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He has carried out a great deal of research and technical survey work as well as several studies in the aforementioned areas with over 170 published international academic works in different languages.",coeditorOneBiosketch:null,coeditorTwoBiosketch:null,coeditorThreeBiosketch:null,coeditorFourBiosketch:null,coeditorFiveBiosketch:null,editors:[{id:"110471",title:"Dr.",name:"Amjad",middleName:"Zaki",surname:"Almusaed",slug:"amjad-almusaed",fullName:"Amjad Almusaed",profilePictureURL:"https://mts.intechopen.com/storage/users/110471/images/system/110471.png",biography:"Amjad Almusaed was born in 1967. He holds a PhD degree in Architecture (Environmental Design) from Ion Mincu University, Bucharest, Romania. He completed postdoctoral research in 2004 on sustainable and bioclimatic houses, from the School of Architecture in Aarhus, Denmark. His research expertise is sustainability in architecture and urban planning and design. He has carried out a great deal of research and technical survey work, and has performed several studies in the above-mentioned areas. He has edited many international books and is an active member of many worldwide architectural associations. 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Various roughly equivalent amplitude-based magnitude scales are in use, of which moment magnitude is the most general.
This paper reviews some of the current questions and research in microseismicity, ranging from acquisition, processing to interpretation. However, before reviewing these aspects, it is important to consider the wider context first and the economic impact of hydraulic fracturing in tight-hydrocarbon fields.
Security of energy supplies, the continuous growth in energy demand, and climate change are among the greatest global challenges that we face. Nearly all projections agree that we will remain heavily reliant on fossil fuels for many years. For example, the International Energy Agency’s ‘business-as-usual’ analysis from 2008 indicates that in 2030 approximately 83% of the world’s energy demand will still be met by fossil fuels. In 2011 this was revised downward to 55% due to high oil prices, government incentives for renewable energies and environmental concerns (EIA, 2011). Technological innovations will therefore be required to (i) find new hydrocarbon reserves or enable recovery from proven resources previously inaccessible or uneconomic; (ii) maximize recovery from producing reservoirs, and (iii) deal with CO2 emissions. Microseismic monitoring and hydraulic fracturing are mainly related to the first two points.
Recovery of hydrocarbons from previously uneconomic yet proven resources such as shale-gas and other tight-gas plays has become possible due to significant improvements in the last 10 years in two key technologies, namely horizontal drilling and hydraulic fracturing. Tight-gas reservoirs are characterized by low porosity and permeability, indicating that little pore space is present and that fluid flow is guaranteed to be slow and difficult, thus severely complicating reservoir drainage. On the other hand, this gas is often located in very thick lithologic units such that the resource volume is large. Horizontal drilling into these units enables drainage over a larger well contact area (2-3 km instead of 100-200m), thus improving fluid flow. In hydraulic-fracture well treatments, fluids possibly mixed with proppants (slurry) are injected under high pressure to induce fracturing of the reservoir, thereby further enhancing reservoir drainage by increasing the effective permeability through the creation of an interconnected fracture network.
The technological advances in these two key technologies have been such that in 2000 only 1% of the total gas production in the US came from shale-gas fields, whereas currently this is estimated to be 20% (IHS CERA, 2010). Figure 1 shows the extent of current and potential shale-gas plays in North America. It is clear that tight-gas and shale gas will remain an important resource for many years to come and further technological improvements will enable economic drainage of additional reservoirs. One of these emerging technologies is microseismic monitoring.
Current shale plays in North America. Source: EIA http://www.eia.gov/pub/oil_gas/natural_gas/analysis_publications/maps/maps.htm
Hydraulic fracturing (also known as fraccing or fracking) leads to brittle failure inside a reservoir, which is typically accompanied by microseismicity. Microseismicity refers to discrete rock-deformation events, analogous to tiny earthquakes, that are generally of moment magnitude < 0. For reference, magnitude 0.2 is the equivalent of the energy released by a large hand grenade (30 g TNT equivalent), whereas a typical small mining blast has a magnitude around 1-1.5, corresponding to 2-2.5kg of TNT. Since magnitude scales are logarithmic, negative magnitude events thus correspond to the energy yield equivalent of milligrams or even micrograms of TNT.
Monitoring of microseismic activity is a geophysical remote-sensing technology that provides the ability to detect and map associated fracturing processes, either in real-time or in post-processing mode. A typical field deployment involves the installation of an array of continuous-recording 3-component geophones within observation well(s) near the zone of interest, and/or a large number of surface sensors. Although relatively new to the oil and gas industry, similar monitoring technologies for earthquakes have been honed and developed by the seismological and mining research communities for decades (e.g. Gibowicz and Kijko, 1994; Bolt, 1984; Stein and Wysession, 2003). The goal of microseismic monitoring is to detect, locate and characterize microseismic events, which often occur in large numbers within cloud-like distributions that reflect underlying fracture networks. This approach enables monitoring of frac treatments in real-time in order to detect the extent of the stimulated rock volume and thus the success of the treatment, as well as predict likely improvements in subsequent reservoir drainage.
Applications of microseismic monitoring within industry, particularly in oil and gas, have seen remarkable growth during the past 10 years (Warpinski, 2009; Maxwell, 2010). This has not been limited to hydraulic fracture treatment for shale-gas and other tight-gas plays, but has included stimulation technologies such as fracturing or steam injection applied to tight-oil or heavy-oil fields and also techniques for maximizing recovery from producing reservoirs. It is estimated that over one million hydraulic fracture treatments have been performed in the US in the past 60 years (King, 2012), and that currently 3-5% of fracs in North America involve microseismic monitoring. Oil and gas companies have made significant expenditures (conservatively $100’s MM) for microseismic monitoring, but face extraordinary technological challenges to fully utilize the results. Their efforts are hampered by a number of factors, including an incomplete understanding of seismological and geomechanical processes associated with induced microseismicity.
In the next sections we will review current pertinent research questions on microseismic acquisition, processing and interpretation. Since many items are intimately intertwined it is inescapable that some points may be revisited throughout the chapter.
Based on the current state-of-the-art for microseismic monitoring, a number of important technological questions are presently under debate, such as:
What conditions favour surface versus borehole microseismic acquisition? Surface acquisition involves the deployment of large numbers of receivers and has the inherent advantage of more extensive azimuthal coverage (solid angle); in principle, this should improve the condition number for hypocentre inversion and moment-tensor analysis (Eaton and Forouhideh, 2011). On the other hand, placement of geophones in deep boreholes (currently the norm for microseismic monitoring in western Canada) has the advantage of better signal-to-noise characteristics due to the closer proximity to the microseismic sources, generally quieter background noise levels (less anthropogenic noise), often better instrument coupling and predominantly horizontal (layer-parallel) instead of vertical (layer-perpendicular) wave propagation leading to less wave scattering. Conversely, surface acquisition is significantly more cost effective as there is no need to drill observation wells or deploy instrumentation inside wells, and permits deployment of one or two orders of magnitudes more instruments.
The current strategy for hydraulic fracturing of tight-gas reservoirs is to minimize acquisition durations to reduce costs. Recently recognized phenomena, such as long-period long-duration events (Das and Zoback, 2011), indicate that much can be learned from the use of exceptionally long deployment times (i.e., weeks rather than days) in order to enable more complete characterization of background noise spectra. Such long recording durations would also enable the evaluation of technology for noise interferometry (cf. de Ridder and Delinger, 2011) to reveal not only what happens during stimulation, but also in the period before and immediately following the slurry injection.
Various formulas are currently used within industry to calculate the magnitude of microseismic events (Shemata and Anderson, 2010). Since magnitude formulas were developed for describing earthquake phenomena, they are calibrated for significantly larger magnitudes. The extrapolation of different formulas to 4-5 orders of magnitude below their calibration range leads to discrepancies in reported values. Accurate magnitude determination is of practical importance for various reasons, including (i) the determination of the stimulated rock volume (Maxwell et al., 2006); (ii) recently implemented controls in the UK on hydraulic fracturing operations are based on a “traffic-light system” (de Pater and Baisch, 2011) in which operations are suspended for several days if any event exceeds ML = 0, and stopped if any event exceeds ML = 1.7; and (iii) on liability issues related to induced seismicity (Cypster and Davis, 1998).
Currently the emphasis is on mapping brittle failure, yet it is hypothesized that the cumulative energy released via brittle failure represents only a minute fraction of the total injected energy, indicating that a large portion of energy release may occur aseismically (i.e., plastically or at very slow deformation rates) (Maxwell et al., 2009). This suggests that there may be an advantage to acquisition of continuous recordings for analysis of the ultra-low frequency spectral content of microseismic activity, which may be diagnostic of certain types of aseismic rock failure (Benson et al., 2008; Pettit et al., 2009; Beroza and Satoshi, 2011).
