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Nano-particles of calcium and phosphorous compounds are made in a highly pure generally amorphous state by spray drying a weak acid solution of said compound and evaporating the liquid from the atomized spray in a heated column followed by collection of the precipitated particles. Hydroxy apetite (HA) particles formed by such apparatus and methods are examples of particle manufacture useful in bone and dental therapies.
1. A method for manufacture of high purity, nano sized particles of a soluble compound capable of precipitation as a solid at ambient temperature, said particles generally sized in the range of less than about 100 μm in mean diameter comprising the steps of:
a) forming a liquid solution of a solvent and said compound;
b) combining said solution with gas through a spray nozzle to atomize the solution;
c) directing the spray into a chamber at a temperature to evaporate the liquid and thereby form nano particles thereof, said spray forming droplets of a size no greater than about 100 μm; and
d) collecting said dried particles.
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This is a utility application based upon derived from and incorporating by reference a previously filed provisional application entitled Nanostructured Bioactive Material Prepared by Spray Drying Techniques filed Apr. 6, 2004 as Ser. No. 60/559,884.
This invention was made during research activities that were supported in part by Grants DE11789 from the NIDCR to the ADAF and carried out at the National Institute of Standards and Technology.
In a principal aspect the present invention comprises apparatus and preparation methods, by a spray drying technique, for nanostructured bioactive material that has high reactivity derived from small particle sizes and high surface areas comprising the material. Such manufactured material has performance advantages in a range of biomedical applications.
The mineral component of bone and teeth consists primarily of non-stoichiometric and highly substituted hydrozyapatite (HA) in poorly crystalline or nearly amorphous forms. The "impurity" components that are present at significant levels in biominerals include sodium, potassium, magnesium, and strontium substituting for calcium, carbonate for phosphate, and chloride and fluoride for hydroxyl ions. Because HA is stable under in vivo conditions and is osteoconductive, synthetic HA has been widely used in hard tissue repair application, such as implant coatings and bone substitutes. Other calcium phosphate phases have also been shown to be highly biocompatible and/or osteoconductive. As a result, with the exception of fluorapatite (FA), all calcium phosphate compounds listed in Table 1 have been used in some form of bone repair applications.
Calcium phosphate compounds are also useful in various dental applications. For example, a slurry or gel that contained MCPM and fluoride was used as topical F agents that produced significant amounts of both tooth-bound and loosely bound F deposition on enamel surfaces. A chewing gum that contained α-TCP as an additive released sufficient amounts of calcium and phosphate ions into the oral cavity and significantly alleviated cariogenic challenges produced by sucrose. A calcium phosphate cement that contained TTCP and DCPA was shown to provide effective apical seal when used as a root canal filler/seal, or as a sealer with as a retrievable master cone. The cement was also effective as a perforation sealer. ACP or a TTCP+DCPA mixture has been used as the mineral source in remineralizing dental restorative materials.
In addition to calcium phosphates, a number of calcium-containing compounds also have significant dental applications. Calcium fluoride, CaF2, which is the major product of most topically applied F (F dentifrices, F rinses, professionally applied F gel, etc.), is the source of ambient F in the mouth that is primarily responsible for the cariostatic effects of F. The greater the amount of CaF2 that adheres to the oral tissue surfaces after a F application, the greater is the oral F retention and therefore the F cariostatic effects. Calcium-silicate compounds, tricalcium silicate and dicalcium silicate, are the major components of mineral trioxide aggregates (MTA), a material that finds wide uses in endodontic procedures, such as root end and perforation fills and for apical closure in the apexification procedure. Calcium silicate hydrates (CSH), xCa(OH)2 ySiO2zH2O, of varying Ca/Si/H2O ratios are among the products formed in MTA.
Defined broadly, the term "nanostructured" is used to describe materials characterized by structural features of less than 100 nm in average size (WTEX Panel Report on Nanostructure Nanodevices, 1999). Clusters of small numbers of atoms or molecules in nanostructured materials often have properties (such as strength, electrical resistivity and conductivity, and optical absorption) that are significantly different from the properties of the same matter at the bulk scale. In the case of calcium phosphates and other bioactive inorganic materials, one of the most small particle size and high surface areas. There are a number of reasons to believe that the combination of small particle size and high reactivity can lead to performance advantages in a range of clinical applications. For example, as set forth in the description of the preferred embedment hereinafter, experimental results showed that nano sized HA, when incorporated into a TTCP+DCPA calcium phosphate cement caused a drastic reduction in setting time from 30 min to 10-12 min. It is anticipated that nano particles of other calcium phosphate phases, which are ingredients of the various calcium phosphate cememts in clinical use, will also significantly improve the setting and other handling properties, e.g., cohesiveness, injectability, etc., of the cements.
