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Polymers 2013, 5(2), 344-360; doi:10.3390/polym5020344
: Reported is a study evaluating the potential of esterified tannins as plastic additives in poly(lactic acid) (PLA). Tannin esterification using anhydrides was investigated as a route to synthesize tannin esters possessing varying ester chain length and degree of substitution (DS). Esterification decreased the tannin UV absorbance, predominately in the UVB region. However, tannin materials with longer ester chain lengths exhibited melt behaviors suitable for processing in plastics. On compounding into PLA, tannin hexanoate esters lowered the PLA glass transition by 5–6 °C. Shorter chain length tannin esters had a reduced effect on PLA polymer properties. The PLA flexural properties were significantly altered with stiffness decreases of up to 15% depending on ester chain length and loading. Artificial weathering of modified the PLA samples suggests the presence of tannin esters may confer a protection role to PLA on extended exposure. Overall, results suggest scope for the use of tannin esters possessing longer ester chain length as plastic additives.1. Introduction
Application and market growth of renewable polymers has been driven by sustainability as much as the emergence and scale of technology to produce these materials. Poly(lactic acid) (PLA) is one bioplastic which has gained market share due to recent increases in production capacity [1]. In the lucrative plastic additives market, sustainable options remain less developed, particularly those additives being both renewable and biodegradable [2]. Plastic additives contribute a range of functionality and processability to plastics including plasticization, nucleation, flame retardancy, heat stability and impact modification [3]. Research evaluating bio-derived plastic additives has included fermentation products [4] and modified vegetable oils [5] to those based on polyphenols such as lignin [6,7]. In contrast, use of polyphenolic tannins remains relatively unexplored with few examples of these compounds blended with plastics [8,9,10]. Condensed tannins are polyphenolic oligomers based on a flavanyl repeat unit (Figure 1) and are ubiquitous in leaves, bark and wood of trees and plants. In plants these compounds offer a range of protective roles, inhibiting pathogens, oxidation and UV degradation [11]. Potentially, these tannin attributes could also be imparted to plastics, and in the case of bioplastics, potentially enhancing performance as well as sustainability credentials.
Condensed tannins are commonly available in industrial quantity due to their historical use in leather tanning and adhesives [12]. While there is potential as plastic additives (antioxidant, light and thermal stability), tannins are inherently hydrophilic, being unsuited to many industrial applications. This necessitates chemical modification, for which tannin etherification and esterification have long been known [12]. In the latter case, this is usually limited to acetylation, but longer chain esters have been used in specific applications [13,14,15,16] as have di-acids for crosslinking [17]. Tannin esterification can be achieved by several routes including conventional approaches such as acyl chlorides and anhydrides to those involving transesterification (Figure 1) using a range of bases as catalysts. Within the literature, there is still opportunity to learn how tannin esterification can be applied, controlled and optimized to target certain properties and direct their application.
In the current paper, various tannin esters have been synthesized and compounded into PLA to evaluate their potential as plastic additives. Anhydride esterification has been used to prepare these tannin esters. This anhydride esterification route is contrasted with other esterification methods comparing ease of preparation with ester chain length, yield and degree of polyphenolic substitution. The impact of tannin ester chemistry on the physical, UV absorption and molecular mobility properties of tannin moieties is investigated. Changes to PLA plastic properties compounded with tannin and esterified tannin additives are compared with ester chain length and after exposure to artificial weathering of the plastic.
2. Experimental Section
2.1. Materials
Tannin was extracted from the bark of Pinus radiata using hot water (90 °C) which was subsequently spray dried and further dried under vacuum before use. Acetic, propanoic, butyric and hexanoic anhydrides and 1-methylimidazole were all general purpose grade reagents (>98%) and used as received. Poly(lactic acid) (3001D injection molding grade) was obtained from Natureworks (USA).
2.2. General Method for the Preparation of Tannin Esters
Tannin (5 g–10 g) was dispersed in 2-pentanone (20 mL) and acid anhydride (acetic, propionic, butyric or hexanoic anhydride) added at varying ratios with or without 1-methylimidazole as catalyst (Table 1). The reaction mixture was heated to 70 °C for 4 h with stirring, allowed to cool and poured into cold water (300 mL). In the case of acetylation, the product was collected by filtration and washed (water) until the pH was ≥ 4. For longer chain esters, the aqueous phase was decanted from the quenched reaction mixture, ethanol added and the mixture gently heated (60 °C, 30 min). The product was isolated by either precipitation into water (propionate and butyrate) or extraction into chloroform (hexanoate).
To prepare tannin hexanoate acetate, tannin (10 g) and hexanoic anhydride (14.5 mL) were combined in acetone (50 mL) and 1-methylimidazole (1 g) added. The reaction was heated in an oil bath at 60 °C for 4 h. Acetic anhydride (12.5 mL) was then added and the reaction continued for a further 2 h. After this time, the acetone solvent was distilled from solution. The reaction contents were then cooled with an iced water bath and 100 mL 10% sodium hydroxide solution poured in the flask with rapid stirring. The product was allowed to settle and then filtered. The product was washed with water (2 × 50 mL) before drying under vacuum.
Product | Acid anhydride ratio | Catalyst level (%) | Yield (%)≠ | Degree of substitution |
Tannin acetate | 1:1 | 10 | 1.2 | |
1:2 | 10 | 2.5 | ||
1:3 | 10 | 3.9 | ||
1:4 | 10 | 4.7 | ||
Excess | 0 | 88 | 4.2 | |
Excess | 1 | 134 | 5.3 | |
Excess | 3 | 131 | 5.3 | |
Excess | 10 | 127 | 5.3 | |
Tannin propionate | Excess | 0 | 37 | - |
Excess | 1 | 136 | - | |
Tannin butyrate | Excess | 0 | 31 | - |
Excess | 10 | 152 | - | |
Tannin hexanoate | 1:2 | 10 | 104 | 2.0 |
Excess | 0 | 0 | ||
Excess | 10 | 147 | - | |
Tannin hexanoate acetate | § | 10 | 176 | 5.3 |
§ two equivalents of hexanoic anhydride, followed by excess acetic anhydride; ≠ isolated yield based on weight % increase on tannin used.
2.3. Compounding and Injection Molding
Tannin or tannin esters were combined with PLA to form a master batch using an OMC EBVP 19/30 high-speed twin-screw extruder. The temperature of the extruder head was 170 °C and the heating zones across the extruder barrel ranged between 170 °C and 185 °C [supplementary material]. Each extruded plastic blend was pelletized creating either 5 or 10% tannin ester PLA master batches.
Injection molding of plastic test specimens was undertaken using a BOY 15S injection molder. Nozzle and heating zones ranged between 195–205 °C and 170–190 °C, respectively and operated with a mould temperature of 32 °C, injection time of 6 sec and cooling time of 22 sec [supplementary material]. Using each master batch, PLA blends were prepared containing 0%, 0.5%, 1.0%, 5.0% and, for selected samples, 10% w/w tannin ester. At least 10 tensile test specimens and 20 flexural bars were prepared for each combination.
2.4. Flexural and Tensile Testing
Flexural and tensile testing was undertaken on an Instron 5566 universal testing machine. Prior to testing, samples were conditioned at 23 °C and 50% relative humidity for at least 7 days. Flexural testing was undertaken according to ASTM D790-00 with 10 specimens (123 × 13 × 3 mm) evaluated per sample. Tensile testing was performed to ASTM D638-01 using type I test specimens with a test speed of 5 mm.min −1. Generally 10 specimens were tested per sample.
2.5. Accelerated Weathering
Testing employed an accelerated weathering tester from Q-Panel Lab Products operating with UVA-340 lamps at an irradiance of 0.77 W/m2/nm. Flexural test specimens (123 × 13 × 3 mm) were exposed to a UV light and water regime according to ASTM D4329-99 with the detailed exposure cycle (Table 2). Samples were randomly rotated every 169 h and were exposed for a total of 504 h. Prior to, and at the completion of accelerated weathering, samples were weighed and CIE L*a*b* color measurements taken using a Konica Minolta Chroma CR-400 color meter to evaluate any changes to exposed samples. Flexural testing was also conducted on weathered samples after conditioning at 23 °C and 50% relative humidity.
Step | Condition | Temperature (°C) | Time (h) |
Step 1 | UV | 45 | 8 |
Step 2 | Water spray | 25 | 0.5 |
Step 3 | Condensation | 40 | 2 |
Step 4 | Water spray | 25 | 0.5 |
Step 5 | Condensation | 40 | 2 |
2.6. Characterization
Solid state 13C NMR spectra were obtained on a Bruker Avance DRX 200 instrument with a 7 mm doubly tuned 1H/X MAS probe (Bruker). Samples were packed into a zirconia rotor fitted with a Kel-F cap and spun at 5 kHz. A cross polarisation-magic angle spinning (CP-MAS) pulse program was used with a 1H preparation pulse of 5 µs, 1H decoupling field of 47 kHz, and an acquisition time of 50 ms. Hartmann-Hahn matching was conducted using glycine to allow semi-quantitative analysis. Integration of spectra for degree of ester substitution determination is further described in the supplementary material. Spin locking experiments and variable contact time experiments were run to determine the molecular spin relaxation measurements of selected samples. T1ρH values were calculated from signal intensity and contact times using methodology and protocols published elsewhere [21].
Differential Scanning Calorimetry (DSC) was undertaken on a Thermal Analysis Instruments Q1000 DSC. Samples (4–8 mg) were placed in standard aluminum pans and then initially heated to 120 °C at a heating rate of 10 °C/min. The samples were then cooled (5 °C/min) below 0 °C and heated in a second heat ramp to 200 °C.
Dynamic mechanical thermal analysis (DMTA) used a Rheometrics DMTA V in three point bending mode. Samples (65 × 10 × 3 mm) were acquired from injection molded flexural specimens. Testing was undertaken using a 3 °C/minute heating rate and employed 1 Hz frequency and strain rate of 0.05%.
Ultraviolet (UV) absorbance measurements employed a Cary 300 BIO UV/Vis spectrophotometer. Samples soluble in either water or chloroform were diluted to 0.25% solids whereas the tannin hexanoate and tannin hexanoate acetate samples were dissolved in dimethylformamide solvent at 0.02% concentration. Measurements were made between 200–450 nm in 5 nm increments using the appropriate solvent as a blank.
