0.001

0.01 0.1 1 10 100 -1 Shear Rate ; Angular Frequency (s )

1000

(b) 10 0.001

0.01 0.1 1 10 -1 Shear Rate; Effective Shear Rate (s )

100

FIG. 8. a Steady-state ow and oscillatory frequency sweeps using the narrow-gap vane and smooth cup. Frequency sweeps were conducted within the LVR of PCS suspensions at concentrations of 5%, 10%, and 17% FIS. b Viscosity versus the effective shear rate 0 for PCS at 17% FIS. Solid lines in a and b are power-law ts to the data.

that deformation at low oscillatory stresses is primarily elastic, although a small viscous component is evident, a phenomenon observed elsewhere in dry shaving foams Meeten 2008 . As the stress is increased, G and G decrease and eventually cross over at the yield point. At low stresses, the elastic stress is equivalent to the oscillatory stress, also indicative of primarily elastic deformation. At moderate oscillatory stresses, however, the elastic stress falls below the oscillatory stress, indicating the onset of gross inelastic deformation. At this point, the elastic stress reaches a maximum and falls precipitously upon yielding. The crossover of G and G and the maximum value of the elastic stress, indicated by arrows 1 and 2 in Fig. 7, are two indicators of yield stress measured by oscillatory experiments Walls et al. 2003 . Oscillatory frequency sweeps indicate strong shear-thinning behavior at all concentrations investigated, in qualitative agreement with steady ow experiments Fig. 8 . Powerlaw coefcients were also very similar at three stover concentrations, ranging from 0.86 to 0.89. The complex viscosity varied exponentially with FIS, increasing 3 to 4 orders of magnitude between 5% and 17% FIS. The CoxMerz relationship is an empirical relationship that posits similarities between the shear rate dependence of the steady ow viscosity and the frequency dependence of the complex viscosity Cox and Merz 1958 . A comparison of steady-state ow and oscillatory experiments Fig. 8 suggests that corn stover suspensions do not follow the CoxMerz relationship at shear rates and angular frequencies tested. At all three concentrations, the complex viscosity is consistently higher than the ow viscosity, although differences are smaller at lower stover concentrations. The relatively low ow viscosities may result from fracturing of the suspensions and/or slip between particles possibly in the form of shear banding . These results were not entirely surprising, however, as other researchers have noted that the CoxMerz relationship was not observed in similar pseudo-plastic uids, such as peanut butter Bistany and Kokini 1983a, 1983b . The viscosity data were re-plotted versus the oscillatory strain 0 multiplied by the , an effective shear rate dened by Doraiswamy et al. 1991 . angular frequency Called the modied CoxMerz rule, complex and ow viscosities were coincident when plotted versus the effective shear rate on logarithmic axes, with a slope of 1 at low effective shear rates, indicative of yield stress behavior. As shown in Fig. 8 b , the

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100000

10000

1000 0 (Pa)

Batch1 - TF - Wide Batch1 - TF - Narrow Batch1 - TF - Narrow Batch1 - TF - Narrow - Serr Cup Batch1 - Stress Ramp - Narrow Batch1 - SAOS G'G'' - Narrow Batch1 - SAOS G'G'' - Narrow Batch1 - SAOS MES - Narrow Batch1 - SAOS MES - Narrow Batch1 - Squeeze Flow Batch2 - TF - Wide Batch2 - TF - Narrow Power Law Fit

100

10

0 = 7.7107 FIS6.0

0.1 1% 10% FIS 100%

FIG. 9. Yield stresses measured using several methodologies for two batches of PCS as a function of FIS. TF and oscillatory measurements G G : crossover between moduli; MES: maximum elastic stress were made using wide-gap and narrow-gap vanes. Gray data points represent vane loadings with a relieved normal force details in Sec. II B . Squeeze ow measurements were made using 40 mm parallel plates.

modied CoxMerz rule is well satised for undiluted PCS measured by controlled-strain frequency sweeps with 0 = 3% and 50%. Flow and dynamic viscosities are nearly identical with a slope of about 1. The modied CoxMerz rule was not obeyed at low stover concentrations, however, possibly due to low yield stresses. E. Effect of insoluble solids concentration on yield stress Although process economics dictate that only the highest workable concentrations of PCS would be used in a biorenery, a range of corn stover dilutions was examined to compare with the decreasing insoluble solids concentration during enzymatic hydrolysis. The effect of FIS on the yield stress measured by TF, oscillatory, and stress ramp experiments using the vane geometries, and by squeeze ow using parallel plates Fig. 9 elucidates a concentration scaling relationship for PCS suspensions. The effect of sieving the suspensions to remove particles larger than 500 m was also investigated and used in combination with the serrated cup to prevent wall slip. Yield stresses measured using the different geometries vary up to tenfold, with yield stresses measured by TF experiments being the highest, followed by oscillatory and then by stress ramp experiments. In TF experiments, a three- to vefold spread in yield stresses was observed between the vane geometries. Although end effects appear signicant for undiluted PCS, reducing the apparent yield stress from about 3000 to 1000 Pa when the axial force is relieved after loading, the difference is within experimental