The apatite crystallites in human bone, enamel, dentin and cementum are all extremely small in size and can be considered as nanstructured materials. Because HA is the prototype for bioapatites, which are in nano crystalline forms, extensive efforts have been made to produce synthetic nano HA materials. Methods that have been used for preparing nano HA material included chemical precipitation, in some cases followed by spray drying or hydrothermal treatment, sol-gel approach, microemulsion techniques, precipitation from complex solution followed by microwave heating, wet chemical methods incorporating a freeze drying step, mechanochemical synthesis, and eletrodeposition. Additional studies reported synthesis of composites of nano HA and bioactive organic components including HA-collagen, HA-chondroitin sulfate or HA-chitosan using direct precipitation method, nano HA-polyamide using HA slurry and solution method, and Ca-deficient nano HA-high molecular weight poly (D,L-lactide) through a solvent-cast technique.
Preparation of microcrystalline and nanocrystalline HA have also been disclosed in the patent literature. U.S. Pat. No. 5,034,352 discloses that Spray drying is the preferred technique for converting the gelatinous precipitate of hydroxylapatite into the fine dry articles suitable for use in the agglomeration process. U.S. Pat. No. 4,897,250 discloses that calcium phosphate, icnlduing hydroxyapatite, precipitated by the reaction can be withdrawn in a powder form by any conventional techniques such as filtration, centrigual separation, and spray drying. U.S. Pat. No. 6,033,780 discloses that manufacturing method of the spherical apatite is that a slurry comprising hydroxyapatite as its main component is dried and powdered to prepare aggregates of primary apatite particles, preferably, spray dried to form spherical particles. U.S. Pat. No. 6,558,512 discloses that one method for preparing dense, rounded or substantially spherical ceramic particles such as calcium hydroxyapatite is by spray dring a slurry of about 20 to 40 weight % submicron particle size calcium hydroxyapatite. U.S. Pat. No. 6,592,989 provides a method of synthesizing hydroxyapatite comprising the steps of preparing a mixed material slurry be dispersing calcium hydroxide powder into a phosphoric acid solution; conducting a mechanochemical milling treatment. U.S. Pat. No. 5,585,318 provides methods for producing non-porous controlled morphology hydroxyapatite granules of less than 8 μm by a spray-drying process. Solid or hollow spheres or doughnuts can be formed by controlling the volume fraction and viscosity of the slurry as well as the spray-drying conditions. Finally, U.S. Pat. No. 6,013,591 discloses a method for preparing nanocrystalline HA that involves precipitating a particulate apatite from solution having a crystallite size of less than 250 nm and a BET surface area of at least 40 m2/g. In all of the prior art methods cited above, HA was precipitated from a solution. The slurry or emulsion containing the precipitated HA was spray-dried to produce fine particles.
In the above methods described in the scientific or patent literature, the nano HA materials are formed in a solution environment, and in most cases, the product is washed with water or other solvents to remove impurity or undesired components. Exposure of the nano particles to additional solution environments is likely to result in significant interactions between the particle surfaces and the solvent, leading to modifications of the surface properties and a reduction in the high reactivity innate to the nano particles. Thus, there has persisted the need to identify methods and apparatus for the manufacture of high purity, amorphous or nearly amorphous nano particles, especially those comprised of [Ca] and [P].
Briefly, the present invention comprises methods for preparing nano particles, such as HA particles, by spray drying of a solution discharged through a nozzle in such a way that the nano particles form via in situ precipitation resulting from generally controlled evaporation of the solution in a chamber. The product formed is essentially free of undesired components or impurities such that the particles do not need to be washed. Thus, the particles need not be exposed to any solution environment and therefore will retain their original, highly reactive surfaces. By adjusting the composition of the solution, e.g., the Ca/P ratio, Na and carbonate concentrations, etc., nano HA particles of a range of Ca deficiency and substitution (Na for Ca and carbonate for phosphate) can be prepared. The spray drying methods and apparatus described hereinafter can be used to prepare not only nano HA, but also nano forms of MCPM, DCPD and/or DCPA, and OCP by appropriately formulating the solution composition which is to be sprayed to form droplets from which the liquid is evaporated.
Many compounds of biomedical interest, such as fluorapatite (FA), have very low solubilities so that a saturated solution would contain little amount of dissolved material. Other compounds, such a calcium fluoride, calcium silicate, etc., have low solubilities that do not increase significantly with increasing acid strength. As a result, the one-solution spray drying method as described hereinafter may not be as commercially useful as desired for preparing nano particles of these compounds. However, availability and use of two-liquid nozzles makes it possible to prepare nano particles of these insoluble salts because the cationic and anionic components of the salt are initially present in two separate solutions each one being dispersed from a distinct, but adjacent nozzle to enable ionic combination upon atomization in a chamber.