A university-led project to acquire microseismic data was undertaken in northern British Columbia, Canada. This experiment involved the recording of several multistage hydraulic fracture treatments performed in two horizontal wells (Figure 2). The microseismic data were collected using both surface and borehole sensors. The borehole tool string consisted of a 6-level broadband system with downhole digitization. Surface sensors included a 12-channel array with a mix of vertical-component and 3-C geophones, and 22 broadband sensors deployed in 7 localized arrays over an area of ~ 0.5 km2.
Experimental setup of the microseismic experiment, as well as the time-frequency transforms of stage H1-4 for one downhole geophone and one broadband station (hot colors correspond to high amplitudes). The stars indicate the position of the perforation shots and hence of the horizontal part of the wells. H1 and H2 are two different horizontal wells. After:
The unusual setup was designed to investigate multiple objectives. First, microseismic monitoring was performed using both surface and borehole equipment to compare acquisition strategies and determine their respective advantages and inconveniences such as ease of deployment, costs, detectability of events, other signals and associated noise levels. In addition, the experiment is unique in that both broadband and short-period equipment are deployed. The approximate lowest recording frequencies for the various equipment are; broadband surface-based seismometers: 0.0083 Hz (= 120 s); borehole equipment: 0.1 Hz; short-period surface array: 5 Hz. Data analysis of the variously recorded signal thus helps reveal if significant energy is present below the 5 Hz limit imposed by most standard monitoring equipment. This may help resolve the observed energy imbalance between injected and seismically released energy.
Conventional analysis of microseismic recordings involves first identifying and extracting individual events, e.g., via a semi-automatic triggering system. This poses problems if many overlapping events are simultaneously recorded and if individual event strengths hover around the noise level. It also may obscure proper identification of so-called slow earthquakes (Ide et al., 2007) occurring on much longer time scales than conventional earthquakes resulting from abrupt brittle failure.
Direct analysis of continuous data streams on the other hand offers much greater flexibility and is not subject to the shortcomings described above. For instance, analysis of continuous recordings of acoustic emissions generated during laboratory rock-fracturing experiments have greatly aided in improving our understanding of active microcracking and deformation processes in volcanoes and the earth in general (Benson et al., 2008; Thompson et al., 2009). These continuous data streams are analyzed using various time-frequency transforms such as short-time Fourier transforms, S-transforms and wavelet transforms (Reine et al., 2009) to examine variations in local frequency content and highlight slow deformation processes. Obviously it remains possible to dissect the recordings to extract individual events as well.
Initial analysis of these data reveals the existence of numerous high-frequency (> 100 Hz) microseismic events with moment magnitudes ranging from -2.3 to -1.4. These events are detected to distances of up to 1.2 km using the borehole system. In addition, perforation shots are well recorded to distances of about 2 km. More interestingly spectral analysis shows the existence of complex rupture patterns such as rapid opening and closing of tensile cracks (Eaton, 2012). Moment tensor analysis on other experiments has shown complex deformation as well in hydraulic-fracturing experiments (Baig and Urbancic, 2010); yet such moment-tensor analysis normally requires two or more observation wells (Eaton and Forouhideh, 2011). The current observations are obtained using a single observation well.
Time-frequency analysis of the continuous recordings demonstrates the existence of resonance frequencies during hydraulic fracturing (Tary and Van der Baan, 2013). The resonances are mainly in the frequency band between 5 and 20 Hz. Other resonances are visible on the broadband recordings. They likely correspond to environmental or anthropogenic noises. Noticeably, the resonances are recorded by the downhole geophones, which are close to the horizontal part of the injection well at depth, and by the broadband arrays A and B, which are near the well head. The broadband arrays C or D, closest to the fluid injection during the first stages, do not exhibit any resonance frequencies. This indicates that the injection well is likely the cause of these resonance frequencies (Figure 2). In other cases, however, resonance frequencies may be indicative of the extent of the induced, interconnected fracture network (Tary and Van der Baan, 2012).
It is clear from the above discussion that many key acquisition questions are intimately linked to the need to enhance our arsenal of tools for processing and interpretation of microseismic data.
Rapid turnaround has been a high priority within the microseismic industry to reduce acquisition durations and deliver analysis results such as event locations in near real-time to completion engineers, who are required to make decisions such as starting a new fracturing stage based on assessment of a microseismic event “cloud” distribution. This requirement has led to the development of near real-time event-picking, classification and hypocentre-location algorithms; such rapid turnarounds demand robust techniques based on straightforward assumptions, often accompanied by large reductions in information content. For instance, in the case of hydraulic fracture stimulations, the fracture size and orientation are often inferred using a few events comprising the edges of the “cloud” of microseismic hypocentres.
Before discussing picking and event location it is important to realize that a principal aspect of microseismic data processing is the recognition and attenuation of coherent noise. Coherent noise is defined here as any repeatedly recorded energy on one or more traces that is not a body wave (P or S) arrival. The noise is often persistent, repeatable, and may be caused by various types of waves travelling in the borehole. A cemented wellbore with steel casing has the potential to propagate many types of waves. P and S waves can be transmitted in a wellbore in the steel casing, or the cement (Raggio et. al., 2007). The P wave can also be transmitted in the fluid in the wellbore. There are also a number of modes of tube waves (Rayleigh waves travelling at the wellbore fluid and adjacent solid interface) that can be transmitted.
St-Onge and Eaton (2011) have observed another type of coherent noise source that may be related to the tuned response of a clamped geophone array. This response is manifested as discrete, high-amplitude spectral peaks that can have a negative effect on weak signals recorded within the primary bandwidth of borehole microseismic recordings (i.e., several hundred Hz). These observations show that noise can be high in amplitude, persistent in time, and may adversely affect the recording of P and S wave signal energy in microseismic data (St-Onge and Eaton, 2011). Due to the nature of the data acquisition, the types of noise observed in microseismic surveys differ from typical noise sources in conventional seismic profiling. In many cases, datasets are contaminated by Lamb waves, which are a type of elastic guided wave that travels along a plate surface such as the cylindrical surface of borehole casing. These coupled longitudinal and transverse waves were first described by Lamb (1917) and in a cylindrical casing exhibit longitudinal, torsional and flexural modes. Lamb waves are dispersive, and their frequency characteristics have been described by Karpfinger (2009). St-Onge and Eaton (Lamb waves recorded in wellbores and their potential to predict cement bond failure, in preparation for Geophysics) are exploring various ways in which these harmonic signals can be suppressed or even exploited to characterize the borehole environment as their propagation velocity is influenced by the bonding characteristics of the cement.
Tary and Van der Baan (2012) divide resonance frequencies into three broad categories, namely those generated by source, receiver or path effects. This categorization can also be applied to microseismic noise if we are interested solely in the microseismic direct arrivals for location purposes and estimation of the associated source mechanism. At the receiver side, resonance frequencies and other noise result from wave reverberations in the borehole (Sun and McMechan, 1988), either the whole borehole or between secondary sources such as the geophones (St-Onge and Eaton, 2011). Resonances and noise can also be due to internal resonance of the geophone if its clamping or damping is flawed.
Along the ray path, resonances arise from constructive and destructive interferences of seismic waves, waves focusing in low-velocity waveguides or multiple wave scattering. Which frequency band is favored depends on the layer spacing, thickness and mechanical properties (van der Baan et al., 2007, van der Baan, 2009). Likewise (multiple) reflections and refractions can also confound the picking of direct arrivals. A prime example on how such secondary arrivals can complicate event picking and location is shown in Kocon and Van der Baan (2012) who demonstrate that mis-identification of arrivals is a prominent source of event mislocations.
At the source side, resonance frequencies can be generated by repetitive events if perfectly periodic, or by the resonance of fluid-filled cracks as in the case of volcanic tremors (Aki et al., 1977). Resonances in fluid-filled cracks are generated by interface waves and depend mainly on the crack geometry, the crack stiffness and the source parameters that trigger the resonance (Ferrazzini and Aki, 1987). The latter are significantly less likely to mask strong direct arrivals; yet they offer promise for enhancing our understanding of the geomechanical reservoir deformations during hydraulic fracturing (Tary and Van der Baan, 2012, 2013) as indicated in the previous section.
Event-detection and time-picking are critical steps for microseismic data processing. Due to the large volume of data acquired during a microseismic survey, these steps are typically performed using an automated method. These steps have been implemented using various algorithms, such as the short- and long-time average ratio (STA/LTA) technique (e.g. Sharma et al., 2010), modified energy-ratio (MER) (Han et al., 2009) and Akaike information criterion (AIC) (Oye and Roth, 2003). Akram et al. (Automatic event-detection and time-picking algorithms for downhole microseismic data processing, manuscript in preparation for Geophysical Prospecting) have developed a dynamic-threshold approach for event detection that reduces false detections and offers improved capability to identify weak signals. They have also developed several hybrid approaches for automatic arrival-time picking that combine existing methods to improve performance with real microseismic data.