Confocal laser scanning microscopy (CLSM) was undertaken on a Leica TCS instrument analyzing flexural test specimens. Filters were used to separate the natural fluorescence of the tannin component into green light. Images were obtained using a 20 × 0.5 dry lens. The images were acquired at a size of 512 × 512 pixels and a total field of view of 500 × 500 μm, yielding a resolution of ~1 pixel/μm. Scans in the z-direction were recorded at 5 μm intervals to a depth of ca. 80 μm. Images from the different depths were then combined to produce a 2D projection of a 3D image. Some 10–20 images were acquired using CLSM. Projected 2D images were then subjected to image analysis to determine the size of residual tannin esters domains in the plastic employing a custom written macro using V++ software (Digital Optics V.4.0). The size of tannin ester features were defined by the image analysis program and their area calculated and expressed as frequency distributions of sizes ranging from 40 and >3000 μm2.
3. Results and Discussion
3.1. Esterification by Anhydride Treatment
Peracetylation using acetic anhydrides is a simple and common approach to alter hydrophobicity of polyphenolics [22]. In the current study, tannin was reacted with varying levels of acetic anhydride and 1-methylimidazole catalyst to determine any control of the anhydride reaction (Table 1). Isolation and work up of various tannin acetates revealed products as pale brown powders with yields varying from modest to excellent. The limited solubility of some products necessitated characterization by solid state NMR which was also utilized to determine the average degree of substitution (DS). Generally, it was observed that with a greater acetic anhydride ratio there were corresponding increases in the carbonyl (169 ppm) and methyl (20 ppm) peaks of pendant acetate groups (Figure 2). Upon esterification the tannin C-3' and C-4' (145 ppm) and C-5, 7, 9 (160 ppm) signals [23] split and moved upfield (2–5 ppm). This was more pronounced for the A-ring signals (Figure 1). While this may indicate substitution was occurring preferentially at the A-ring phenols (hydroxyl sites), only at high anhydride ratio was there evidence for these phenols being fully esterified. The degree of tannin esterification could be controlled by the level of anhydride addition (Table 1). A maximum DS of 5.3 was achieved with excess acetic anhydride and was indicative of full esterification of all hydroxyls of the pine bark tannin flavanyl unit [24]. Lastly, the degree of acetylation gave no relationship to the resulting tannin acetate solubility. The presence of both free phenol hydroxyls and acetate groups gives a relatively insoluble product compared to either full esterification (organic solvent soluble) or native tannin extract (water soluble). This suggests a minimum DS is required to permit a change in solubility (hydrophilic to hydrophobic) or greater ester chain length for hydrophobicity.
Esterifying tannin with varying catalyst content and differing chain length anhydrides can give variable results (Table 1). With acetylation, the use of only 1% w/w 1-methylimidazole catalyst proved equally effective as use with 10% catalyst. However, with higher chain length anhydrides, a 10% catalyst was required to maximize both DS and yield. With progressively higher chain length esters, isolated yields decrease, being less than anticipated for full esterification. NMR also suggests lower DS values were achieved with increasing anhydride chain length (Figure 3). This was visually evident with the relative intensity of the ester carbonyl and methyl peaks decreasing across products isolated from acetic to hexanoic anhydride treatments. For example, excess anhydride produces a tannin hexanoate only partially esterified with a DS < 3 when compared with acetylation (Figure 2, Figure 3). This result indicates esterification via anhydride treatment may become sterically inhibited at some phenol centers with greater chain length. Practically, it was also found using a longer chain anhydride requires a more involved isolation step to remove the corresponding acid by-product (Figure 1) compared with acetic acid and acetylation. Overall, these results suggest anhydride treatments should be tailored to deliver only two long chain ester groups via anhydride treatment with full esterification achieved by subsequent acetylation. This was demonstrated by preparing tannin hexanoate acetate (Table 1). This mixed ester approach enabled efficiencies in ester product work up, isolated yield with the additional benefits of minimizing reagent use and improved solvent miscibility, as similarly achieved with tannin-fatty acid conjugates [15].
In comparison to anhydride treatment, acyl chlorides are preferable for the synthesis of longer chain length esters (Figure 1), due to the relative unavailability of such anhydrides, atom efficiency and ease of product work up [19,20]. As with anhydrides, control of the tannin:acyl chloride ratio can give defined DS values. Moreover, full esterification of the flavanyl unit phenols was achievable with long alkyl chain length acyl chlorides [19] compared to anhydride use (Table 1). This result, and the relatively high yields, suggests acyl chloride reactions with tannins are not subject to steric hindrance as observed with longer chain anhydride treatments (Table 1). However, if a lower stearic acid chloride ratio is employed, the tannin stearate product tends to be only partially soluble [15,19] as found with acetylation (Table 1, Figure 2). As above, partial esterification and inherent insolubility may be overcome by acetylation of residual phenols, giving the respective mixed ester tannin stearate acetates, which are soluble in organic solvent [15]. Transesterification is an alternative approach to synthesize tannins with high specificity for substitution of the tannin flavanyl B-ring [20]. This method can be performed in several solvents, does not require anhydrous conditions and offers efficiencies in product workup. However, typically, transesterification achieves a DS < 1, being independent of the ester chain length and this, together with long reaction time employed, may not suit industrial application.
3.2 Tannin Ester Properties
While tannin esterification may enhance hydrophobicity and miscibility in oils [15], chemical modification may alter fundamental tannin properties including reduced antioxidant activity [20], ultraviolet (UV) light absorption or those associated with tannin macromolecular behavior. For example, evaluation of various tannin esters (Table 1) found a range of UV absorption profiles, with key differences observed in the UVB (285–315 nm) and UVA (315–385 nm) regions (Figure 4). In general, unmodified pine bark tannin has the highest absorption over the UVA and UVB region which decreases upon esterification as evident for tannin acetate (DS = 5.3, TanAc). This decrease in UV absorption upon esterification correlated with the level of substitution. Tannin hexanoate (DS = 2, TanHex) retains good absorption in the UVB range similar to unmodified pine bark tannin, but this absorption diminishes in the UVA region. However, despite differing levels of substitution, the various tannin esters show potential as UVB absorbers.
Tannin esterification and ester chain length can alter the relative molecular mobility within the polyphenolic flavanyl unit and tannin oligomers. By employing solid state NMR and comparing native tannin with tannin propionate (TanPr, DS = 5.3), differing molecular motion characteristics were determined about the tannin flavanyl unit (Figure 5). Spin-lattice relaxation (T1ρH) values show the relative molecular motion of some carbons increase on adding propionate ester groups to the flavanyl unit. This increase was most significant at C-2,3, C-5,7,9 and C6'. This suggests the presence of propionate groups has increased the molecular mobility about these carbon centers. This characteristic, together with introduced hydrophobicity, has the potential to influence compatibility and polymer properties when integrated into a plastic.
An evaluation of tannin ester properties by differential scanning calorimetry (DSC) was undertaken to assess the potential melt processing and polymer properties of modified tannins. DSC analysis revealed thermal behaviors were dependent on ester chain length (Figure 6). Both tannin and tannin acetate do not have obvious melt features nor physically melt [18]. However, modified tannins bearing longer chain esters show melt features, decreasing both in broadness and temperature with longer chain length. This broadness in the melt feature may be associated with the range of tannin oligomers present in the extract [25] together with extent and randomness of esterification about the tannin flavanyl unit. In the case of ester chain lengths of 4 to 6 carbons, a board melt occurs between 80 °C and 160 °C. Such melt behavior is generally below typical plastic melt processing temperatures [3]. In contrast, tannins bearing ester groups with 12 to 18 carbons melt below 50 °C [19]. These melt behaviors are at physiological temperature and also suited for application in unsaturated resin systems [15]. Overall, DSC analysis revealed tannins bearing ester chain lengths greater than propionate were likely suitable for processing into plastics.
3.3. Tannin Ester Modified Poly(Lactic Acid)
Based on the relative ease of anhydride treatments and their favorable properties, tannin esters with C2 to C6 chain lengths were compounded into poly(lactic acid) (PLA) at varying levels from 0.5% to 10% (w/w, Table 1). Generally, the presence of these tannin additives color PLA, with this dependent on the ester and concentration in the plastic [supplementary material]. Analysis of the compounded plastic by fluorescence microscopy revealed the relative dispersion of each tannin ester (Figure 7). In the case of TanAc this was retained as relatively distinct domains within the plastic matrix indicative of poor miscibility or phase separation. These domains were present across the TanAc concentration range (0.5%–5%). In contrast, TanHex appeared fully dispersed within the plastic. In progressing from tannin acetate to hexanoate, it was evident the ester chain length determined how the tannin ester dispersed into the plastic. Tannin propionate and butyrate derivatives respectively show progressive dissolution and diminishing particle domains within the PLA compared to tannin acetate.
To evaluate any effect the tannin esters have on PLA thermal properties, both DSC and dynamic mechanical analysis (DMTA) were conducted on injection molded samples. Analysis revealed 10% TanHex and TanHexAc contents in PLA reduce the PLA glass transition (Tg) but does not impact the PLA melt (Table 3 and Figure 8). DMTA revealed both tannin esters significantly lowered the Tg onset compared to unmodified PLA (ca. 50 °C). However, shorter chain length esters and lower quantities of tannin ester gave a reduced impact on PLA thermal properties [supplementary material]. The observed reduction in PLA Tg with tannin hexanoate while significant was less than that which can be achieved (≤ 38 °C) when blending PLA with poly(ethylene glycols) (PEGs) or citrates [26,27]. DSC analysis of the modified PLA samples was consistent with DMTA, showing a decrease in Tg of 6–7 °C upon addition of TanHex or TanHexAc and no change in the melt temperature (ca. 168 °C). The onset temperature of crystallization within samples decreased with greater tannin ester content (Figure 9, Supplementary Material).