Thus, the invention is generically described as methods comprising preparation of nano structured materials using a spray drying technique employing a one-liquid or multiple liquid nozzles. An important feature of the inventive spray drying process comprises evaporation of the liquid from which the nano particles are derived thereby leading to in situ precipitation of HA (or another compound of interest) that is essentially free of undesired components or impurities. In this way the nano particles formed do not need to be washed and therefore not be exposed to any solution environment that could modify the particle surfaces. This process requires that the solution being sprayed contain only calcium and phosphate ions (or constituent ions of the salt to be prepared) and an acid component in water solution, if needed, to solubilize the calcium phosphate compound. The acid must preferably be sufficiently volatile so that it can be readily evaporated in the spray drying process. To achieve this, the volatile acid must preferably also be a weak acid such that no significant amounts of the acid anions, which are not volatile remain present by the end of the evaporation process. Precipitation of HA, for example, resulted from evaporation of water in the spray drying process causing a decrease in solution pH to about 4.0. This, I turn, makes the weak acid become increasingly more undissociated and therefore readily evaporated. Carbonic and acetic acids are examples of good candidates for the purpose. In the specific example of HA particle formation, HA-saturated solutions can be prepared by dissolving HA in a dilute acetic acid (for example, 17.5 mmol/L) solution (acetic acid-HA solution) or carbonic acid (266 mmol/L) solution (carbonic acid-HA solution).
Other examples of the method of the invention include formation of nano particles of other components. For example, compositions of solution to be spray dried for preparing nano particles of various calcium phosphate phases are set forth in Table 2. Because MCPM is highly soluble, the solution for the nano MCPM production can be prepared by dissolving an appropriate amount of MCPM or other sources of Ca (for example CaCO3) and P (for example H3PO4) in a solution of the desired concentration (Table 2). For the preparation of nano particles of other calcium phosphates, a volatile weak acid is used to facilitate solubilization of the calcium phosphate ions. The examples in Table 2 show acetic and carbonic acid as the volatile weak acids but other acids of similar properties could also be used. With the exception of MCPM, the amount of a calcium phosphate that can be dissolved is strongly affected by the concentration of the volatile acid. Table 2 shows examples of the solubility of various salts at two concentrations of carbonic acid or acetic acid. In general, a minimum amount of the volatile weak acid, necessary to keep the calcium and phosphate ions in the solution, is used to facilitate the removal of the acid in the spray drying process.
The spray formation and drying process in one embodiment thus comprises introduction of a solution of the compound or compounds described through a spray nozzle (nozzles) into a heated chamber where the spray particles are deliquified thereby resulting in high purity, solid, generally amorphous, nano particles collected in a precipitation. Two nozzles may be utilized for certain applications where the compounds would not otherwise adequately dissolve in a weak acid solution.
Thus, it is an object of the invention to provide methods for manufacture of nano particles of various compounds by a process which facilitates formation of high parity particles.
Another object of the invention is to provide methods for manufacture of nano particles that is efficient, and which avoids complex procedures.
A further object of the invention is to provide a method for manufacture of nano particles by spray drying techniques.
These and other objects, advantages and features of the invention will be set forth in the detailed description which follows.
In the detailed description which follows, reference will be made to the drawing comprised of the following figures:
The apparatus referring to
The nozzle utilized in the apparatus is selected to provide spray droplets of minimum size. Thus, the nozzle preferably has a diameter of the nozzle outlet passage in the range of about 12 to 15 microns for the compounds tested. The temperature in the dehydration chamber is typically in the range of 100� C. to about 200� C. without dissociation or adverse impact upon the formed particles. On the other hand, materials such as DCPA and DCPD are dehydrated at a temperature adequately under 200� C. to avoid dissociation or other adverse effects upon the formed particles. Of course, the flow rate of the clean air into the system will affect temperature in the forming chamber. The air may or may not be preheated.
The size and shape of the evaporation chamber will also comprise a factor affecting air flow rates, temperature and evaporation. An arrangement which avoids spray condensing or collecting on the chamber walls is highly preferred. The pH of the acid solution is also preferably controlled for reasons noted previously and preferably is about 4.0 or less. Of course, as the liquid evaporates to leave the powder particles, the effective pH increases. A weak acid is desired to preclude inclusion of acid based artifacts in the formed particles.