Calculation and interpretation of the locations of seismic events (hypocentres) are critical first-order components of microseismic monitoring. Compared to conventional earthquake methods, borehole microseismic surveys are relatively poorly constrained because of the fewer number of geophones and less desirable azimuthal coverage (Han, 2010; Jones et al., 2010). Most hypocentre localization methods require knowledge of P- and S-wave arrival times (Xuan and Sava, 2009). For borehole microseismic surveys, the distance between source and receiver can be computed using the arrival time difference of P- and S- waves and azimuth and dip information obtained from polarization analysis (Albright and Pearson, 1982; Eisner et al., 2009; Han, 2010; Jones et al., 2010). A probability density function can also be computed from the observed and modeled arrival time delays of P- and S-waves (Michaud et al., 2004). Surface microseismic methods are better suited to migration-based methods, which do not require P- and S-wave arrivals time picking information and can locate weak events by focusing energy at the source using time reversal (Gajewski, 2005; Chambers et al., 2009; Fu and Luo, 2009; Xuan and Sava, 2009). The drawbacks of the migration-based methods include high computational cost and their requirement of data redundancy (Xuan and Sava, 2009; Han, 2010). A semblance-weighted stacking method can also be used for microseismic source location, where the maximum value of the product of P- and S-wave semblances on a time window define the location of microseismic source (Eaton et al., 2011).
There are also several techniques (for example, hypocentroidal decomposition and double-difference tomography), which determine the relative location of the seismic source (Shearer, 1999). It has been recognized that the near real-time hypocentre locations may have large associated uncertainties, preventing high-resolution post-treatment interpretation (Figure 3). A first concern is that different service companies may obtain different event locations, even for the same dataset. This is caused by fundamental uncertainties in how to determine the most appropriate velocity model, the use of different event location algorithms but also elemental problems on how to pick consistently P- and S-wave arrivals in large datasets (sometimes consisting of 1000s of events recorded by 10s or 100s of 3-component receivers).
Much current research focuses on improved workflows for direct estimation of absolute hypocentres and on accurate relative event locations. Multiplet analysis can for instance be used to address the issues of unknown velocity models as well as inconsistent picking on final event locations (De Meersman et al., 2009; Kocon and Van der Baan, 2012). A doublet is a pair of events produced by nearly identical source mechanisms from closely spaced locations; a multiplet is a group of three or more of such events. The waveforms of multiplets are nearly identical, with the principal exception of additive random noise. Multiplets can be readily identified using cross correlation (Poupinet et al. 1984; Arrowsmith and Eisner, 2006). All events in each multiplet group are then relocated to improve their relative location accuracy (Figure 3), thereby revealing lineations and active faults planes.
Microseismic events contain a wealth of information that can be used to determine planes of weakness along which fluid migration could occur. (a) Original source locations; (b) new source locations after application of a high-resolution relocation technique; (c) multiplets extracted and best fault plane solutions depicted in two major clusters; (d) obtained fault planes overlain onto the top-reservoir fault map interpreted from 3D surface seismic data (after
This approach has two important advantages. First the method is rather insensitive to the chosen velocity model since any inaccuracies will not obscure revealed geologic features but only change their size (Got, 1994, De Meersman et al., 2009). Secondly, mispicks and missing picks are automatically corrected for via the cross-correlation procedure. In addition, a crossplot of waveform correlation coefficients versus hypocentre separation distances of every event pair automatically reveals hypocentre location errors by examining location distances of identified multiplets. This technique enabled Kocon and Van der Baan (2012) to ascertain that events could be mislocated by 350m in a heavy-oil dataset due to erroneous traveltime picks.
Once the multiplet groups are detected, the double-difference method can be applied. This is a relative relocation method that seeks to reduce the effects of errors due to unanticipated velocity heterogeneities in the structure (Waldhauser and Ellsworth, 2000). An advantage of this method is that no master event is needed, which induces spatial limitations, since all events must be correlated with the reference event. The main assumption in this method is that ray paths between two events will be very similar if their hypocentral separation is small compared to the source-receiver distances; therefore, the relative travel-time difference at a common station will be mainly due to the spatial offset between both events. In other words, the effects of most velocity heterogeneities will cancel out, such that only knowledge of the velocities in the source region is required. Castellanos and Van der Baan (2012) apply this method to data from a mining environment. Results clearly reveal a linear feature after relocation, possibly related to horizontal drilling activities.
Likewise, De Meersman et al. (2009) use relative locations to delineate a graben-like extensional structure in the caprock of a producing reservoir in the North Sea, UK (Figure 3). This graben-like structure was not visible in the original absolute locations which revealed solely two large microseismic clusters. Next they re-examine temporal changes in anisotropy as found by Teanby et al. (2004a) using the automated shear-wave splitting methodology of Teanby et al. (2004b) for this same dataset. They then argue that their integrated analysis of relocated sources, seismic multiplets, and S-wave splitting supports a model whereby stresses in this reservoir recharge cyclically. Effective stress builds up in response to reservoir compaction as a result of oil production, and stress is released by means of microseismic activity once criticality is reached on slip planes. These changes cause variations in seismic anisotropy and the microseismic source mechanisms over time.
The microseismic case studies by De Meerman et al. (2009) andCastellanos and Van der Baan (2012) do not include fluid injection; yet they already demonstrate that analysis of the microseismic cloud of event locations can reveal important insights into the local geology and subsurface deformations. Pore pressure and stress changes during hydraulic fracturing lead to a propagating cloud of microseismic events, which can be recorded and analyzed to constrain the volume of the stimulated zone. Because pressures and stresses diffuse/propagate beyond the fluid-filled fractures and affect the (generally jointed) rock mass in all directions, the microseismic cloud represents a volumetric map of the extent of shear and opening of naturally fractured rock.
A key element in current research is to develop interpretation methods that bridge the gap between geophysical data analysis and engineering applications of microseismic data. Ultimately, operators would like to know how to optimize the fracturing treatment given the in situ stress regime, dominant natural fracture orientations, pre-existing faults and other zones of weaknesses, and the prevailing lithologies. Phsyically, there exists an intimate link between the above geologic features, employed stimulation strategies and resulting microseismicity. Existing unknowns can be summarized using the following two fundamental questions: (1) Given a known stress field, geology, rock mass fabric and injection strategy, what are the most likely resulting microseismic characteristics (e.g., hypocentres, source mechanisms and magnitudes)? (2) What does measured microseismicity reveal about the existing stress field and local geomechanical properties of the rockmass? The first question involves solving the forward model (given the physical parameters, what are the resulting observations?) The second question involves solving the inversion problem (given our observations, what can we determine about the current physical state?).
From an engineering point of view, answering these questions will have an immediate impact on first creating optimal drainage and fracturing strategies and then confirming their success or failure prior to starting production. From a geophysical perspective, recorded microseismicity and integration of the results with surface seismic data should significantly enhance our understanding of the existing subsurface geologic conditions and the geomechanical behavior of the reservoir, thus providing pertinent information to the completion engineers.
Pertinent considerations include: (1) Obtaining accurate locations for microseismic events to support meaningful volumetric analysis of the associated microseismic cloud. (2) Inferring the failure mechanism (i.e., are fractures opening, closing or shearing?). (3) Determination of why failure is occurring in specific locations but not in others (why are fractures not always symmetric with respect to the injection well and what is the geomechanical behavior of the reservoir)? The last question, in particular, is difficult to answer from the recorded seismicity alone since the geomechanical behavior depends on the in-situ stress field, the local rock properties (lithologies), and any existing areas of weakness including faults, fractures and joints (Grob and Van der Baan, 2011, Chorney et al., 2012).
Robust characterization of microseismic sources has the potential to provide important information about deformation mechanisms. Borrowing from earthquake seismology, seismic moment tensors can be used to describe microseismic point sources in general terms of a set of force couples. Moment tensors can be represented in terms of source type (Hudson et al., 1989), a classification scheme that includes shear slip (double couple), dipole, compensated linear vector dipole and volumetric sources. The reliability of these classification schemes depends critically upon the use of a recording array with a suitable geometry that satisfies geometrical requirements for azimuthal coverage of the source region (Eaton and Forouhideh, 2011).
Other fundamental descriptions of microseismic sources include the seismic moment and associated energy release, in addition to spectral source characteristics that reveal the time- and spatial-scales of rupture. Recent developments in earthquake seismology suggest that rock-deformation processes commonly occur across a broad spectrum of time scales (and frequency), wherein earthquakes merely represent a high-frequency end member (e.g., Beroza and Ide, 2011). We postulate that rock deformation processes associated with hydraulic fracturing obey scaling laws that are similar to earthquakes. If so, microseismic activity recorded conventionally using geophones, which are relatively insensitive to ground motion below their natural frequency (typically ~ 10 Hz), could represent a high-frequency end member of the complete deformation spectrum.
Seismic moment-tensors provide a general mathematical representation of seismic point sources (Ben-Menahem and Singh, 2000). Inversion techniques to estimate moment tensors from seismic recordings are well developed in earthquake seismology, but are only starting to be used in microseismic monitoring applications (Baig and Urbancic, 2010). The determination of moment tensors can potentially provide useful insights into rupture processes, but care is required to ensure that survey design is adequate (Eaton and Forouhideh, 2010; 2011).