Additive | Cycle 1 | Cooling | Heating Cycle 2 | |
Tg (°C) | Crystallization (°C) | Tg (°C) | Melt (°C) | |
1% TanHex | 58.0 | 155.9 | 63.8 | 168.0 |
5% TanHex | 56.1 | 145.0 | 63.6 | 167.3 |
10% TanHex | 54.7 | 139.3 | 57.3 | 167.2 |
1% TanHexAc | 59.6 | 155.9 | 63.7 | 168.3 |
5% TanHexAc | 56.1 | 144.9 | 59.6 | 167.1 |
10% TanHexAc | 53.8 | 139.1 | 57.8 | 166.7 |
1% Tannin | 58.6 | - | 63.5 | 168.2 |
5% Tannin | 58.3 | - | 64.4 | 168.2 |
10% Tannin | 57.6 | - | 64.5 | 167.9 |
A comparison of PLA flexural and tensile properties show the presence of the tannin esters can impact PLA mechanical properties contributing up to 15% decreases in PLA stiffness (Table 4 and supplementary material). On addition of tannin acetate, similar modulus of elasticity (MOE) values as PLA (3894 MPa) were observed with up to 5% TanAc content. With longer ester chain length the MOE values decreased with greater tannin ester contents. For TanPr and TanBu, only 5% loadings achieved a significant decrease in PLA stiffness (<3800 MPa). However, both TanHex and TanHexAc exhibit decreases in MOE values across their entire loading range (0.5% to 10%). At 10% loading, decreases in MOE of up to 15% were achieved with TanHex (3480 MPa) and TanHexAc (~3400 MPa), respectively. Typically more significant decreases in PLA stiffness are observed with plasticizing additives such as PEGs or citrates [27,28]. In the case of adding unmodified tannin, this had a contrasting effect, stiffening PLA with increased MOE values at higher tannin contents (3915 MPa). This result indicates the native tannin likely acts as a filler, as observed with unmodified lignins in PLA [6,7]. The flexural strength decreased upon addition of all tannin esters compared with PLA (133 MPa). This was related to tannin modifier content for C2–C4 chain length esters, but appeared independent of loading for TanHex samples. Tensile testing revealed the presence of tannin modifiers in ≥1% loading decrease PLA tensile modulus values. For 5% TanHex, the tensile modulus was lowered by some 15%. Similarly, PLA tensile strength values were also reduced, with values dependent on tannin modifier loading.
Sample with tannin ester loading | Prior to artificial weathering | Post artificial weathering | ||||||
Modulus | Strength | Modulus | Strength | |||||
(MPa) | StdDev | (MPa) | StdDev | (MPa) | StdDev | (MPa) | StdDev | |
0.5% TanAc | 3902 | 25 | 111 | 1 | - | - | - | - |
1% TanAc | 3826 | 38 | 111 | 1 | 3922 | 22 | 110 | 1 |
5% TanAc | 3868 | 62 | 104 | 2 | 3929 | 61 | 107 | 1 |
0.5% TanPr | 3904 | 16 | 105 | 1 | - | - | - | - |
1% TanPr | 3872 | 41 | 107 | 1 | 3896 | 33 | 112 | 0 |
5% TanPr | 3787 | 21 | 104 | 1 | 3835 | 127 | 105 | 2 |
0.5% TanBu | 3879 | 39 | 108 | 2 | - | - | - | - |
1% TanBu | 3885 | 44 | 108 | 2 | 3903 | 77 | 111 | 2 |
5% TanBu | 3770 | 34 | 105 | 2 | 3855 | 161 | 106 | 1 |
0.5% TanHex | 3846 | 14 | 105 | 1 | - | - | - | - |
1% TanHex | 3749 | 27 | 104 | 0 | 3753 | 171 | 106 | 2 |
5% TanHex | 3605 | 19 | 95 | 1 | 3532 | 121 | 96 | 1 |
10% TanHex | 3480 | 19 | 85 | 0 | 3160 | 263 | 80 | 4 |
1% TanHexAc | 3771 | 25 | 104 | 1 | 3785 | 88 | 107 | 2 |
5% TanHexAc | 3654 | 16 | 95 | 1 | 3614 | 86 | 97 | 1 |
10% TanHexAc | - | - | - | - | 3429 | 223 | 69 | 16 |
1% Tannin | 3805 | 34 | 104 | 1 | 3807 | 121 | 109 | 1 |
5% Tannin | 3915 | 23 | 99 | 1 | 3895 | 110 | 101 | 4 |
10% Tannin | - | - | - | - | 3996 | 74 | 92 | 2 |
3.4. Artificial Weathering
Although PLA is unsuited to exterior application [29], the PLA samples were subjected to accelerated weathering as a means to artificially age the plastic and evaluate any retention of PLA properties due to the presence of tannin esters. This test included both water condensation and UV irradiation (Table 2) with samples expected to exhibit some degradation due to PLA hydrolysis and UV-promoted oxidation [7,29]. Results reveal that after 500 h of artificial weathering, the PLA flexural modulus increased, but this was not statistically significant due to high variability between test specimens (Table 4). This variability marred all test specimens after aging. Flexural modulus values for aged TanAc, TanPr and TanBu modified PLA samples were similar to original values, but this did not differ to PLA at the 95% confidence level. For the TanHex and TanHexAc samples, a 5% loading led to retention of flexural properties after exposure. This result suggests both TanHex and TanHexAc may confer a protection role which may be as a UV absorber within PLA. Evaluation by DSC analysis revealed aged samples lose crystallinity, but retain similar Tg and melt temperatures (Figure 9). Results also show any changes in sample weights after accelerated weathering were negligible.
The results from the colorimetric analysis of tannin ester-modified PLA after accelerated weathering are shown in Table 5. This revealed some variability in color stability with samples typically lightening in color. Unmodified PLA showed the smallest change in ∆E, a likely consequence of this polymer being transparent with little scope for significant color change. Of the modified PLA samples, those modified with TanAc had the highest variability and may be linked to the dispersal of TanAc (Figure 7). TanHex offered the best color stability of the samples which was probably due to the even dispersion of TanHex throughout the PLA matrix (Figure 7).
Sample | ∆L | ∆a | ∆b | ∆E |
TanAc 1% | 4.60 | 7.51 | 2.14 | 9.06 |
TanAc 5% | 12.43 | 1.36 | 1.48 | 12.59 |
TanPr 1% | 6.75 | 0.57 | 6.08 | 9.10 |
TanPr 5% | 9.58 | 0.19 | 0.31 | 9.59 |
TanBu 1% | 4.89 | 3.75 | 4.14 | 7.42 |
TanBu 5% | 9.32 | 0.61 | 0.65 | 9.36 |
TanHex 1% | 5.08 | 0.58 | 3.56 | 6.23 |
TanHex 5% | 5.42 | 0.89 | 3.69 | 6.62 |
4. Conclusions
Esterification of tannin by acid anhydrides is a preferred synthetic route to enhancing tannin hydrophobicity. In this study, tannin esterification by anhydride treatment was dependent on the level of catalyst and anhydride chain length employed. An absence of catalyst gives a reduced degree of substitution, with this more apparent with increasing ester chain length. While preparation of tannin acetate with 1% catalyst achieved maximal substitution, synthesis of higher chain length tannin esters becomes increasingly difficult. This was likely due to increased steric hindrance about the tannin flavanyl unit within oligomer chains. In contrast, esterifying tannins via acyl chlorides is not subject to steric hindrance with longer ester chains. The current study also shows the degree of ester substitution can be controlled by modifying the tannin:anhydride ratio as demonstrated with acetic anhydride. In the case of tannin hexanoate (TanHex), only 2 equivalents of hexanoic anhydride was sufficient to modify tannin properties and increase its miscibility with plastic.
Modifying tannin with increased ester substitution and ester chain led to some changes in fundamental tannin properties, none more so than solubility. Esterification reduced UV absorbance in the UVB region with the extent of this shift dependent on the tannin DS. Tannin esterification also alters the relative molecular mobility within the tannin flavanyl unit as well as polymer properties. NMR spin-lattice relaxation (T1ρH) measurements show increased molecular motion about the flavanyl unit on esterification with relatively short chain propionate groups. More significantly, esterification of tannins can lead to melt behavior. A range of melt behaviors can result with this primarily dependent on ester chain length, but also DS. Typically, a lower temperature melt feature was observed with longer ester chain length. An implication for this work is those tannin esters bearing chain lengths greater than three carbons melt below common plastic processing temperatures. This potential for processing into plastic, coupled with retention of UVB absorption and antioxidant properties and mobility introduced by alkyl ester chains, make tannin esters attractive as plastic additives.
Compounding tannin esters into PLA led to modification of some plastic properties including color. Thermal analysis revealed minor changes to PLA Tg values with the Tg onset lowered some 5–6 °C when modified with C6 ester chains (TanHex and TanHexAc). While there were no appreciable differences in PLA melting, the onset of PLA crystallization was dependent upon the presence and quantity of tannin ester. Evaluation of the PLA mechanical properties show the flexural properties of PLA were significantly altered on the addition of tannin esters. A decrease in flexural modulus with increasing chain length (Ac to Hex) and loading was evident. A 10% TanHexAc loading achieved a 15% reduction in PLA stiffness. In contrast, addition of unmodified tannin acts as a plastic filler, stiffening PLA. Flexural strength values reveal addition of all tannin esters led to reduced flexural strength.
PLA samples were subjected to accelerated weathering to determine any potential protection role offered by the presence of tannin esters. After 500 h of artificial weathering, the PLA flexural modulus increased, but was marred by high variability between test specimens. While flexural modulus values for aged TanAc, TanPr and TanBu modified PLA samples were similar to original values, there was no statistical difference to PLA. With both TanHex and TanHexAc modified samples, the flexural properties were retained upon weathering. This suggests as plastic additives, tannin esters may act to reduce PLA stiffness as well as confer a protection role to PLA. Overall, this study reveals significant scope for the use of longer chain tannin esters as plastic additives, with on-going evaluations in other plastics still to be reported.
The authors are grateful for the confocal microscopy assessments contributed by Carmen Schrade, a visiting intern from the Department of Applied Chemistry, Reutlingen University. This work was supported by Biopolymer Network Ltd., through funding by the New Zealand Ministry of Business, Innovation and Employment. JB, CL and JAE are each grateful to studentships provided by Scion through BSc(Tech) placements (University of Waikato).
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So happy for this new week! Last week was a complete blur. I didn't quite feel right. Just a little stressed after the Christmas break.
Yesterday after church, I made some treat bags to deliver to some of my Young Women. In my church, we have "callings" or assignments, which we do willingly (for free). My calling is to be the President of the Young Women's organization. I am responsible for 44 sweet girls ages 12-18. Of course, I have a lot of other helpers who have callings to assist and counsel with me. It's a busy job for us but one of my favorites in the church.
We have a new girl who just moved into our ward one week ago and it was her birthday. This is what I dropped off.