Characterization of the Nano Particles
XRD (Rigaku DMAX 2200, Rigaku Denki Co. Ltd. The Woodlands, Tex.) was used to determine the crystalline phases present in the formed nano particle product. Scans were performed between 10�<2θ<50�. The estimated standard uncertainty of the 2θ measurement is 0.01� and the mass fraction of a crystalline phase to be detected by XRD is about 3%. It was anticipated that the product will contain primarily amorphous materials and the location and the intensity of the broad peak were noted.
A ThermoNicolet NEXUS 670 FT-1R spectrometer (Thermo Nicolet, Madison, Wis.) was used to record the infrared spectra of the nano powders. The formed nano particle powders were mixed with IIR quality KBr at a mass ratio of =1:400 and finely ground in a mortar and pestle.
The misture was then pressed into a pellet in a 13 mm diameter evacuated die. The sample KBr pellet to cancel the impurity bands. The absorbance spectra were acquired over the range of 400 cm−1-4000 cm−1 using a DTGS detector and KBr beam splitter, with a resolution of 2 cm−1. Each spectrum was scanned 32 times to increase the signal-to-noise ratio. The estimated standard uncertainty of wavelength was �4 cm−1.
Multipoint Brunauer-Emmett-Teller (BET) surface area analyses were done (Gemini 2375 Surface Area Analyzer, Micromeritics, Norcross, Ga.) with ultra high purity nitrogen as the adsorbate gas and liquid nitrogen as the cryogen. The pressure sequence was (0.05, 0.10, 0.15, 0.20, 0.25) P/Po and the evacuation time was three minutes. The analysis mode was equilibration with the equilibration time of 5 s. The samples were dried in air overnight at 110� C. (Micromeritics Flow Prep station) before the measurement. Analyses were conducted on replicate samples to established standard deviation. In this and other measurements in the present study, the standard deviation was taken as the standard uncertainty.
A TA Q500 thermo gravimetric analyzer (TA Instruments—Waters LLC, New Castle, Del.) was used to determine the weight loss of the nano powder sample with the increase of temperature. The temperature range was from 25� C. to 950� C., and the heating rate was 10� C./min. Estimated standard uncertainty of temperature calibration was �5� C.
Samples of the nano materials were analyzed for calcium (Ca) and phosphate (P) by spectrophotometric methods and carbon (C) by combusting the sample at 1000� C. in a constant oxygen flow and detecting the carbon dioxide by infrared absorption using a LECO CHN 000 Analyzer (St. Joseph, Mich.) [35,36]. This information was used in conjunction with FTIR data to estimate the chemical composition of the nano samples.
Transmission electron microscopy (TEM) was used in characterizing the particles. For this purpose, particles were deposited onto Cu grids, which support a "holey" carbon film. The particles were deposited onto the support grids by deposition from a dilute suspension in acetone or ethanol. The particle shapes and sizes were characterized by diffraction (amplitude) contrast and, for crystalline materials, by high resolution electron microscope (JEOL, Peabody, Mass.), equipped with a Gatan Image Filter (with parallel EELS) and a light element EDS system.
The transient nature of the dissolution behavior of HA was taken into consideration when conducting the solubility measurements as follows. The solubility experiments were conducted by dissolving the nano HA sample in solutions pre-saturated with crystalline HA at pH (5.0, 5.5, and 6.0). Based on calculations using a commercially available software "Chemist" (MicroMath, Salt Lake City, Utah), the solutions were prepared by equilibrating crystalline HA in 8.1 mmol/L, 2.7 mmol/L, and 0.92 mmol/L phosphoric acid solutions, that also contained 150 mmol/L KNO, as an electrolyte background, until saturation followed by filtration. In each solubility measurement conducted at (21�1) � C., a pre-calibrated combination pH electrode [60110B, Extech Instruments Co., Waltham, Mass.] and a Ca-ion specific electrode [Orion 97-20 Ion Plus, Thermo Electron Co., Woburn, Mass.] were placed in 100 mL of a HA-saturated solution under constant stirring (52.4 rad/s or 500 rpm), and stable electrode readings were recorded ever 10 s, 5 mL of the equilibrating slurry was removed at (1, 2, 3, 4, 5 and 10) min and immediately filtered for analysis of [Ca] and [P] concentrations using spectrophotometric methods [34]. The pH, [Ca], and [P] values were used to calculate solution ion activity products (IAP) with respect to HA [Eq. (1)] and other calcium phosphate phases using the software "Chemist"
Once brushed off the precipitator plates, the nano HA had the form of a white fine powder. Powder X-ray diffraction (XRD) patterns showed that the material was amorphous (
Fourier transformed infrared (FTIR) analyses of the samples showed a pattern indicative of HA with the presence of some acid phosphate (874 cm−1, 1356 cm−1, 1389 cm−1), absorbed water, and acetate (670 cm−1, 1417 cm−1, 1462 cm−1, 1568 cm−1).