The spatial dimensions of microseismic events are encoded in the spectra of the radiated seismic waves. Microseismic events can therefore be analyzed using spectral methods (e.g. Eaton, 2011), providing an alternative approach for characterizing sources. For example, models for shear slip on a circular crack (Brune 1970, 1971; Madariaga, 1977) predict the shape of source spectra and provide scaling relationships between spectral parameters and source parameters (slip area and seismic moment). These source attributes complement those derived from moment-tensor inversion.
Tensile microseismic events are believed to play an important role during hydraulic fracture treatment of unconventional reservoirs (Baig and Urbancic, 2010). Tensile microseismic events may be associated with self-propping (remnant aperture), or wedging open of natural fractures because of the induced strain field. Walter and Brune (1993) developed a model for far-field source spectra for tensile rupture, and compared these with modeled far-field spectra for shear-slip events and showed that anomalously low S/P spectral amplitude ratios are a diagnostic characteristic of tensile rupture. Building on this approach, Eaton et al. (“Scaling relations and spectral characteristics of tensile microseisms”, manuscript in preparation for Geophysics) investigate source characteristics of microseismic events induced by hydraulic-fracturing, with application to microseismic data from the previously described multistage treatment in northeastern British Columbia. They show that although spectral estimates of magnitude are relatively unaffected by uncertainty in seismic attenuation, for typical microseismic magnitudes accurate knowledge of seismic attenuation is necessary to estimate some spectral parameters. They also document microseismic events with spectral characteristics that reflect a complex rupture pattern, such as rapid opening and closing of tensile cracks.
As indicated above, the reliability with which moment tensors can be determined depends strongly on the acquisition geometry (Eaton and Forouhideh, 2010; 2011). There is thus a need for alternative and complementary analysis methods to reveal more about the in situ stress field. Fortunately, independent information on the in situ stress field can also be obtained by analyzing the frequency-magnitude distribution of microseismic events. This is achieved by plotting the distribution of event magnitudes on a semi-log plot (Figure 4). This distribution, also called the Gutenberg-Richter relation, usually shows a power law behavior. Its linear slope gives the so-called b-value. Schorlemmer et al. (2005) have shown that this b-value changes depending on the stress regime by plotting b-values versus rake angles (indicating slip direction of the hanging wall) for a large variety of earthquakes. For a b-value less than 1, the vertical stress is the least principal compressive stress and we are in a thrust-fault regime. If the vertical stress is intermediate, the b-value will likely be around 1, indicating a strike-slip faulting regime. And if it exceeds 1, then the stress regime is extensional, with the maximum principal stress vertical, creating a normal fault regime.
The case study of Grob and Van der Baan (2011) using a microseismic dataset recorded over a heavy oil field drained using cyclic steam stimulation revealed that the in situ stress state changed from extensional to compressive with an intermediate strike-slip regime, indicating initial opening and then closing of fractures. This occurred over an 8-month period where pure injection in the first four months was followed by combined injection and production in different parts of the field (Figure 4). We postulate that analysis of the statistical b-values will provide complementary information to temporal and spatial variations in the in situ stress field as determined by moment-tensors inversions, and therefore contains a wealth of information to facilitate reservoir management.
Analysis of frequency-magnitude variations in microseismic events recorded over a heavy-oil field drained using cyclic-steam stimulation (after
Various observations suggest that microseismic events tend to occur preferentially in specific lithologies only (e.g., a sand) but not in some others (e.g., a shale), even if fluids are known to traverse both lithologies in a hydraulic fracturing experiment, shown in Figure 5 (Rutledge et al., 2004, Pettitt et al., 2009). This suggests that deformation in some rock types may occur aseismically, especially in higher-permeability, ductile shales, or simply that the radiated elastic energy for microseismic events in some rock types may occur at frequencies that are too low to be detected using conventional recording systems. Moreover, anecdotal information suggests that the abundance and intensity of microseismic events may not necessarily correlate to the effectiveness of the fracture treatments (Maxwell et al., 2008; Boroumand and Eaton, 2012).
Hydraulic fracturing of a tight-gas sand. 1408 events are recorded over 5 hours. Events are colour shaded by time: green (earliest) to red (latest). Events occur in two formations with very few detected events in between. Yet the event history reveals that brittle failure occurs first in the right-most part of the bottom formation, and then suddenly jumps to the top formation indicating the presence of a possible aseismic fault. After
The concept of microseismic efficiency represents the ratio of radiated seismic energy (Vassiliou and Kanamori, 1982) to the total deformation energy. Analysis of deformation energy is being done by using pressure, rate, fluid/proppant volume and other relevant data curves produced from the surface equipment in order to calculate the total energy/work produced to generate fractures in the ground. Often substantial differences are estimated between the total input energy inferred from fluid injection rates and pressures, the fracture energy to pry apart the walls of a single very large fracture, and the radiated energy observed from recorded seismicity. The injected energy is 104–107 times larger than the estimated radiated seismic energy, and the fracture energy is inferred to be 15–40% of the input energy (Maxwell et al., 2008; Boroumand and Eaton, 2012).
The three most likely factors to dominate the geomechanical behavior of a reservoir are the local in situ stress regime, pre-existing fractures (and other zones of weaknesses), and the actual rock properties (e.g., whether they are more ductile or brittle as expressed by their Young’s modulus or Poisson’s ratio and thus the Lamé parameters). In order to better understand why the seismic efficiency is so low, and what precisely happens when we are injecting fluids at high pressures into rocks we need to improve our understanding of what the various geophysical observations (moment tensors, hypocentres, resonance frequencies, etc.) truly reveal of the newly induced fracture networks specifically, and the geomechanical reservoir response in general. Three general options to achieve this objective are analogues, computational modelling, and physical modelling in the laboratory.
Dusseault et al. (2011) use analogues to explain many of the fracturing processes that may occur when fluids and/or proppants are injected at high pressure into intact and naturally fractured rock. They consider a medium composed of rigid blocks and injection of a solid. This leads to many insights despite the fact that this is clearly a great simplification of reality.
In Figure 6 a solid material is injected into a material composed of rigid blocks, producing tensile mode I fracturing (i.e., wedging) at the tips of the proppant inclusions, and mode II (i.e., shearing) in the surrounding areas due to block rotations. Wedging creates fracture openings well beyond the proppant tips (or infiltration extents) due to normal extensional forces on the surfaces of the joint leading to tensile (mode I) failure and facilitating slurry/proppant penetration. It also leads to a large increase in the effective permeability in a zone beyond the proppant infiltration.
Analogues can help us understand how fluid and/or proppant injection into a reservoir zone affects the resulting rock deformation. In this case a solid material is injected into a material comprised of rigid blocks, showing clearly where propping, wedging, rotation and shearing will occur. Such observations provide important clues on the anticipated moment tensors throughout the resulting microseismic event cloud. From:
Block rotation continues beyond the area of proppant infiltration and tensile opening at the proppant tips. It involves large changes in both the normal and shear forces excited on the joint surfaces, yielding predominantly mode II fracturing (i.e., shearing). This may cause slip on existing joints in naturally fractured rocks, and even facilitate fault reactivation if the effective stresses are sufficiently to close to criticality. Shear displacement along natural fractures is associated with self-propping where irregular joint surfaces after slip create remnant apertures, facilitating subsequent fluid flow (Dusseault et al., 2011). Such observations provide important clues on the anticipated moment tensors throughout the resulting microseismic event cloud, demonstrating that tensile source mechanism are likely to dominate close to the proppant tips, but double-couple events in all other areas.
Fluid and/or proppant injection into a reservoir zone will create new fractures, as well as close, shear or pop open existing fractures. The various failure mechanisms may lead to a larger microseismic cloud surrounding the area of injected fluids, thereby improving reservoir drainage. The microseismic events are therefore also characterized by a variety of earthquake mechanisms. Their analysis can yield a wealth of knowledge on the underlying failure mechanisms beyond mere locations. From:
Obviously fluid and/or proppant infiltration into naturally fractured rock is significantly more complex since the exact behaviour will depend on the situ stress field, pre-existing in natural fractures and lithologies. The interaction of brittle failure in intact rock and the slip/shearing in naturally fractured areas can be complex (Figure 7); yet the principles deduced from the study of analogues should help unravel the various competing processes.
Analogues provide a first understanding on how fluid and/or proppant injection is likely to deform the surrounding rock mass (Figures 6 and 7). They also provide pertinent clues on where to expect brittle failure (and thus microseismic events) and their most probable failure mechanism (source mechanism). Geomechanical modeling is subsequently a great aid for improving our understanding on links between fluid-induced rock failure, the occurrence of microseismicity and underlying geomechanical behaviour, beyond the assumption of rigid blocks and no fluid diffusion (i.e., no leak off).