subset: commoncrawl


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The Flintstones: A Love Letter
From the Editor's Desk: INTRODUCING ... DARKSEID DESIGN BY JIM LEE!
Of all the villains being reintroduced within DC – THE NEW 52, none have been anticipated more than this one. He has not appeared inside a DC comic since early 2009 — DARKSEID!
DC UNIVERSE PRESENTS: A new arc and a new creative team beginning with Issue #6
A spotlight series starring a different hero in each story arc, DC UNIVERSE PRESENTS will be getting a new creative team with issue 6 – co-writers Dan DiDio and Jerry Ordway, with Ordway providing art.


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I spotted one feather untucked from all the rest on this not so shy Segull photo subject perched on The Sooke Lion's Rotary Peir.
2 responses
daniele castellucchio gave props (21 Sep 2010):
great capture!!
Cindy Griff said (30 Sep 2010):
Thankyou Daniele, I was thankful he stayed still for me to shoot him up close!


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There are a number of heart conditions which often qualify for Social Security Disability benefits. While you may apply for Social Security Disability benefits for any heart problem which causes you to be unable to work, there are a number of heart conditions which are specifically listed by the Social Security Administration. These heart problems have specific guidelines regarding how the SSA will determine whether or not to consider you totally disabled.
If you are applying for Social Security benefits with a heart problem, be sure that you have all the necessary medical documents.
Like most disabilities, the severity of your heart problem carries as much or more weight than what kind of heart problems you have. Even if your heart problem does not meet the criteria for total disability as listed by the SSA, you may still qualify for Social Security Disability if you can show how your heart problem precludes you from doing any kind of work which you have done or for which you could be trained. In addition to medical records and employability, the Social Security Administration will examine how your heart problems affect your daily activities.
While not exhaustive, here are some of the more common heart problems which often qualify sufferers for Social Security Disability:
- Chronic Venous Insufficiency. The hearts of those with chronic venous insufficiency are unable to pump blood from the legs back to the heart. This generally results in swelling, difficulty standing, and painful ulcers. To qualify for Social Security Disability with chronic venous insufficiency, you need to have ulcers that don't heal in 3 months.
- Recurrent Arrhythmias. This condition causes your heartbeat to be irregular; to race; or to beat slowly. To qualify for Social Security Disability due to recurrent arrhythmias, you must demonstrate that your condition causes you to pass out or to have frequent spells in which you come close to passing out.
- Chronic Heart Failure. Also called congestive heart failure, there are medical tests administered to measure the flow of blood from your heart. Your heart needs to be performing at 30% capacity to qualify as totally disabled. Additionally, you need to demonstrate that your heart problem causes you pain, even while not exerting yourself.
- Ischemic Heart Disease. This is a pre-heart attack condition which is caused by problems with your arteries. Those who have this condition have poor oxygen flow within their blood stream. This condition is normally diagnosed as a result of a particularly poor stress test or angiography.
- Hypertensive Heart Disease. In order to qualify for Social Security Disability, your hypertension must be so serious that you would also meet the criteria for disability from ischemic heart disease or chronic heart failure.
Bear in mind that you may still qualify for Social Security Disability benefits even if your heart problems do not fall strictly within the guidelines for total disability, so long as you can convince the Social Security Administration that your heart problems make it impossible for you to engage in any work. In addition, you must show them that your heart problem makes training for a job other than your original impossible. A qualified disability advocate can help you determine whether you should pursue a Social Security Disability claim.
If you think you might qualify for Social Security Disability benefits based on a heart problem, the two people you should get in your corner are your doctor and a Social Security Disability attorney. Your doctor will need to substantiate the medical information, as well as document what attempts are being made to control or improve your heart condition. An attorney who specializes in Social Security Disability gives you the best chances of having your disability claim accepted, as well as helping you through the appeals process, if it should become necessary.


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Uncyclopedia:Imperial Colonization/message
From Uncyclopedia, the content-free encyclopedia
edit Imperial Colonisation needs YOU
Ahoy, mateys! Imperial Colonisation (or colonization for those that fought colonial rule) has had a strong and proud history. We strive always to civilise the untamed areas of this great globe of ours, and we have had great success. We have covered the past, and the future. We have brought forward great leaders and artists with out efforts. We have enlightened and educated the masses. And of course, as part of changing the world, we have changed YOU!But there are still parts of this great world that need te help of people like yourselves, so to the end, the lobsterbacks are being called on again. And we need you to help us with our latest project. So slap on your redcoats, shoulder your rifles, and head to the colonies!
This has been sent to you as a previous member of IC. If you don't want to receive any more messages relating to IC, inform PuppyOnTheRadio, and he might do something about it.


text:
Spiral Arm Formation Sequence
Dark, Mysterious Cloud: A dark, wispy cloud of dust (extending from the center, right) seems to billow out from a bright explosion in this false-color image in infrared light from the Spitzer Space Telescope. These views have revealed that the mystery cloud, called M17 SWex, is forming stars at a furious rate but has not yet spawned the most massive stars, known as O stars. To the left, on the trailing end of the dark cloud, such mammoth O stars create a dramatic contrast of brilliant light near the image's center.
Image: Penn StateUntitled
The Timetree of Life from an assembly of individual timetrees. Each of the 1,610 terminal branches represents a family or family-level taxon.
Image: Penn StateBanana
Artist's concept of the upgraded Hobby-Eberly Telescope. The VIRUS spectrographs are contained in the curved gray.
Image: Penn StateUntitled
Image: Penn StateUntitled
The Gran Telescopio CANARIAS, located in the Canary Islands off of the northwest coast of Africa, includes a mirror almost 35 feet wide and is situated at one of the world's best locations for star-gazing.
Image: Penn StateUntitled
When an exoplanet transits across the face of its host star atoms and gases in its atmosphere absorb some of the starlight at specific wavelengths. These absorption wavelengths form a unique fingerprint, allowing researchers to identify the presence of Potassium.
Image: Penn StateUntitled
The special-purpose telescope of the Sloan Digital Sky Survey is now engaged in a number of new astronomical surveys that will continue through 2014, ranging from the discovery of new planets to mapping the large-scale structure of the universe.
Image: Penn State