Elemental analysis showed that the materials had a carbon content of 5.79% mass fraction (5.79%) from acetate residue. Because calcium acetate is quite soluble and this may mask the true solubility of the nano HA, solubility measurements were not performed on this material.
The nano HA particles were used as seeds to determine whether the setting time of a calcium phosphate cement (CPC) could be reduced. Cement hardening or setting time was measured with a Gilmore needle apparatus using a heavy Gilmore needle (453.5 g load, 1.06 mm diameter). The sample was considered set when the needle fails to leave a visible indentation when placed over the surface of the cement. Two CPC mixtures were prepared. The control CPC consisted of equimolar amounts of TTCP (72.9%) and DCPA (27.1%), and the experimental CPC was a mixture that consisted of 95% control CPC and 5% nano HA seeds. The setting times of the control and experimental CPCs were 30�1 min (n=2) and 12�1 min, respectively. These results showed that the nano HA produced dramatic effects on the TTPC+DCPA cement setting times. Because of the similarities in setting reaction mechanism, the nano particles of calcium phosphate materials are expected to produce similar effects on setting times of CPCs of different compositions.
Properties of Nano HA Prepared from a Carbonic Acid-HA Solution.
The sample was a white powder. XRD patterns showed that the material was amorphous (
FTIR showed the pattern of amorphous calcium phosphate with the presence of some acid phosphate (870 cm−1), adsorbed water (3407 cm−1), molecular water (16435 cm−1), and a large amount of trapped CO2 (2342 cm−1) as well as some carbonate incorporation in the structure (870 cm−1, 1422 cm−1, and 1499 cm−1). Elemental carbon analysis showed the material also contained 9.1 percent mass fraction (9.1%) of carbon.
Solubility experiments were conducted by dissolving the nano HA in a solution presaturated with well crystalline HA. The HA-presaturated solution was prepared by equilibrating crystalline HA in a 0.92 mmol/L phosphoric acid solution that also contained 150 mmol/L KNO3 as an electrolyte background until saturation followed by filtration. The solution had [CA] and [P] concentrations of 0.75 mmol/L and 1.22 mmol/L, respectively, and a pH of 6.07. Dissolution experiment results showed that both the [Ca] and [P] concentrations as well as the pH increased rapidly with time (
Thermal gravimetric analysis (TGA) showed that sample mass losses occurred at (60 to 120)� C., (210 to 380) � C., (440 to 580) � C. and (650 to 750) � C. Most of the trapped CO2 was lost after being held for one hour in vacuum at 600� C. (
The solubility results showed that in each dissolution experiment, the [Ca] and [P] concentrations as well as the pH increased rapidly with time. This indicated that the nano-HA was much more soluble than the crystalline HA. For dissolution experiments conducted with pH 5.0 and pH 5.5 HA-presaturated solutions, rapid increases in [Ca] and [P] were followed by gradual decreases in these concentrations starting at about 2 min., while the pH continued to increase. This observation suggested that a less soluble HA phase began to precipitate as the nano HA continued to dissolve. The calculated PiAP(HA)=−log [IAP(HA)] (see Eq. (1) for IAP definition) values were (mean�standard deviation; n=2) 99.7�0.2, 97.2�0.4 and 93.5�0.3, respectively, for data obtained from dissolution experiments with HA-presaturated solutions having pH 5.0, 5.5 and 6.0. The smaller IAP values (more positive pIAP values), observed at the lower pHs probably was, in part, a result of the simultaneous dissolution-precipitation phenomenon.
More specifically, HA prepared from carbonic acid would likely be more soluble than crystalline HA, both because of its small particle size and CO2 content. An IAP(HA) value as high as 3.3�10−94 (pIAP=93.6), compared to 1�10−117 for crystalline HA, was obtained from experiments in which the nano HA was dissolved in the pH 6 HA-presaturated solution. In this dissolution run, the [Ca] concentration increased from the initial value of (0.75�0.01) mmol/L in the crystalline HA-presaturated solution to a near a plateau value of (4.5�0.2) mmol/L at 10 min when the experiment ended. The [P] concentration similarly increased from the initial value of (1.2�0.1) mmol/L to a stable value of (3.5�0.2) mmol/L at 5 min. The pH of the solution continued to increase and reached 7.03�0.01 at 10 min. Dissolution of the same nano HA into the pH 5 HA-presaturated solution led to initial increases in [Ca] and [P] concentrations as in the pH 6 experiment. However, the initial increases were followed by continued decreases in these concentrations beginning at about 2 min to levels that were below the starting [Ca] and [P] concentrations. These results suggested that addition of nano HA to a pH 5 HA-saturaed solution led to sustained precipitation of crystalline HA. Such a process might be useful for remineralizing dental carious lesions or for occluding open dentinal tubules as a treatment for dental hypersensitivity.