Bonded-particle modeling is becoming an important computational tool for modeling the complex dynamical behavior of rocks rupturing given a set of boundary conditions (Potyondy and Cundall, 2004). This approach simulates rock deformation using an assemblage of rigid, round particles that are bonded together. This grid of particles can deform freely and bonds can be broken to represent local failure. Bonds are characterized by normal and shear strengths as well as friction coefficients to model respectively tensile and shear failure. Such a discontinuum-based approach seems more appropriate to model rock deformation through failure since it eliminates the need for complex constitute relations required for continuum approaches (Hazzard and Young, 2000). Also microseismic moment tensors can be inferred by integrating local bond failure in both space and time (Hazzard and Young, 2004).
Chorney et al. (2012) use bonded-particle modelling to examine resulting seismicity for triaxial compression tests using different confining pressures. The resulting Hudson plots (i.e., moment-tensor distribution) show a surprising similarity with those obtained for real data by Baig and Urbancic (2010) from field observations of hydraulic fracturing (Figure 8). Baig and Urbancic (2010) find dominant failure mechanisms of double couple (shearing) and fracture opening and closing (tensile failure and closing). This confirms insights gained from the analogues (Figures 6 and 7) where shearing and tensile failure seem to dominate, respectively, in the surrounding area and at the tips of the proppant infiltrations.
Hudson plots of the failure mechanisms for microseismic events in the bonded-particle simulations for triaxial compression tests with confining pressures of 0 MPa (left) and 40 MPa (right). The colors represent the time: pre-peak stress events are in black; events happening around peak stress are in red and post-peak events are displayed in blue (modified from
Chorney et al. (2012) also monitor the total input energy of the system, the total kinetic energy emitted from bond breakages, and the energy deduced from the moment magnitudes of the microseismic events. The kinetic energy represents approximately 5% of the input energy; the radiated seismic energy is 50-100 times smaller than the kinetic energy. The radiated energy calculated using the Gutenberg-Richter relationship between moment magnitude and energy may thus underestimate the energy incurred from brittle failure. Both the radiated and kinetic energy from brittle failure are substantially lower than the input energy. This confirms observations by Maxwell et al. (2009) and Boroumand and Eaton (2012). Ductile or slow, aseismic deformation must thus constitute a significant term in the energy budget for both these numerical simulations of triaxial compression and for hydraulic fracturing experiments in general.
Approaches such as bonded-particle models are thus useful to study the anticipated geomechanical behavior of a reservoir; in particular anticipated brittle failure (as expressed by a microseismic event) as well as any aseismic deformation (due to semi-brittle or plastic flow). Ultimately, they may help to investigate how resulting deformation and microseismic emissions depend on (1) in the in situ stress regime, which relates to the magnitude and ratio of the vertical stress Sv and the maximum and minimum horizontal stresses SH and Sh; (2) pre-existing fractures and other zones of weakness most likely to break; and finally (3) the local rock properties defined by the Young’s modulus and Poisson’s ratio (both related to the Lamé parameters). Constraints on many of these factors can be obtained using the processing and interpretation techniques described previously.
Unfortunately, discontinuum-based methods such as bonded-particle approaches may be less suitable to simulate fluid injection as fluids can only be described as small particles. Continuum-based approaches such as finite-element methods may be required for coupled fluid-flow and geomechanical simulation (Dean et al., 2003; Minkoff et al., 2003; Angus et al., 2010). On the other hand, particle-based methods are highly appropriate to modelling crack propagation and brittle failure. Although this is feasible with continuum-based approaches it leads to highly expensive computations. Angus et al. (2010), for instance, circumvent the requirement for modelling fracture propagation by assuming that the differential effective stress tensor at the local point of failure is a first-order approximation to the local failure mechanism (Zoback and Zoback, 1980). For failure in intact rock this is likely a reasonable assumption, but not for failure along pre-existing weaknesses (Gephart and Forsyth, 1984).
Ultimately physical modelling in the laboratory is required to confirm our inferences from the study of analogues and numerical simulations, thereby completing the circle between fluid-induced rock failure, the occurrence of microseismicity and underlying geomechanical deformation. Many authors have studied the links between microseismic event locations and fracture growth in both triaxial compression and hydraulic fracturing tests (Solberg et al., 1980; Sondergeld and Estey, 1981; Kranz et al., 1990; Lockner et al., 1991; Lockner, 1993; Chitrala et al., 2010). Most of these studies were successful in determining the event hypocenters; yet few provided reliable full moment tensor solutions. The latter are essential for better understanding the actual rock failure mechanisms.
The analogues are very useful for building a first understanding on what to expect when injecting fluids and/or proppants into the rock matrix (Figures 6 and 7) but the combination of numerical simulations and their verification using physical experiments in the laboratory will help to bridge the gap between geophysical data analysis and engineering applications of microseismic data by providing a framework for advanced interpretation strategies, thereby facilitating completion of the the circle between acquisition, processing and interpretation.
The recent surge in development of unconventional resources such as shale-gas and heavy-oil plays has created renewed interest in microseismic monitoring. Pore pressure and stress changes during fluid and/or proppant injection lead to an expanding cloud of microseismic events, due to brittle failure in intact rock and additional slip/shearing in naturally fractured rock. The microseismic cloud represents thus a volumetric map of the extent of induced fracture shearing and opening; yet integration of event locations with moment tensors, other geophysical observations and geomechanical constraints is required to determine ultimately the size of the interconnected fracture network, thereby excluding isolated fracturing/shearing, since only the former contributes to the enhanced effective porosity and permeability, required for predicting actual reservoir drainage.
Due to a strong desire for near-real time information by completion engineers, acquisition and service companies have focused predominantly on providing hypocentre locations and moment magnitudes. Microseismic recordings contain, however, a wealth of information beyond event locations, including moment tensors and resonance frequencies. Thus, many pertinent research questions on microseismic acquisition, processing and interpretation remain to be answered before full use of microseismic recordings can be achieved.
Nonetheless, microseismic monitoring has a bright future with long-standing applications such as monitoring of shaft stability in mines and the creation of engineered geothermal systems; more recent applications involve monitoring of hydraulic stimulation of "tight" hydrocarbon reservoirs and steam-injection in heavy-oil fields. Future applications may incorporate surveillance of CO2 storage as well as slurried waste solids disposal through continuous injection.
The first two authors would like to thank the sponsors of the Microseismic Industry Consortium for financial support. Arc Resources, Nanometrics and ESG Solutions are particularly thanked for their support of the field project. All authors would like to thank their collaborators, students and postdocs whose work has contributed tremendously to this paper.
The use of adhesives dates back to approximately 3000 years ago. Several types of adhesives based on specific applications have been developed, particularly for the manufacturing of wood and paper products, among other products. Therefore, thousands of adhesive products have been developed. Factors that affect the selection of the adhesives are cost, assembly process, bonding strength, and durability.
\nThe fabrication of wood-based panel products involves a “preparation and recombination of wood unit” process wherein wood adhesives play a crucial role. Adhesives play a vital role in wood processing because their quality has a direct impact on the performance of the final wood product.
\nSynthetic and natural resins are the most commonly used adhesives in the wood industry. Some examples of synthetic resins are urea-formaldehyde resin; phenolic resin; melamine formaldehyde resin; and copolycondensation resin, which include phenol-urea-formaldehyde resin (PUF) and melamine–urea-formaldehyde resin (MUF). Some examples of natural resins are soy protein adhesive, tannin resin, lignin adhesive, and starch adhesive.
\nAlthough synthetic resin has high weathering resistance and mechanical strength, its raw materials are derived from nonrenewable petrochemical products that are volatile and expensive. Additionally, these products emit formaldehyde, which is toxic and carcinogenic.
\nThe awareness of environmental protection and personal health has been emphasized in recent years. Therefore, natural resins with renewable resources as the main materials have attracted considerable amount of attention. Research and application of the tannin resin have been highly successful in some countries because its phenolic structure enables its use as adhesives and as a partial or complete substitute for phenols in adhesives. This chapter provides a comprehensive discussion of the situation of the existing tannin resources, reaction mechanisms involved in the synthesis of tanning resins, and general application of tannin resins in the wood industry. This information could provide ideas for the scholars and broaden the application scope of tannin resins in the wood industry.
\nThe production of tannin for leather manufacturing peaked immediately after World War II and has progressively declined. Tannin adhesives were first successfully commercialized in South Africa in the early 1970s. Subsequently, mimosa tannin adhesives were used instead of synthetic phenolic adhesives to manufacture particleboard and plywood for external and marine applications. Tannin resin adhesives have been used in Australia, Zimbabwe, Chile, Argentina, Brazil, and New Zealand [1].
\nTannins are extracted from agroforestry biomaterials, such as wood, bark, leaves, and fruits, by the water extraction method. Tannins can be categorized as hydrolyzable tannin or condensed polyflavonoid tannin. The latter is one of the main objects of wood adhesive research and accounts for 90% of the global tannin output. The annual industrial output of tannin reaches up to 200,000 tons.