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Hey everyone, I'm looking for a tennis partner, level 3-4, for week nights/week ends. I'm usually available starting at around 6:30 PM during the week. I usually play in nun's island, but I own a car, and therefore I can play somewhere else. If anyone is intersted, let me know! (Fluent in french here!)
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Thursday, June 01, 2006
Yes, the AP bullshit on Reid is done deliberately.
There's no other explanation.
I think I'm on a blogger ethics panel at Yearly Kos, where we will solve these problems once and for all.
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Tropical Fish Keeping - Aquarium fish care and resources
- Aquarium Photography
- - Photos of my Piranha
Photos of my Piranha Here's a couple of pics of my Piranha, the jury is still out as to the exact species but it's either Serrasalmus Marginatus (Spotted Piranha) or Serrasalmus Compressus (Compressed Piranha)...both very similar species and this one shows characteristics of both. Without having the location of it's collection it's going to be hard to make a definite identification. I'm not particularly fussed either way, he's a great little Fish to have. In case you're not familiar with them they are solitary species unlike the red bellied Piranha that most people associate with the name Piranha. They will kill other tank mates, including their own kind so must be kept alone. They survive by taking chunks out of larger Fish's fins and body, they will also eat smaller Fish and the parasites that are on other Fish...usually red bellies. http://i264.photobucket.com/albums/i...ginatus003.jpg http://i264.photobucket.com/albums/i...ginatus002.jpg |
wow! those are some good looking fish :) |
Thanks, I'm really proud of him. He's pretty rare in the hobby, even amongst Piranha keepers. I should strees that they're not for everyone, some can be very aggressive and attack anything that moves (finger chasers) but believe it or not they can also be very timid and will often just sit in one spot all day, usually hidden. The only time you'll see them is when they feed which may only be 2-3 times a week. They also need a huge tank for their size and you can't keep anything else so they're definitely an acquired taste. |
Oh he's just one fish! Very cool indeed. I see what you mean about acquired, I will just live vicariously through your piranha keeping! I have little tetras so I wouldn't even consider it! |
Yeah sorry, that wasn't very clear. I feel I have to point out that they're actually quite boring and difficult to keep because I see so many people getting bored with them and selling them on, not looking after them properly, keeping inappropriate Fish with them (that never ends well) and/or feeding them all sorts of live stuff for entertainment. He does help me to cull the odd deformed Guppy though that I get because I'm breeding those at the moment too. |
Wow he is amazing!! What about a hole tank shot?? And how big is the tnak? |
I haven't got the camera at the moment but I'll get a whole tank shot when I get the camera back. It's a bare tank (no gravel for cleanliness) with potted plants and java fern on bogwood. The tank size is a bit odd, it's 36"L x 15"W x 21"H which works out at about 50 US gallons which is just about big enough for him to get to full size if he turns out to be a Marginatus (about 8" max), if he's a Compressus (about 9" max) I'll have to increase to something like 48" x 18" x 18"...I'm planning on doing that regardless at some point. As you can see, they need alot of space for their size. |
Yeh they need loads of space!!!!!!!!!!! |
He's currently living on a diet of Scallops and squid, he eats better than I do:lol: |
If fish are supposed to lower your blood pressure... does that apply to finger bitting pirahnas? hehe :lol: |
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It's a year of huge cornerback contracts, with A.J. Bouye and Stephon Gilmore breaking the bank. But will these big-money contracts, and the big-time gambles associated with them, pay off?
21 Jul 2004
With apologies to John Madden; actually, we co-wrote a book. We're proud to announce that Football Outsiders and Football Project have combined forces to produce Brassey's Pro Football Forecast, which will be in bookstores this preseason.
This is the book that was Pro Football Prospectus for the last two years. Unfortunately, due to reasons beyond our control, it isn't going to be Pro Football Prospectus in 2004. The name has changed but the content is better than ever -- plus, we wrote some of it.
(I'm glad they put the best player in football on the cover, but the Ravens are totally screwed now. This book has a curse like Madden. Brian Urlacher was on the first cover and the Bears were terrible that year. Michael Vick was on last year's cover. Uh-oh.)
The first section of the book also contains a long essay on DVOA -- how it works, and why it is better than conventional football numbers. The second part of the book features two essays for each team, one that looks at expectations for the team in 2004 and one that explores a research question related to the team. The essays are written by a number of different folks, including the writers from Football Project like Sean Lahman, Todd Greanier, Dan Lewis, and Brandon Williams, as well as four different Football Outsiders: Aaron Schatz, Michael David Smith, Al Bogdan, and Russell Levine. Here's a list of the essays contributed to the book by Football Outsiders:
Yep, that's a lot of new Football Outsiders material, plus you get all of Football Project's work, like a projection system for 2004 player statistics that will help you prepare for your fantasy football draft. It's the one preseason book you need. Buy yours today.
Anyway, we have two winners who managed to get three correct answers (not counting coaches already hired). Manas Pradhan correctly guessed that Warren Sapp was going to Oakland, Terrell Owens was going to Philadelphia, and Ty Law was staying in New England. Lindsay Oliver also had Ty Law correct, predicted Keyshawn Johnson would go to Dallas, and guessed that Chicago would hire Lovie Smith before they actually filled the job. As our winners, Pradhan and Oliver will both be getting free copies of Pro Football Forecast in the mail.


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What does taking food with Viracept do?Sep 30, 1997 Hi Doc, Some of your other readers have asked about the amount of food they should be taking with Viracept.With the three-times-a-day routine, I end up snacking (meaning an apple or a rice cake) on the two later pill times,because the second round falls between meals and the third falls at bedtime.I'm just not that hungry at those times. I might be a little more motivated if I knew WHY food should be taken with the drug.I think some drugs bond to the fatty acids in food to distribute themselves, right? Does Viracept need food to increase its' efficacy, or is the food intended to buffer the stomach? I also wanted to say thanks for answering an earlier question I had. I had misread the dosing on my Viracept,and fortunately, you questioned what I wrote, causing me to read the label again. I was only 3 days into the regimen, so, THANKS! While three Viracepts a day was a lot easier on my stomach,I don't want to give those little #%$&*#! any more chance to mutate than I have to. |
Response from Dr. CohenThe reason for taking food with Viracept (nelfinavir) is not to decrease side effects, as it is with Norvir (ritonavir), but to enhance absorption. While I can't say how much food is enough, it's my guess that an apple or a rice-cake might be a little too frugal. Glad to hear you caught your error in time! | ||||||||||
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Great Smokey Mtns National Park
7 responses
Davide Simone (Deleted) gave props (26 Jul 2012):
Simply, Stunning !
Raymond Fausel gave props (26 Jul 2012):
cool shot
Susan Littlefield gave props (26 Jul 2012):
Lines, gritty texture, light and shadows....this one has it all!!
Patty Gross (Deleted) gave props (26 Jul 2012):
What an interesting and creative B&W shot. I love the textures and lighting in this photo, Bruce. A very professional shot!!
Cheryl Andrews gave props (26 Jul 2012):
LOVE this shot, the tone and textures and that one spot of 'particled' light!
Bailey Cooper gave props (2 Aug 2012):
I love the particulate particularly.
Kelly Nichols gave props (14 Aug 2012):
It's wonderful that you caught the dust floating in the shaft of light. Very cool image.