Both nano HA samples, prepared with acetic acid and carbonic acid, appeared amorphous in SRD, but the former HA was crystalline as revealed by high resolution TEM despite the extremely small particle sizes of 5 nm to 10 nm. It is noted that this sample for the high resolution TEM analysis was suspended in ethanol for 2 days and there is a possibility that a phase transformation may have occurred during this period. However, under similar sample handle conditions, the carbonic acid derived nano HA remained amorphous under TEM analysis. Because the acetic acid- and carbonic acid-HA solutions had identical [CA] and [P] concentrations and the spray drying processing conditions were essentially the same, the differences in crystallinity of the nano HA samples prepared from the two solutions may be attributable to factors related to the nature of the acids.
Process Comparison
As described above, by using a minimal amount of a volatile weak acid to prepare the spray drying solutions, the process is capable of producing HA materials that contain little or no impurity components. In practice, a fair amount of acetate was found in the nano HA sample prepared with the acetic acid-HA saturated spray drying solution, and a large amount of trapped CO2 was present in the nano HA prepared with the carbonic acid-HA saturated solution. The amount of residual acid components in the spray dried product could be reduced by using a more dilute solution, i.e., with lower [Ca] and [P] concentrations, because a smaller amount of acid would be required to prepare the solution. A complication with HA preparation in general is that HA has a high "affinity" for carbonate. Carbonate is readily incorporated into the HA structure in conventional HA preparation processes unless measures are taken to exclude CO2 from the system. Because HA is the most alkaline salt among all calcium phosphates that can be prepared in an aqueous system, a larger amount of acid is needed to prepare HA saturated solutions compared to saturated solutions of the other calcium phosphates. Consequently, the residual acid problem is most pronounced in the HA preparation. Preliminary data indicates that no residual acid was present in dicalcium phosphate dihydrate nano particles prepared by this process. These observations indicate that the spray drying technique should be useful for preparing nano particles of a range of calcium phosphate phases with minimum impurities.
Multiple Nozzle Techniques
Many compounds of significant biomedical of industrial interests have low solubilities under all pH conditions. As a result, the spray drying technique described above using a one liquid nozzle is not useful because it is impossible to prepare a solution that contains a significant amount of dissolved mass of the salt. Availability of a two liquid nozzle makes it possible to prepared nano particles of these compounds because the cationic and anionic components of the salt are present in separate solutions that are combined only at the time of spraying. Nozzles that can simultaneously spray than two liquids can be constructed following the same principle as that for the single liquid nozzle. Thus, the spray drying process described here can be used for multi-liquid systems when needed to keep incompatible components in separate liquids, which are mixed at the time of atomization and spray drying.
The compositions of the solutions to be spray dried for preparing nano particles of several compounds are given in Table 3. It is noted that in some cases, such as in the preparation of F-substituted apatites, solution 1 will contain (Ca(OH)2 and solution 2 will contain H3PO4 and HF. Upon mixing and spray drying the two solutions, only water needs to be evaporated to produce FA or a F-substituted apatite. In other cases, an acid (or a base) is needed to solubilize the cationic (or anionic) component, and the acid will also need to be evaporated during the spray drying process. An example for this is the preparation of calcium silicate hydrate (CSH). Because SiO2 is insoluble in acid but is slightly soluble in concentrated alkaline, amorphous SiO2 is dissolved in a NH4OH solution, and NH3 will be evaporated together with water during the spray drying process.
The spray drying apparatus (
Results of Example of Two Nozzle Spray Method
Nano particles of CaF2 was prepared by spray drying a 10 mmol/L Ca(OH)2 solution and a 20 mmol/L ammonium fluoride (NH4F) solution that were combined at the time of atomization. XRD analysis (
Preparation and Properties of Nano Calcium Fluroide, CaF2, Particles Using a Spray Drying Method Employing a 2-Liquid Nozzle
A 2 mmol/L Ca(OH)2 solution and a 4 mmol/L ammonium fluoride (NH4F) solution were atomized and spray dried. Mixing of the Ca(OH)2 and NH4F) solutions led to formation of CaF2 and NH4OH; the latter was removed as NH3 gas in the drying process. The CaF2 nano particles were collected by the electrostatic precipitator as described before. XRD analysis showed crystalline CaF2 with trace amount of DCPD also present due to contaminations from the precipitator plates. SEM examinations indicated that particles ranged from <50 nm to about 500 nm in size. The larger particles exhibited numerous spherical protuberances on the surfaces, suggesting that they were formed during the spray drying process through fusion of the much smaller particles. This suggests that well dispersed small particles could be produced by using a much lower spray rate. Chemical reactivity of the nano CaF2 was evaluated by stirring (300 rpm) 33 mg of the nano CaF2 in a 30 mL of a solution pre-saturated with crystalline CaF2. Specific ion electrodes for Ca and F and a combination pH electrode monitored the changes in [Ca] and [F] concentrations and pH. The results showed that both the [Ca] and [F] concentrations increased nearly by a factor of 2 and the solubility product (Ksp_ of the nano CaF2 was (2.3�0.2)�10−10 which is about 6 times greater than the Ksp of value of 3.9�10−11 for crystalline CaF2. These results indicated that the nano CaF2 is significantly more reactive than macro CaF2.