\nThe distribution of tannin resources in the world has regional characteristics. For example, black wattle tannin is mainly manufactured in Brazil, South Africa, India, and other countries. Quebracho tannin is mainly manufactured in Argentina. Chestnut tannin is mainly manufactured in Italy and Slovenia. Pine bark tannin is mainly manufactured in Chile and Turkey. Oak tannin is mainly manufactured in Poland. Tannin from grape residues, such as skins and seeds, is mainly manufactured in France. In China, tannin is mainly synthesized from larch, poplar, and acacia bark.
\nHydrolyzable tannin comprises different types of unit structures, including gallic, digallic, and ellagic acids (see Figure 1), as well as sugar esters, which usually exist in the form of glucose [2, 3].
\nUnit structures of hydrolyzable tannin.
Condensed tannin comprises monoflavonoids or flavonoid units that have undergone various degrees of polymerization. These units are associated with their precursors, such as flavanes-3-ol and flavanes-3,4-diol, among other flavonoids [4, 5]. Each flavonoid contains two types of phenolic nuclei, which are A- and B-ring, as shown in Figure 2. The A-ring includes resorcinol and phloroglucinol, whereas the B-ring includes pyrogallol and catechol, among other rare phenols. The A-rings of different tannins possess different chemical structures. The A-rings of tannins extracted from mimosa/wattle, quebracho, Douglas fir, and spruce include resorcinol, whereas those of pine include phloroglucinol.
\nMain structure of condensed tannin.
The main polyphenolic pattern is represented using flavonoid analogs that are based on the resorcinol A-ring and pyrogallol B-ring (I type in Figure 3). This unit structure accounts for 70% of tannin. Unit structure II constitutes 25% of tannin and comprises a resorcinol A-ring and catechol B-ring (II type in Figure 3). The remaining 5% is a mixture of phloroglucinol-pyrogallol (III type in Figure 3) and phloroglucinol-catechol (IV type in Figure 3) flavonoids. These four patterns constitute 65–80% of mimosa bark extract. The remaining components are non-tannins, which are simple carbohydrates, hydrocolloid gums, and nitrogen compounds, i.e., amino and imino acids. Gums and pectins are the most important components of tannins and have a significant effect on the viscosity of the extract despite their low concentration, i.e., 3–6%. These non-tannin substances can attenuate wood failure and can decrease the water resistance of glued products.
\nMain units of condensed tannin.
Pine tannin mainly presents two patterns: one is represented by phloroglucinol A-ring and catechol B-ring structures (V type in Figure 3) and the other is represented by phloroglucinol A-ring and phenol B-ring structures (VI type in Figure 3).
\nFlavonoid units can be bound through their 4,6- and/or 4,8-linkages to form polyflavonoids. Wattle-extracted tannin comprises 4–5 flavonoid units joined together through 4,6-linkages. Each unit of wattle-extracted tannin has an average mass number of 1250. The average mass number of quebracho tannin and pine is 1784 and approximately 4300, respectively. Pine tannin is phloroglucinolic in nature and its flavonoid units are joined together through 4,8-interflavonoid linkages. Linear polymeric tannins have only 4,6- (V) or 4,8-linkages (VI). However, 4,6- and 4,8-linkages may simultaneously exist in the presence of resorcinolic and phloroglucinolic A-rings. This phenomenon results in the synthesis of angular rather than linear polymeric tannins (VII). Matrix-assisted laser desorption/ionization time-of-flight revealed that mimosa tannin is highly branched owing to the presence of high proportions of angular units in its structure. On the contrary, quebracho tannin is almost completely linear. These structural differences contribute to the considerable differences in the viscosity of tannin water solutions [6].
\nThe low reactivity of hydrolyzable tannins with formaldehyde limits their application in the wood industry, which can be attributed to their simple phenolic structures (Figure 1).
\nTannin extracts usually contain sugars and gums, which are not involved in the synthesis of resin adhesives. Commercially available tannin extracts from black wattle and hardwood typically contain 70–80% of natural phenolic polymers, whereas those obtained from pine contain only 50–60% of natural phenolic polymers. Sugar dilutes the actual solid content, thus affecting the final properties of resins. Gum considerably affects the strength of the resin and water resistance of the adhesive. Due to the presence of non-tannin components, unmodified tannin adhesive is unsuitable for the production of wood products with high requirements. Therefore, tannin adhesives must be modified.
\nNormally, the viscosity of tannin resin adhesives is higher than that of synthetic resins at the same concentration due to (1) the presence of high molecular weight tannins in the extract and (2) the existence of hydrogen bonding and electrostatic interactions between tannin and tannin, tannin and gum, and gum and gum. Effective methods for decreasing the viscosity of tannin extracts in aqueous solutions include the following: (1) acid or alkaline hydrolysis of high molecular weight carbohydrates, e.g., with acetic anhydride, maleic acid anhydride, or NaOH [7, 8]; (2) addition of small amounts of hydrogen bond breakers (e.g., 3% urea based on the solid content of the extract); and (3) destruction of heterocyclic ether in tannin molecules through sulfite or bisulfite treatment.
\nTannin being phenolic in nature undergoes the same alkali- or acid-catalyzed reaction with formaldehyde experienced by phenols. Alkali-catalyzed reactions are predominantly used in industrial applications. Nucleophilic centers on the A-ring of any flavonoid unit tend to be more reactive than those on the B-ring. Thus, the reaction for inducing polymerization between formaldehyde and tannin mainly occurs on the A-ring through methylene bridge linkages. The A-ring of the condensed tannin molecules contains flavonoid units that possess one highly reactive nucleophilic center each. The reactivity of the resorcinol A-ring (e.g., wattle) toward formaldehyde is comparable with that of resorcinol. On the contrary, the phloroglucinol A-ring (e.g., pine) behaves as phloroglucinol. Pyrogallol or the catechol B-ring are unreactive and may only be activated via anion formation at a relatively high pH [9, 10]. Hence, the B-ring does not participate in polymerization except at a high pH (pH = 10). However, the reactivity between the A-ring and formaldehyde influences pot life because it is too fast to control.
\nIn general, only the A-ring structure participates in crosslinking to build networks in tannin resin adhesives (Figure 4). However, owing to their size and shape, tannin molecules become immobile at low levels of condensation with formaldehyde. Thus, a large distance between the available reactive sites for further methylene bridge formation results in the incomplete polymerization of tannin resin adhesives. Incomplete polymerization, in turn, results in the formation of weak and brittle adhesives. Bridging agents with long molecules, such as phenolic and amino-plastic resins [10, 11], have been used to overcome this limitation by bridging the distances that are too large for interflavonoid methylene to bridge.
\nReaction mechanism of tannin with formaldehyde.
Catechol and catecholic B-ring do not react with formaldehyde at a pH value less than 10. Adding zinc acetate to the reaction mixture induces the B-ring to react with formaldehyde at low pH values, the optimum pH being in the range of 4.5–5.5, as shown by the high amount of formaldehyde being consumed. This finding implies that the further crosslinking of the tannin-formaldehyde network could be achieved through the participation of the B-ring in the reaction in the presence of zinc acetate. Strength can be improved through the addition of zinc acetate at economically acceptable levels (5–10% in resin solids). Nevertheless, improved strength is not comparable with the strength of fortified tannin resin.
\nCrosslinking is sometimes performed through the addition of isocyanate. The highly reactive diphenylmethane diisocyanate (MDI) can be used to assist the participation of B-ring in the crosslinking reaction [12]. Additionally, the reaction between polymeric diphenylmethane diisocyanate (pMDI) and carbohydrates or hydrocolloid gums can help in increasing the bonding strength of wood products. The reaction rate of wattle and pine tannins with formaldehyde is slowest in the pH range of 4.0–4.5 and 3.3–3.9, respectively.
\nFormaldehyde is a major aldehyde used for the synthesis, setting, and curing of tannin resin adhesives. It is normally used as a liquid formalin solution or in the form of the polymer paraformaldehyde, which is capable of fairly rapid depolymerization under alkaline conditions. The formaldehyde reaction with tannin can be controlled by the addition of alcohols to the system. Under these circumstances, some of the formaldehydes are stabilized by the formation of hemiacetals, such as the formation CH2[OH][OCH3], if methanol is used. When the adhesive is cured at an elevated temperature, the alcohol is driven off and formaldehyde is progressively released from the hemiacetal. These effects minimize formaldehyde volatilization when the reactants reach curing temperature and extend the pot life of the adhesive.
\nHexamethylenetetramine (hexamine) may also be added to tannin resins owing to its formaldehyde-releasing action under heat. Although hexamine is unstable in acidic environments, formaldehyde is liberated under alkaline conditions when heated. This effect indefinitely extends pot life at the room temperature. However, in most cases, hexamine does not decompose formaldehyde and ammonia in the presence of chemical species with highly reactive nucleophilic sites, such as melamine, resorcinol, and condensed flavonoid tannins. Instead, unstable intermediate fragments can be reacted with highly reactive nucleophilic sites, such as tannin or melamine, among others, to form amino methylene bridges before yielding formaldehyde. Any species with a strong negative charge under alkaline conditions can react with the intermediate species formed by the decomposition of hexamine far more readily than formaldehyde. This characteristic accounts for the capability of wood adhesive formulations based on hexamine to render bonded panels with extremely low formaldehyde emission [13].