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Feb 1, 2012
Valentine's Day Sewing -- YEA or NAY?
Readers, let's be honest. As bad as the modern world can sometimes seem, all one has to do is take a peek back in time to realize that we've come a long way as a culture.
Gone are the days when the "little lady" would stitch herself up a special Valentine's Day duster (pictured up top) to surprise her other half, who would most likely surprise her with a toaster or other chrome-plated kitchen appliance. (My mother herself experienced this in the Fifties and she wasn't happy about it.)
Speaking of the bad old days, last night I watched the cloyingly false, yet undeniably watchable nun-athon, 1966's The Singing Nun starring Debbie Reynolds (Did Charles Schultz dream up that ad copy?). Worst. Nun. Movie. EVER.
That said, if you like the song Domenique, you might enjoy The Singing Nun. The fact that the real singing nun, Jeanine Deckers, upon whose life the film was (very loosely) based, later left the convent, came out as a lesbian, and killed herself in a bizarre double suicide love pact, needn't spoil the joys of watching Agnes Moorhead, sans Endora makeup, as Debbie's sour sidekick.
But let's get back to Valentine's Day sewing. Friends, it should come as no surprise to you that I strongly resent holidays like Valentine's Day, Mothers' Day, Fathers' Day, and the like, when we're supposed to march in lockstep to the Hallmark Card aisle of our local Rite Aid drugstore and robotically purchase an overpriced greeting card which we're to dutifully sign, seal in an envelope, and hand to our loved one on February 14th, perhaps along with a cheap box of Whitman's chocolates.
Thankfully, as sewers, we have so many other options!
I don't quite understand why a woman would want a Valentine's Day apron, since, let's face it, she'd have to make it for herself. I suppose it might be a sexy surprise if she showed up wearing nothing but the apron, but I don't think that was the original intention. Or was it?
If an apron feels too retrograde, perhaps a Valentine's Day vest (upper left corner, below) might fit the bill?
Of course, little girls love Valentine's Day, at least according to the pattern companies. What's cuter than a two year old decked out in hearts, ribbon, and lace? Sadly, she doesn't come dipped in chocolate with creamy caramel centers.
If you wish, you can spend the next two weeks making Valentine's Day decorations, to fill your house with the spirit of the season. A heart wreath!
A heart quilt!
Heart-shaped jewelry cases!
A...um...what is this, exactly?
Readers, in closing, will you be sewing something special for Valentine's Day? Have you ever given -- or received -- a homemade Valentine's Day gift? If so, was it appreciated?
Valentine's Day sewing -- Yea or Nay?
PS -- What's your favorite nun movie?
59 comments:
- VictoriaRFebruary 1, 2012 at 11:10 AM
I will not be doing any Valentine's sewing. I, too, hate the contrived Hallmark Holidays. I have happily escaped that for Valentine's day. It is my daughter's birthday. (She will be 12, a challenging age for all involved.) We forgo all hearts for plain old birthday. This sets my husband and I free to celebrate our love in other ways. I like the idea of being sure you take the time to appreciate your loved ones, but just not in a sappy card way. Whether or not I sew for Valentine's Day depends far more on whether or not I have the time and inspiration. I've given up objecting to holidays based on their Hallmark Corruption Factor, since it's basically inevitable, inescapable, and universal. I'd end up not celebrating any holidays at all. So, theoretically, I might sew a heart-shaped apron just because it was cute and I like deep red, even though I don't need any more aprons and don't have a Valentine.
This year I'm making duct tape roses (in classic industrial gray) to send to my other single friends, and we're all going to drink $4 champagne and listen to death metal and &!#ch about stuff. Not because we're angry alcoholics, though; just on principle, to balance out the cheery-pinkness of it all.In elementary school back in the early 1960's we used to make hand made valentines for school & our friends. I don't recall any special Valentines' Day sewing projects. I might do so this year but over the decades I have found that it is very hard to find an appropriate Valentines' Day item for a male partner or husband. Most of the suggested items are for women- I don't think he'd appreciate an apron with hearts-
ReplyDeleteSuch a downer about the holidays! But I dislike the commercialism of it, as well. I have young children, so I love to get into the spirit of holidays. My husband is more of the opinion, "I am supposed to show my love to you everyday, not just one day dictated by the calendar." And I agree with that.
I love the Trouble with Angels!Ohmigod! I JUST finished a darling, Vintage, pink, apron with heart pockets, and it's not even for Valentine's Day. It's being donated for a silent auction in April. I WILL be sewing a red sweater for my son for Valentine's Day. Last year I made him a heart pillow with arms and legs. He LOVES it. There's no way I can make him anything that he will love that much, so a sweater it is. LOVE the apron patterns!
ReplyDeleteMy bf of 18 yrs and I usually exchange cards and sometime gifts. Nothing is set in stone. If one of us forgets that's cool. When I was single I never fretted over these holidays because I thought they included friends and family as well and didn't consider living alone and not dating bad. I think that's the upside of being an only child-being okay with singlehoodness.
Favorite nun movie is "Song of Bernadette." When I was preschool age I watched that with the intensity of how kids used to watch Barney.Sometimes I would throw a towel over my head in order to channel her otherworldly powers. Nothing appeared.
Back to Valentine's day: Love the '40's and '50's patterns but notice how frou frou-y stuff got later on? Ick.No Valentine's sewing for me. First of all pink hearts and ribbons aren't my thing. Secondly, Valentie's Day was never a holiday I thought much about gift-giving. I mean, yeah, we did cards and stuff in school, and my dad likes to buy everyone chocolate, but other than that not so much. Besides, we all know the REAL holiday is the day after Valentine's - when all the candy wrapped in pink foil goes on sale at the grocery store!
ReplyDelete- SondraGFebruary 1, 2012 at 1:42 PM
I can't imagine spending the time it takes me to sew to make something that is worn for only one day per year.
DH is not the Hallmark holiday type. Some friends find it surprising, but I don't expect a valentines gift, and I don't worry about it.
Nuns - the Penguin, in the Blues Brothers. :) I don't even know how to answer this question because all I can think about now is making a Martin Luther King Junior Day Quilt. I need one. Everyone needs one.
I'm actually thinking of making fabric valentines this year. I figure it shouldn't be too hard and I got this huge grab bag of lace for 2.99 this past summer and it's just taking up space, so it's this or open a lingerie store... But I don't think I would make a day-specific garment for any holiday, it's just too much work and you look demented.
It's not a whole movie devoted to nuns, but the original Bedazzled has this great convent sequence, it's awesome.
strugglesewsastraightseam.wordpress.com- Karen SFebruary 1, 2012 at 1:56 PM
I bought the singing nun movie recently but haven't watched it yet. I'll have to now that you said it's so bad.
I usually don't make V-day gifts and it's not a holiday I've celebrated too often-mostly when I was young and had a boyfriend and expected a gift.
The women on the envelope of Simp 1359 don't look too happy to have those aprons either. I get very annoyed with the expensive and corny gift cards--especially during Valentine's Day. However, if you are in the position to have someone(s) special to share holidays with (especially Valentine's day), I also know its more important to consider what the other person is expecting/desires. And if that means a sappy store purchased card, flowers that will die, sticky candy, or a candlelight dinner, so be it. It's a small price to pay to make the Holiday's special for someone else.
I applaud anyone who can make "everyday" special. I honestly don't have that kind of energy. I struggle with keeping the cap on the toothpaste and ensuring items are returned to their proper place daily. I do, however, use the opportunities that Holidays present to make special occasions. Eventually, over time, we build our own non-commercial traditions and memories.
That being written, I would never sew anything for someone on Valentine's day, or any other day, unless I knew they wanted that. The only singing nun movie I know is
"The Sound of Music" which I really do loveValentine's sewing? Huh? I'm lucky to remember to don an apron at all - ever - let alone a themed one!
However, if someone wanted to gift me with one of those lovely chrome appliances pictured, I would swoon, and give it a place of honor in my kitchen. The lines on a vintage (or vintage-inspired) kitchen appliance are usually to die for, imho.
I'm with Debbie - The Sound of Music - of course it counts!I wouldn't mind a new appliance, but then again, I have really expensive taste. Vitamix, anyone?
I will be sewing the Hubster a pair of boxer shorts for V-day. Mostly because I'll embroider my name, tattoo style on the back. That way I can tell people he has my name written on his butt. lolWell, pink and hearts is a bit dainty for me. But I do have a pair of boxers for Phin cut and waiting to be sewn. So maybe I'll have to finish them for Vday. We usually do make plans to spend the day together doing something fun, but it's never the typical dinner/roses/chocolate kind of affair. I think this year homemade chocolate truffles are on the agenda.
ReplyDeleteWould it be too strange for me to admit that I own McCalls 2282? Granted, I did *not* specifically buy it--it came in a large lot of vintage patterns, and I'd never make it. It looks, well, dorky! And I've dressed the girls in heart-printed fabric, but not specifically for Valentine's day. Around here, it's an excuse to make sugar cookies for the girls to eat!
ReplyDelete- AnonymousFebruary 1, 2012 at 5:26 PM
Valentine's Day means chocolate, roses and red which are all my favorites. I don't sew for Vday because although i love the heart motif, I will only wear it in the form of jewelry. I have a collection of heart-shaped pendants. I don't know why but I thought Vday is for the guy to give the girl something. So, I have never given hubby a Vday gift. Maybe I should start sewing this year as I have always wanted to make a boxer for him out of valentine theme fabric. I am not sure if he will wear it though. On second thought, maybe a red robe will be more appreciated.
Sue LOATHE the Hallmark holidays, particularly this one! How many ways can you demonstrate "artificial"?
Don't know about going au naturel beneath the apron, but wasn't there once a woman named Maribel (sp?) Morgan who advocated greeting the mister wearing nothing but Satan wrap?
Ah, the good old days.- GuidingDuckFebruary 1, 2012 at 7:29 PM
Valentine's Day usually makes me want to barf. I will be making red velvet cupcakes for my kids to take to school, but mostly just because I wanted to try the recipe and that seems like a good way to not pig out on them.
Nun movie: Nuns on the Run with Robbie Coltrane - GuidingDuckFebruary 1, 2012 at 7:43 PM
Let me clarify that... VDay STUFF makes me want to barf. Spending time with my husband is always a pleasure, and we tend to do the loving each other everyday as opposed to just one;)
ReplyDelete - AnonymousFebruary 1, 2012 at 8:07 PM
Favorite nun movie? BLACK NARCISSUS (1947), SOUND OF MUSIC & BEDAZZLED (1967), the latter with Peter Cook & Dudley Moore as nuns in the order of the Leaping Berylians :)
Micky - Elaine (nobody you know)February 1, 2012 at 8:07 PM
No Valentine's sewing. I will be too busy in therapy trying to get over the fact that I was never delivered a flower (check that, food coloring colored carnation) from an admirer during high school home room. Wasn't Sally Field a nun? A surfboarding one, right? She gets my vote.
ReplyDelete - KristinaFebruary 1, 2012 at 8:21 PM
No sewing, but I did make a baby quilt for a gift that had pieced heart squares, a folk shorthand for "this baby is welcome"! My favorite nun movie is The Nun's Story, where Audrey Hepburn is trained in Belgium and goes to the Congo to serve in a medical mission, and falls in love with the doctor, and eventually goes back to Belgium and leaves the nunnery for good. No memorable music, but Inspiring to my 14-year-old self.
ReplyDelete If we are all barfing, why are Hallmark and their ilk still in business? Because of all that pent up Catholic guilt from too many nun movies !!! Lol. Anyway no fluffy aprons, but the best homemade Valentines ever are the sticky ones that your babies make in school and proudly carry home to you. There's Nothing like it...ever. Best nun movie ever? Has to be Black Narcissus with Deborah Kerr. It is a very compelling psychological thriller, not to be missed !
ReplyDeleteWhat about the Flying Nun? I know it's a TV show but I didn't realize until I read this post and the comments how many Nun related movies there were out there. It seems all these movies were made back in the days when people didn't need to be scandalized to be entertained...Real Nun's of Orange County is probably a hard sell, the convent life doesn't lend itself to scandal quite as well. It's more interesting to watch people glorify consumerism than glorifying God I guess, but you never know there is now that show "Virgin Diaries" so it might just happen. I'd be down to see what Nuns do I don't know anything about them really, there is a convent in my neighborhood, randomly, so they are out there.
ReplyDelete- RobertaFebruary 1, 2012 at 9:39 PM
Not a fan of Valentine's Day. Never was. The only good thing about V-Day is that I get to stuff myself with chocolate and drown out all the memories of not getting valentine cards in school -- kind of like Charlie Brown. My mom died on Feb 13, so that doesn't help, either.I do like the vintage, cutsie aprons, but I won't be sewing any to wear on this contrived one-day holiday. (Bitter, much? :) )
ReplyDelete I had my very first sewing lesson (and basically my first real try at sewing) on a 14th Feb, so it is not known as VDay around here, but "Sewing day". And this year it'll involve some cosy movie, chocolate, fondling of expensive fabric and leafing through my Burda stash (no sewing on weekdays, alas). Maybe some online fabric shopping, too, ooops :)
ReplyDelete- GuidingDuckFebruary 2, 2012 at 10:24 AM
QM, that sounds like an awesome way to spend VDay! The only way to make it better would be for my husband to enjoy the fabric fondling as much as I would. I guess there's always other things to fondle.....
ReplyDelete The concept of Valentine's Day is nice, the commercialism... not so much. My husband and I cook dinner together. We pick and ethnic theme, do a little research, and work together on a 3 course meal. He usually buys me flowers, but I prefer carnations to roses and it's sometimes a struggle. Some years he has "disappeared" at the grocery store for a few minutes and flowers (paid for) appear in the cart. I find that amusing.
ReplyDeleteI'm generally opposed to sewing for holidays other than Christmas, Halloween, and every now and then New Years (sparkly dresses, yay!) -- but I will say that I love pulling out the bright red satin cocktail dress I sewed a few years ago for a Christmas party and wearing it for Valentine's Day (at home, because restaurants on VDay are even worse than cards, IMO).
So no Valentine's Day sewing for me, but years ago a friend talked me into making hand-made Victorian-esque cards to give to all our friends, and I *loved* it. Cutting out little pictures from magazines, gluing on bits of lace and ribbons, specializing each for each specific friend, it was lovely. I haven't made the time to hand-make Valentine's Day cards since then, but I could see doing that in lieu of Valentine's Day sewing. I think I would rather send unexpected Valentine's Day cards to friends and family than send the expected "Wishing you and yours a happy holiday season!" Christmas cards. Hmm hmm, I wonder what I have in my stash that could make this happen this year...- AnonymousFebruary 3, 2012 at 9:35 AM
I'm afraid you hit too close to home with the wearable art "Seasonal Vests" pattern (a distant cousin to bad Christmas sweaters...). I have many, many bad early 90s theme clay buttons left over in my button stash -- hearts with little black stitching on them, die-cut fabric calico hearts and fat quarter packs to coordinate...followed closely by sunflowers, birdhouses and watering can themes. Throw in some Mom jeans, a t-shirt with the sleeves rolled up, and you are "good to go".
I wince at the very thought of it.
Gail Those patterns look cheesy, like the holiday itself. I've never been a fan of Valentine's Day. I think it stems from the over-the-top showiness of it. Watching friends receive mountains of chocolate and flowers while talking my ear off about being soooo in love and the best couple ever...only to break up two days later.
Imagine my surprise when my husband asked if we could celebrate it this year. I begrudgingly accepted at first, but now I'm looking forward to cooking a really nice meal for him (and watching American Psycho is a brilliant idea).- UstabahippieFebruary 3, 2012 at 8:50 PM
What was the name of the Whoopi Goldberg nun movies? They're my faves.
I have directions for some heart potholders, but just can't seem to get to them. I knitted some tiny wool hearts to stuff with lavender or catnip, depending on the recipient. They take about 5 minutes each, felt, sew 2 together and stuff, perfect.