In another test, mixtures containing a macro (median size 1.6 μm) DCPD and either the nano CaF2 or a macro CaF2 were mixed with water (1 g/1 mL) and the pastes were left in 100% humidity at 37� C. for 24 h. XRD patterns showed that there was no reduction in the amount of the macro CaF2 whereas the nano CaF2 was partially consumed by reacting with the DCPD forming a larger amount of apatitic product. DCPD was nearly completely consumed in either mixture. These results showed the nano CaF2 was more reactive than the macro CaF2. It also indicated that the nano CaF2 was not as reactive as the macro DCPD, suggesting that it would be necessary to use even smaller nano CaF2 particles in order to have the CaF2 dissolve in time for the reaction.
A Filter Paper Model for Evaluation of Fluoride Deposition by a Nano CaF2 Prepared by the Spray Drying Method
The ability of the nano CaF2 to be attached to tooth and other oral substrate surfaces was evaluated in vitro using a filter disc model. Five filter discs (Millipore, Bedford, Mass.) with a pore size of 0.2 μm and pore volume of 75% were placed in 20 mL of a nano CaF2− water suspension or a NaF solution (250 ppm total F in either case). After 1 min of exposure, the filters were rinsed twice in 50 mL of a solution saturated with respect to CaF2 to remove particles that were not firmly attached on/in the disc or remove unreacted F ions. Firmly fixed CaF2 particles would not be lost to the washing solution by dissolution because the solution was presaturated with respect to CaF2. The F content in each disc was them determined by a F ion selective electrode method. F deposition on samples immersed in the nano CaF2 suspension was 2.3�0.3 μg/cm2 of surface area (n=5) which was significantly 9p<0.001) greater than that (0.31�0.06 μg/cm2) produced by the NaF solution. These results showed that the nano CaF2 particles were able to penetrate into the pores and fixed onto the substrate. Previous studies have shown a good correlation between the F deposition on the filter disc substrate and that on sound enamel. Thus, the results suggest that the nano CaF2 suspension should be more effective than the currently used NaF solution for increasing oral F level.
Effect of a Nano CaF2 Oral Rinse on Salivary F Levels
This study evaluated the effects of an oral rinse with the nano CaF2− water suspension used in the above experiment on salivary F levels. Five subjects (1 hour without food or drink) rinsed for 1 min 20 mL of a nano CaF2− water suspension (10.3 mg CaF2 in 20 mL, 250 ppm total F) or a control F rinse (250 ppm F from NaF) and expectorated the rinse. Saliva sample was collected 1 hour post rinse and analyzed for F significantly (p=0.004, a log-transformation was performed to obtain normally distributed samples) higher F level (158 μg/mL) compared to that produced by the control rinse (36 μg/mL). This observation suggests that the nano CaF2 rinse should be significantly more effective than the currently used F regimens. Because the nano CaF2 material used in this study had a wide range of particle sizes (from <50 nm to about 500 nm), it is likely that an even more effective rinse could be developed by using nano CaF2 with an optimal particle size distribution.
Summary of Factors Affecting Methods of Particle Formation
The methods disclosed in the invention are useful for preparing nano particles of any compound that can be formed by precipitation from an aqueous solution. The temperature under which the spray during process occurs is controllable by controlling the inlet air temperature and the temperature of the column (
The inventive method is suitable for preparing particles from 1 nm to 100 μm in size.
The particle size can be controlled by (1) the concentration of the compound in the solution to be spray dried, (2) size of the atomized droplets, i.e., nozzle design. Droplet size is preferably less than the final particle size and thus less than about 100 μm. Chamber design is also a factor. The chamber is generally designed to minimize collection of condensate i.e., liquid from on the chamber walls.