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uncertainly Fig. 9 . End effects are insignicant for dilute suspensions, with axial forces less than 0.5 N. At dilute stover concentrations, yield stresses measured with the widegap vane were generally the highest, followed by the narrow-gap vane and serrated cup using sieved stover , and then by the narrow-gap vane and smooth cup. However, for undiluted stover suspensions at about 17% FIS, similar yield stresses were observed for all three vane geometries, indicating that wall slip did not signicantly affect yield stress values measured via TF experiments. Yield stresses measured via oscillatory experiments with the narrow-gap vane and smooth cup were slightly below yield stresses measured by TF experiments. Values dened by the crossover of G and G were 20%40% greater than those dened by the maximum value of the elastic stress, in agreement with Walls and co-workers 2003 . Squeeze ow resulted in substantially lower yield stresses than the vane geometry. Unfortunately, radial ltration hinders the use of squeeze ow measurments for PCS, necessitating the assumption that only interstitial uid is squeezed from between the plates during the experiment. This assumption may result in overpredicted values of FIS, and actual solids concentrations are likely to be lower, resulting in better agreement with the other rheological methods. Strong power-law correlations between the yield stresses and FIS were observed, a result of more abundant interparticle interactions at higher concentrations. Exponents ranged from 5.2 to 6.5 for individual data sets with coefcients of variation in excess of 94%. A power-law model for all rheological methods is shown in Fig. 9, with an exponent of 6.0 0.4 95% condence interval , with a slightly lower coefcient of variation of only 90% resulting from the aggregation of methodologies. It is unclear why yield stresses in the current study scale with solids concentration to such a large power. Prior studies, mentioned earlier, typically observed exponents of about 13 in several types of particle suspensions. One hypothesis is that the brous nature of the PCS particles, with large aspect ratios and disperse size distributions, imparts more extensive interparticle interactions. Thus, changes in the insoluble solids concentration or particle volume fraction result in changes to the yield stresses that are larger than measured in other studies. IV. CONCLUSION The rheology of PCS slurries encountered following pretreatment and preceding enzymatic saccharication in a biorenery was investigated. Advantages and disadvantages of several ow geometries were evaluated, with the goal of establishing an accurate, reproducible rheological methodology. As with other rheological studies of soft solids, eliminating wall slip was a major concern. Several geometries and ow regimes were tested, including parallel-plate and vane geometries under shear, torsional, and biaxial extensional ows. The vane was found to be the most effective geometry, easiest to reproducibly load, and reduces or eliminates wall slip. Biaxial extensional ows were also used to ensure deformation, resulting in yield stresses that agreed reasonably well with those measured with the vane, although radial migration of interstitial uid must be accounted for. Slip was most prominent with smooth parallel-plates, and controlled-strain ow experiments resulted in meaningless torques that scaled linearly with compressive force. Roughened parallel plates mitigated slip, but the yield stresses exhibited a great deal of variability and were especially sensitive to the compressive force upon loading. Additionally, the stover fractured and was ejected from between the plates after a few strain units. PCS suspensions at concentrations ranging from 5% to 17% FIS were found to act as soft solids, exhibiting primarily elastic deformation at low strains prior to yielding, and elastic moduli that were typically tenfold greater than viscous moduli at low oscillatory

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stresses. TF, oscillatory, and stress ramp experiments provided the simplest and most reproducible estimates of the yield stresses. Other rheological experiments, such as creep and biaxial extensional ows, proved time consuming and resulted in less reproducible measurements. Though the vane geometry was most reliable, a relatively large measurement uncertainty was still observed, with coefcients of variation of about 10%50%, possibly due to the underlying heterogeneity of stover particles and batch-to-batch variability. Nonetheless, yield stresses were strongly dependent on the concentration of stover, scaling with solids concentration to the sixth power, a dependency that is much stronger than observed in several other studies on soft solids and concentrated suspensions. The difference between PCS and other soft solids may be due in part to the brous nature of PCS. Additionally, the PCS slurries were strongly shear thinning and obeyed a modied CoxMerz relationship. Finally, the rheological methods described in this work form the foundation of more extensive rheological testing, including the effect of enzymatic hydrolysis on the stover rheology. ACKNOWLEDGMENT Support for this research was provided by the Department of Energy and the National Renewable Energy Laboratory Golden, CO through Subcontract No. ZDJ-7-77605-02.

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