\nIn the absence of highly reactive species with strong negative charges, hexamine decomposition proceeds rapidly and results in formaldehyde formation. Formaldehyde emissions from wood particleboards bonded with pine and wattle tannin-based adhesives with paraformaldehyde, hexamine, and tris(hydroxyl)nitromethane hardeners have been measured using the perforator method. All particleboards manufactured using wattle tannin systems with three different hardeners satisfied grade E1 requirements. On the contrary, only particleboards made with pine tannin and hexamine hardener satisfied grade E1 requirements. This tendency was attributed to the curing mechanism of the hardener, the reactivity of the tannin molecule toward formaldehyde, and rapid reactivity of pine tannin toward formaldehyde [13, 14].
\nFormaldehyde is substituted with other aldehydes given that the methylene linkages may be too short to form cross-linkages. Pizzi and Scharfetter have shown that furfural-aldehyde is an efficient cross-linking agent and an excellent plasticizer for tannin resin adhesives [15, 16]. The complete replacement of formaldehyde with other aldehydes is unfeasible owing to their slow reactivity with tannins. For example, the water resistance of cured tannin-formaldehyde networks was improved by substituting 10–30% of formaldehyde with other aldehydes with saturated hydrocarbon chains but not by the cosmetic addition of water repellents such as waxes. Tannin adhesives prepared and/or set and/or cured with other adhesives only or with mixtures of formaldehyde and high proportions of other aldehydes yielded cured bonds weaker than those obtained with formaldehyde alone or its mixtures with furfural.
\nThe metal ion effect on phenol-formaldehyde reactions can be applied to condensed tannins of the flavonoid type with some degree of success. The acceleration effect of the metal ions follows the order of PbII, ZnII, CdII, NiII > MnII, MgII, CuII, CoII > MnIII, FeIII ≫ BeII, AlIII > CrIII, CoIII.
\nTannin is subjected to two competing reactions when heated in the presence of strong mineral acids: (1) degradation leading to anthocyanidin and catechin formation and (2) condensation as a result of the hydrolysis of heterocyclic rings (p-hydroxybenzyl ether links). The created p-hydroxybenzyl carbonium ions condense randomly with nucleophilic centers on other tannin units to form phlobaphenes. Other modes of condensation such as free radical coupling of B-ring catechol units cannot be excluded in the presence of atmospheric oxygen [17].
\nThe interflavonoid bonds of condensed tannins with phloroglucinolic A-rings are susceptible to cleavage under even mild alkaline conditions. This characteristic could increase the reactivity with aldehydes. Increased reactivity and autocondensation can be introduced through heterocyclic ring opening.
\nA drastic increase in the reactivity can be attributed to the liberation of the phloroglucinol species of intermediate products. Model compounds have been used to demonstrate that alkaline-catalyzed rearrangements increase tannin reactivity. Nevertheless, some researches have considered model compounds to demonstrate that tannin structural rearrangements can increase or decrease reactivity toward aldehydes.
\nThe autocondensation reactions that are characteristic of polyflavonoid tannins have recently been utilized in adhesive preparation processes, i.e., adhesive hardening in the absence of aldehyde. Autocondensation reactions are based on the opening of the O1–C2 bond of the flavonoid repeat unit and the subsequent condensation of the reactive center formed at C2 with free C6 or C8 sites of a flavonoid unit on another tannin chain under alkaline or acidic conditions (Figure 5). Although this reaction increases the viscosity considerably, gelling does not generally take place. Normally, gelling occurs (1) in the presence of a small amount of dissolved silica (silicic acid or silicates) catalyst or some other catalysts and (2) on a lignocellulosic surface.
\nAutocondensation of tannin resin.
In the case of highly reactive pine tannin, cellulose catalysis is sufficient to induce hardening and to produce boards with strengths that satisfy the relevant standard requirements for interior-grade panels. The addition of dissolved silica or silicate catalyst to low-reactive tannins, such as mimosa and quebracho, is the best approach to achieve the required panel strength. The amount of silicic acid or silicates affects gelling. Gelling accelerates as silicate content increases and stabilizes after reaching a certain value. Although tannin resin adhesive that was manufactured through autocondensation increases the dry strength of panels, the strength of the resulting crosslinking is insufficient for exterior-graded panels [18]. Aldehyde curing agents should be added for the preparation of exterior-graded panels. Nevertheless, hardening through tannin autocondensation without any aldehyde addition is also possible. The mechanism of polyflavonoid autocondensation has been examined using carbon-13 nuclear magnetic resonance and electron-spin resonance spectroscopy, among others [19, 20, 21].
\nZinc acetate also appears to induce a similar type of autocondensation reaction that is slower than that induced by an aldehyde. The reaction induced by zinc acetate mainly occurs at high curing temperatures. Consequently, the effect of zinc acetate is too weak to hinder interflavonoid bond cleavage and pyran ring opening in procyanidins. Therefore, in the presence of zinc acetate, the autocondensation of prodelphinidins to prodelphinidins and prodelphinidins to procyanidins will occur, whereas that of procyanidins to procyanidins will never or will rarely occur [22].
\nThe autocondensation of polyflavonoid tannin is facilitated by the reaction that occurs on cellulose and lignocellulosic substrates. Cellulose-induced polyflavonoid autocondensation and Lewis acid-induced polyflavonoid autocondensation have different mechanisms but involve similar subsequent reactions [23].
\nTannin sulfonation is one of the most useful reactions in flavonoid chemistry and can be particularly useful for the preparation of tannin resin adhesives. The drastic differences between the sulfite treatment products of resorcinol A-ring type tannins (e.g., black wattle tannins) and those of resorcinol A-ring type tannins (e.g., pine tannins) are mainly attributed to the different stabilities of the linkage bonds between their units relative to those of heterocyclic ether bonds. When sodium bisulfite is used to treat black wattle tannins, heterocyclic ether bonds first open because of the relative stability of the connecting bonds between units. Then, sulfonate is added to C-2. In this situation, tannin molecules are negligibly degraded.
\nThe reaction of 5,7-dihydroxy proanthocyanidins with sulfite ions under normal pH conditions proceeds through the cleavage of the interflavonoid bond with the formation of flavan-4- or proanthocyanidin-4-sulfonates, as indicated by the scheme shown in Figure 6.
\nSulfonation of tannins.
Sulfonated products can be obtained from phloroglucinolic tannins without the opening of the etherocyclic ring because interflavonoid bonds are easily cleaved. Flavan-2,4-disulfonates are also formed readily.
\nThe involvement of interflavonoid bond cleavage in the sulfonation of phloroglucinolic condensed tannins affects the utilization of these tannins because their molecular weights can be tailored to suit their applications such as wood adhesives. Additionally, sulfonation affords tannins with reduced viscosity and increased solubility through the following mechanisms:
The elimination of the water-repellent etherocyclic ether group.
The introduction of the hydrophilic sulfonate group and another hydroxyl group.
The reduction in polymer rigidity, steric hindrance, and intermolecular hydrogen bonding through the opening of the etherocyclic ring.
The hydrolysis of hydrocolloid gums and interflavonoid bonds under acidic conditions.
However, sulfonation may be disadvantageous because sulfonate groups promote sensitivity to moisture and thus aggravate the deterioration of adhesive. This problem could be solved through desulfonation. The desulfonation of 2,4,6-trihydroxybenzyl sulfonic acid and sodium epicatechin-(4β)-sulfonate is a facile reaction under mild alkaline conditions (i.e., pH > 8.0 and ambient temperature). Hydroxyl benzyl sulfonic acids with resorcinol or phenol functionalities resist desulfonation at a pH value of 12 and a temperature of 90°C. Therefore, sulfonation not only reduces molecular weight while improving the viscosity and solubility of tannin resin adhesives but also prevents sulfonic acid functionalization and affords aldehyde condensation products that are insoluble in water [24].
\nTannin resin adhesives can be cured under high heat (thermosetting) or at room temperature (coldsetting) [25]. Thermoset tannin resin adhesives are used in the preparation of plywood, particleboard, wood preservation resin, and impregnated resin, among other wood composites. Coldset tannin resin adhesives are used to manufacture glulam, laminating veneer lumber, and finger joints.
\nTannin resin adhesives are used to prepare plywood (Figure 7). However, adhesives manufactured with conventional formulations and technology fails to meet the requirements set for the exterior plywood adhesive. Thus, tannin resin adhesives must be modified by mixing them with other synthetic resins or organic or inorganic modifiers and by optimizing resin synthesis parameters and hot-pressing conditions. Additives can effectively solve the problems of tannin resin hydrophobicity and formaldehyde release and can improve the physical and mechanical properties, especially weather resistance, of the final wood products. Plywood products assembled with modified tannin resin adhesives meet the demand of exterior-grade plywood, have better properties than plywood assembled using phenolic resin, and have a certain commercial potential [26, 27, 28, 29, 30].