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Taboo at Muskoka Sands
Hwy 11 north to Hwy 169 - Bethune Drive cut off. Follow Bethune north to Winewood, turn left then take first right, Muskoka Beach Road. Follow Muskoka Beach Road to Resort.
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More Muskoka Golf Courses:


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They were both wormed and given vaccines and looked nice and healthy. There were no fleas or ticks and just one scabby ear that showed a tooth hole. Seems the litter did some rather rough playing. It's well on the way to healing, so it's not a problem.
Dr B was rather charmed by the little ones and all the techs in the place came out to hold them. They are giving off some amazing puppy breath, so we all had a good fix.
Until the pups have had another round of vaccines and the boys are well, they're being kept apart. Morgan is the only one who has met them, and she wasn't impressed. The pups are living in the library which is off limits to the big dogs. We set up a crate and attached a little run for them so they have room to play, but are confined to one area that's easy to maintain. They're in the room above me as I type this and it sounds as if they're moving the furniture. Their favorite activities are wrestling in the grass and tugging on pantlegs. The larger one is also quite a singer.
So, though it's been a very busy time, it's been good.


text: Asus Eee PC 1000H Reviewed (Best Eee Yet, Except the Price)matt buchanan6/18/08 9:40pmFiled to: Asus eee pc 1000heee pc 1000h1000heeeAsusEee PC24EditPromoteShare to KinjaToggle Conversation toolsGo to permalink Asus's Eee PC 1000H is the least Eee-like Eee yet—big, pricey ($649) and it has a regular ol' platter hard drive. Laptop Mag says the extra screen real estate makes it the most productive yet, too, even though the colors don't pop as much as the Wind. And the keyboard: "To say it's an improvement over the cramped keyboard found on earlier Eee PCs is an understatement." Performance from Atom and its 1GB RAM is solid, and the move to a HDD from a SSD doesn't hurt too much, even on startup—battery isn't hit too hard either, 4 hours and 28 minutes with Wi-Fi. Overall, everything's gravier than past models, 'cept the price. [Laptop Mag] Reply24 repliesLeave a reply


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(807 quotes found)
"I was warned that Mr. Thomas and the Garden would launch a campaign to smear me, and I am not surprised, nor will I be, at any false and vicious accusations that they may spread about me and my family. This is all a diversion. In court, they will have no choice but to deal with the real issues of my complaint."
Anucha Browne Sanders
"We expect to get up to $12 million from the highway administration and have a capital campaign underway, which we'll be able to discuss once we have a full plan in June."
Alexis Faust
"There's a point where we may not be able to mount a credible campaign (with someone else). We may or may not have passed that point yet, but we're close."
Al Cárdenas
"The opposition parties don't want the public to misunderstand that we are campaigning for cabinet portfolios."
Abhisit Vejjajiva
"There are still going to be a lot of ups and downs in this campaign for the next week or so, but I'm going to do what I've been doing all along, which is keep talking straight to New Yorkers."
Anthony Weiner
"No campaign materials are allowed inside the polling place. Either on the person or signs."
Ann Beard
"Overall, in the short term this is not going to deter the Fed from continuing its measured rate tightening campaign,"
Alex Beuzelin
"I got to know Mark during the campaign, and he is a good guy. I think he has a grasp of the issue, and we both agree that something needs to be done. I look forward to working with him on the project."
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"It's not only the largest, in our opinion it's the most important and most significant campaign in Louisiana due to the research we have conducted that revealed to us that people have misconceptions about Louisiana after the storm."
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The Saint Joseph's College Orchestra will make its debut on Sunday, December 2 with its first Orchestra Concert. The concert will be held in the Evans Arts and Science Building Theatre at 2:00 pm CST on the SJC campus. The public is welcome to attend free of charge.
The Orchestra will perform several well-known pieces, including Ludwig van Beethoven's "F�r Elise," "Rule, Britannia!" by Thomas A. Arne, and "Calgary Fiddler's Waltz" by Ned Landry.
"I am very excited for the premiere of the Saint Joseph's College Orchestra," said Director of Orchestras Maxim Zheleznyak. "I encourage people to attend and show support for the orchestra members' hard work and to help continue the Orchestra's growth by spreading word of its excellence."
Zheleznyak, an accomplished violinist, is a regular member of the Manhattan Chamber Orchestra, Manhattan Contemporary Chamber Ensemble, and the Finger Lakes Chamber Music Festival.
For more information, contact Professor Zheleznyak at 219.866.6299 or firstname.lastname@example.com.
Saint Joseph's College, named a "character-building college" by the Templeton Foundation and a "best Midwestern college" by the Princeton Review, is a four-year, Catholic college offering 27 majors, 4 group majors, 34 minors, and 9 pre-professional programs, complemented by the nationally acclaimed Core Program. Founded and sponsored by the Missionaries of the Precious Blood, SJC is located in Rensselaer, Indiana, approximately 90 minutes from both Chicago and Indianapolis, on a park-like campus of 180 acres and has an enrollment of 1,100 students.