\nTannin resin adhesives for plywood manufacturing: (a) profile image; (b) wood failure.
The use of tannin resin adhesives in particleboard production has been accepted in many countries and is used in the manufacturing of industrial particleboard in many countries except in Asian countries. For example, mimosa tannin resin adhesives are used in industrial particleboard manufacture in South Africa and South America (Figure 8).
\nTannin resin adhesives for manufacturing particleboard.
Although tannin resin adhesives have been successfully used for the production of interior and exterior particleboards, the synthesis processes and formulas of tannin resin are drastically different [31]. Generally, tannin resins polymerized with formaldehyde have higher weathering resistance than those polymerized with other nontoxic and nonvolatile aldehydes in accordance with the reactivity of tannin. Particleboards manufactured using tannin resin adhesives with formaldehyde contents that have been partially or completely replaced with acetaldehyde have very low formaldehyde emission or even free from formaldehyde release and have mechanical properties that meet the requirements of interior-grade application [32]. At the same time, particleboards prepared with tannin resin synthesized via an aldehyde-free process can also meet the requirements of interior-grade applications [33]. An appropriate amount of paraformaldehyde or curing agent must be added to increase the weathering resistance of particleboards prepared with tannin resin adhesives. Sometimes phenolic resin is also mixed with tannin resin. The properties of particleboards produced with 60% tannin resin still meet the requirements of exterior-grade application [34].
\nTannin resin adhesives for particleboard production have high requirements for curing agents. Different types of tannin resin adhesives require different curing agents. The performances of tannin, i.e., tannin structure and curing agent selection, and the properties of the particleboard will be affected by hot-pressing conditions, including pressing temperature, time, and pressure. Selecting an appropriate curing agent can accelerate tannin resin curing, reduce formaldehyde emission, and most importantly, can ensure that the performances of the particleboard meet exterior-grade application requirements [35]. Kim et al. found that the reactive speeds of tannin resin adhesives for black wattle tannin followed the order of paraformaldehyde > hexamine > trinitromethane, whereas those for pine tannin followed the order of hexamine > paraformaldehyde > trinitromethane [36].
\nAdditionally, modified tannin resin can be used to prepare particleboards from different sources, such as wheat straw [37], rice husk [38], cashew nut shell [39], and chestnut shell [40]. The elastic moduli, internal bonding strength, and water-absorbing thickness swelling of the prepared particleboards meet the requirements of European standards.
\nWood preservation is vital for protecting wooden products. Traditional approaches for wood preservation include the treatment of wood with various chemical agents to prevent attack by different organic microorganisms and insects. Although traditional wood preservatives confer good effects and strong durability, they inevitably introduce various other problems, such as environmental pollution and carcinogenic effects. Tannin is a natural fungicide and good preservative that can be used to prevent fungal and bacterial damage [41]. Most plant pathogens secrete enzymes that degrade cellulose and lignin. Tannin can effectively inhibit the activity of these enzymes and prevent the proliferation of pathogens by complexing with protein [42]. Pizzi and Conradie confirmed that the antifungal activity of wood treated with flavonoid tannin resins is twice as intense as that of neat wood [43]. Additionally, veneer treated with tannin resin modified with a small amount of boric acid avoided the fungal attack and exhibited high durability, mechanical strength, and fire resistance because tannin and boric acid can simultaneously inhibit bacterial and fungal growth (Figure 9). Meanwhile, the fixation of boric acid in wood with tannin resin and hexamine prevented loss and exerted a good preservative effect that met the requirements of the European standard EN 113 [44, 45, 46].
\nTannin resin adhesives for wood preservation.
Melamine formaldehyde resin has been widely used in the decorative impregnated paper industry. The addition of small amounts of urea can drastically cut costs without affecting performance. Melamine resin-impregnated paper is widely used for the production of laminated wooden floors and panel furniture overlays [47]. Phenolic resin-impregnated paper has limited applications in the production of floor and furniture panels owing to its black color, but it is widely accepted and popular in some particular applications, such as the impregnation of architectural template veneer paper, owing to its good adhesive property and high strength [48].
\nThe flavonoid phenol structure and properties of tannin are similar to those of phenols. Therefore, there are no theoretical constraints for using tannin resin in paper impregnation. Abdullah et al. [49, 50] synthesized a low-viscosity tannin resin, which was used to impregnate paper with a glue amount of 172 g/m2 and hot-pressed on wood-based panel substrates. The final overlay paper exhibited a very smooth surface, high wear resistance, scratch resistance, and water steam resistance. The performances of the optimized overlay paper were even superior to those of overlay paper impregnated with MUF resin (Figure 10). Similar to phenolic resins, overlay paper impregnated with tannin resin has potential use in template production.
\nOverlay paper impregnated with (a) tannin resin; (b) MUF resin.
Natural fiber composites have been developed to overcome the limitations associated with petrochemical resources. They have extensive prospective applications in the automobile and aerospace industries because their raw materials are derived from biomass and they possess unique characteristics. Fibers impregnated with tannin resin can be used to synthesize different types of fibers or wood-based fiber composites (Figure 11). These composites possess high elastic moduli and tensile strength and good water-absorbing expansibility [51, 52, 53, 54].
\n(a) Tannin resin impregnated fiber; (b) laminated composite with tannin resin impregnated fiber; (c) wood composites with veneer and tannin resin impregnated fiber; (d) tannin resin impregnated fiber overlay on the particleboard.
Adhesives for finger joint lumber and glulam must meet high standard requirements because of the rigorous application environment of these materials (Figure 12). These adhesives must possess high mechanical strength and weather resistance. Acacia tree tannin has been widely used to prepare low-temperature curing resin adhesives for finger joint and laminated veneer lumbers [60]. Acacia tannin resin adhesive has a low curing temperature and excellent bonding performance. Additionally, the cost of acacia tannin is lower than that of phenol resorcinol formaldehyde resin. The performance and cost of tannin-resorcinol-formaldehyde resin adhesives must be balanced. The tannin content of such adhesives could reach up to 95% after optimization. The polymerization of resorcinol units is replaced by that of a large number of flavonoid tannin natural phenol units. Resin adhesives with high tannin contents can be cured at room temperature, can exhibit good performances, and can be used to produce veneer and finger joint lumbers and glulam [61, 62]. Other nonvolatile or nontoxic aldehydes, such as glyoxal and glutaraldehyde, are also used to synthesize coldset tannin resin adhesives to effectively reduce the problem of formaldehyde release. Although only a small amount of paraformaldehyde is used to cure tannin resin adhesives, the prepared wooden products demonstrate good mechanical strength and water resistance [63].
\nColdset tannin resin adhesives for wooden product application: (a) glulam; (b) laminates.
Tannin has significant application prospects as a promising natural phenolic polymer. However, this raw material continues to exhibit limitations, such as reactivity, high viscosity, short pot life, and poor weather resistance, among others. Future works must address these problems. Research on tannin resin adhesives should focus not only on wood panels but also on other advanced wooden composites. In addition, the industrialization of tannin resin adhesives in the field of wood manufacturing field is necessary.
\nThis work is supported by the following grants and programs: 1. National Natural Science Foundation of China (NSFC 31760187); 2. Yunnan Provincial Applied and Basic Research Grants (2017FB060); 3. “Ten-thousand Program”-youth talent support program; and 4. Yunnan Provincial Reserve Talents for Middle & Young Academic and Technical Leaders.
\nThere is no conflict of interest in this field.
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After obtaining a Master's degree in Mechanical Engineering, he continued his PhD studies in Robotics at the Vienna University of Technology. Here he worked as a robotic researcher with the university's Intelligent Manufacturing Systems Group as well as a guest researcher at various European universities, including the Swiss Federal Institute of Technology Lausanne (EPFL). During this time he published more than 20 scientific papers, gave presentations, served as a reviewer for major robotic journals and conferences and most importantly he co-founded and built the International Journal of Advanced Robotic Systems- world's first Open Access journal in the field of robotics. Starting this journal was a pivotal point in his career, since it was a pathway to founding IntechOpen - Open Access publisher focused on addressing academic researchers needs. Alex is a personification of IntechOpen key values being trusted, open and entrepreneurial. Today his focus is on defining the growth and development strategy for the company.",institutionString:null,institution:{name:"TU Wien",country:{name:"Austria"}}},{id:"19816",title:"Prof.",name:"Alexander",middleName:null,surname:"Kokorin",slug:"alexander-kokorin",fullName:"Alexander Kokorin",position:null,profilePictureURL:"https://mts.intechopen.com/storage/users/19816/images/1607_n.jpg",biography:"Alexander I. Kokorin: born: 1947, Moscow; DSc., PhD; Principal Research Fellow (Research Professor) of Department of Kinetics and Catalysis, N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Moscow.\r\nArea of research interests: physical chemistry of complex-organized molecular and nanosized systems, including polymer-metal complexes; the surface of doped oxide semiconductors. 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