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Bank of England chief Mark Carney has dug himself into a hole of his own making over forward guidance. And he\'ll need all of his PR skills to convince markets that he\'s got it right this time if the bank chooses to shift course on Wednesday.
Most economists expect the Bank of England to shake up its forward guidance alongside the release of its quarterly inflation report, according to a Reuters survey. But they have little idea how the U.K.\'s central bank will go about it. Will it lower its 7% unemployment threshold? Scrap the policy entirely? Or maybe give a forecast of when a rate hike might come?
One thing they do believe: A clear majority anticipate that Carney will make a strong verbal commitment to keeping rates low.
\"Dropping guidance is unlikely, as it was introduced to such fanfare just six months ago,\" said Rob Wood, chief U.K. economist at Berenberg, in a note.
\"Instead, we expect the BOE to move to focusing on a range of slack measures. That is what inflation targeting did, so this fudged guidance will mean little.\"
\"Sequels rarely top the original, though. In our view, guidance 2.0 will be cheap talk, worth very little,\" he added.
Cheap talk or not, the 375-billion-pound question is how exactly the Monetary Policy Committee will revamp the BOE\'s framework, and whether Carney can save face while doing so. Pressure has been mounting on the central bank to communicate exactly what will happen to interest rates, when the joblessness level actually falls to the 7% level. Economists have come up with five options open to the MPC — noting some are more likely than others.
1. Go \"Fed\" style: The BOE could say it will keep rates low \"well past\" the point when unemployment falls below its threshold.
\"We expect the MPC to reassure the markets that rates will still be on hold for some time and will eventually rise only gradually, with reference to a range of slack indicators and the inflation forecast, rather like the Fed has done in the U.S.,\" analysts at HSBC said in a note.
The U.K. central bank has pretty much already done that, with Carney doing his best to stress that rates aren\'t going up any time soon. Even at Davos, the BOE boss stressed that there is \"no immediate need to increase interest rates\".
2. Go \"Draghi\" style: This is seen as one of the more likely outcomes. With this, the bank makes a broader commitment to keep policy loose for many months to come, without specifying which indicators it\'s using to assess the strength of the British economy.
It would echo the European Central Bank\'s approach: President Mario Draghi has repeatedly said its interest rates will remain low for \"an extended period of time.\"
3. Publish an interest-rate forecast: There are two options here: The bank could publish an interest-rate fan chart (as seen at the Swedish Riksbank) or release individual forecasts from MPC members as to the date of the first rate hike.
Eventually, the BOE will introduce some sort of interest-rate forecast, analysts say. But it\'s probably too soon to do it right now.
4. Switch to a new quantitative threshold: Scrap the unemployment threshold and replace it with another measure. If the BOE chooses to do this, wages would be the most likely benchmark. This shift is unlikely to be adopted, according to prevailing wisdom.
5. Lower the unemployment threshold: Not a very likely choice, economists say. Wood from Berenberg explains why:
\"Guidance is meant to provide clarity about how policy is set. Shifting the goalposts would do the opposite. It would undermine BOE credibility.\"
The Bank of England is not alone in facing pressure on updating its forward-guidance tool. Just like the MPC, the U.S. Federal Reserve has seen the joblessness level improve much faster than anticipated, bringing forward the question of a rate hike.
New Fed chief Janet Yellen was Tuesday grilled at the House Financial Services Committee about what will happen to the U.S.\'s ultra-low interest rates as the unemployment rate drops closer to the 6.5% unemployment threshold? Supposedly nothing. The chairwoman bluntly declared that the Fed won\'t act just because the threshold is reached, which is expected within the next few months.
For U.K. investors, the suspense will end Wednesday at 10:30 a.m. London time, or 5:30 a.m. Eastern Time, when the inflation report comes out. Financial markets could be in for a volatile day, depending on what the MPC goes for. Doing a \"Fed\" will probably disappoint, while a new interest-rate framework would be easy and clear for investors to understand, Wood said.
\"I think the BOE is more likely than not to go for the more disappointing measures, and within that to be relatively hawkish. The reason is that the economy is tightening on most measures, so I don't believe they will want to signal a rate hike is delayed for a long time.\"
\"My forecast is a rate hike in the first quarter of 2015 with a 30% chance in fourth quarter 2014,\" he said.
– Sara Sjolin
– Follow Sara on @sarasjolin
– Follow The Tell blog on @thetellblog
More must-reads from MarketWatch:
Yellen stresses continued low-rate policy
George Soros\'s hedge fund regains title as world\'s most successful
How to find conflict-free diamonds


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Your senior baseball season is over with. You capped it all off with a great showing in the postseason, winning several "all-everything" local and state awards. You are one of the most talked about high school baseball players in the whole state. There have been rumblings and rumors of scouts watching your every move on the diamond and checking out your background for potential faults.
The week before the amateur baseball draft is a blur. Scouts from several teams call giving you a prediction where a team might draft you. First they say not before the first ten rounds. Then they say maybe within the first 8 rounds. The final calls say they can't make any guarantees besides within the top 10. Rumor has it that teams are scared of drafting you early because of a somewhat solid commit to the university.
The draft day is upon you. Unlike the other major sports in the United States, the baseball amateur draft is not nationally televised or hyped up. This is simply because not many players make it to the big league. The players won't be ready to contribute to a major league team for a few years (with closers being the exception). Instead of being televised, the draft is webcast.
Your normally techno phobic parents hunch over the computer screen listening to the pre-draft coverage. You feel the need to get out of the house, so you go hang out at a friend's house. You come home in the evening to see your mother on the front door step waiting for you. When you exit the car, she sprints over to you yelling, "You got drafted! You got drafted!"
This is where the story branches off into several points, to explore several different outcomes. Hopefully this will give you an idea of what could happen depending on where you were drafted.
Scenario #1
Your mother is crying hysterically.
You are too shocked for words. You numbly walk into the living room to the fax machine. There sits an official Texas Rangers memo saying they were willing to offer you a whole bunch of zeroes.
This situation is definitely hard to deal with. On one hand, you have a full-ride scholarship to one of the top college baseball programs in the country.
Both your parents want you to have a college education, so you have a fall-back plan if baseball doesn't work out. However, a million dollar signing bonus also seems like a good fall-back plan.
On the other hand, there is the prospect of playing in the minor leagues right out of high school. Studies have shown that through the years, players drafted in the 1st round have a better shot at making the big leagues than any of the rounds following it (there are 50 total rounds).
Having that million dollars lessens the blow of not attending college in the near future. Since you are the team's No. 1 pick, you can guarantee that the organization will pay attention to you for the next 3-5 years, even if you stink, meaning you will not be overlooked simply because the team has so much invested in you.
The Decision:
It is hard to ignore being drafted in the first round. Unless you get drafted by a team you see no chance of advancing because of a loaded system, or a lowball bonus offer, it's probably in your best interests to sign. Most teams also help pay for college education for some of their minor league players.
Scenario #2
Your father comes out to your car and offers you a firm handshake. You have just been drafted in the 2nd or 3rd round (play along).
The team that drafted you is willing to offer you around half a million to sign. It's still a pretty good offer, considering you get half a million no matter how bad you play for the first few years.
But still, that college offer is there and it's hard to pass up. Should you take the plunge and play in the pros, or go to college?
This decision is actually harder than scenario #1, because you won't be treated as a jewel of the organization's farm system unless you put up big numbers. Also, you could go to college for three years and come back and get big money in the first round, depending on your performance.
The Decision:
2nd and 3rd rounders also have a decent chance of making it to the big leagues, regardless of whether they were in high school or college. Obviously if you don't get the bonus you were hoping for, you can use the college option as leverage in negotiations. This is a hard decision no one can make without getting a grip on the whole situation.
Scenario #3
In this situation you were drafted between the 4th and 10th round. You are lucky to get a decent bonus, or if a team is really keen on you, they could throw big money at you to help steer you away from going to college. You are most likely going to play in low rookie ball upon signing, and will have to shine to get any notice from the bigwigs in the organization.
The Decision:
Unless they throw big money at you to keep you from signing, go to college. If you do well in college, you can re-enter the draft in three years with a better chance of landing in the first three rounds.
Scenario #4
Something happened, and now you have been drafted past the 10th round.
The Decision:
This is a much easier decision than the rest. Unless they throw big money at you, go to college, simple as that. If you do decent in college, you will probably be drafted in the first 10 rounds.
Hopefully this article helped you in understanding what can go on during draft day. The decision is never easy, but if this was at least informational, then it has served its purpose. Remember to learn the ins and outs of contract negotiations if you find your self in this situation. Learn the rules about hiring agents.