The nature and composition of the compound that will be formed will depend on the solution composition. In many cases, the solution pH is the most important factor because, for calcium phosphates and other compounds that are salts of weak acids, it is the pH that determines the solid phase that would precipitate as the water evaporates from the solution.
The purity of the compound prepared, i.e., being free from undesired components, is dependent on the ability of spray drying process to remove the acid or base used to dissolve the compound in the spray drying solution. The acid/base must be a weak acid/base so that a substantial portion of the acid/base is in undissociated form, and the acid/base is almost totally undissociated as the last portion of the liquid is evaporated. The undissociated acid/base must also be sufficiently volatile to facilitate evaporation of the acid/base.
The nano particles prepared by the methods disclosed in the invention are useful in any application in which the compound is currently useful but a performance advantage can be gained by having a higher reactivity and/or smaller particle size. Examples of this include (1) accelerated hardening of calcium phosphate cements when one or more calcium phosphate nano particles are included in the ingredients, (2) accelerated hardening of mineral trioxide aggregate (MTA) when one or more calcium silicate nano particles are included in the ingredients, (3) desensitization of teeth by effective obturation of exposed dentin tubule opening with calcium phosphate nano particles, (4) deposition of fluoride in/on oral tissue by application of agents that contain calcium fluoride or other fluoride nano particles. (5) as a source of calcium, phosphate, or fluoride in remineralizing dentifrices, gels, rinses, chewing gums, and candies; and (6) as a source of calcium, phosphate, or fluoride for formulating scaffolds for bone defects repair.
Thus, examples of compounds of biomedical interests that can be prepared by the spray drying method:
Examples are the monobasic, dibasic and tribasic phosphate salts of sodium, potassium, and ammonium.
While various techniques and apparatus have been described with particularity the invention is subject to variations and this is to be limited only by the following claims and equivalents thereof.
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This be that murder business, little Timmy got that semi
Lyric Meaning
"Little Timmy" is a term used in video games meaning a young player. Now that Rocky made it in the major league (with LiveLoveA$AP and now his first solo LP), Little Timmy is a big player. He got his gun (album) in this murder business (rap game), he'll come to your house and would even kill your children (your children will love his music and play it in the house), and he even has a crew of goons with him to kill everybody (the A$AP Mob).
This could also be a nod to the song Murda Bizness by Iggy Azalea (featuring T.I.), the rapper who he was rumored to have relations with.
Lupe Fiasco had a similar Little Timmy character in "Little Weapon"
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Leaves branch out behind the ear, held into place by a rose stud. Sold as pairs. Available in sterling silver with bronze leaves or bronze with sterling silver leaves.
20.8 mm x 12.5 mm
Please note that the silver roses with bronze leaves are pre-order pieces that will ship in 10-12 weeks.


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Do I Really Need a Lawyer if My Divorce Is Uncontested?
You may begin your divorce amicably, thinking that you and your spouse agree on everything. That's right, everything. It is natural to ask, "Does either of us really need a lawyer?" The short answer is that unless you truly have an uncontested divorce, you need a lawyer.
What Is an Uncontested Divorce?
To file an uncontested divorce, you and your spouse must agree on all issues — children, property, money and support. If you do disagree on even one issue, then you will have to file for a contested divorce. The process in an uncontested divorce is relatively quick and easy. Each party completes a financial statement and submits a joint petition for divorce, listing the terms of their agreement. The decree and petition are then filed, and the divorce will soon be finalized by the court.. Your only interaction with the court may be to answer a few questions from the judge to make sure that both parties understand the terms of their agreement.
It sounds simple, but once you disagree on anything, it's time to call a lawyer. At Pollack Law Group, P.C., our attorneys have years of experience handling all types of divorce cases and can advise you about your options. If we believe that you do not need an attorney for your divorce, we will tell you. Call us today at 800-299-DIVORCE (800-299-3486) or contact us online to schedule your free initial consultation.
Why You Need an Attorney for Most Divorces
Many people think that they can take care of an uncontested divorce by themselves, but they do not know what they are getting themselves into. Whenever a divorcing couple says, "We don't need lawyers," there's a reason our attorneys become wary. When one of the spouses is self-employed, has a high net worth or is not as financially savvy as the other spouse, "wary" turns to downright suspicious. With more than 100 years of combined experience, our attorneys have seen the same scenario play out over and over again: the more financially savvy spouse doesn't want attorneys or accountants involved so he or she can gain the financial advantage without his or her scheme being discovered.
Making a mistake during an uncontested divorce can cost both of you money, sometimes a significant amount of money. An attorney can identify issues and concerns you may not have thought about and help protect you from having your divorce become costly.
Divorce Services That Make the Cost Reasonable
At Pollack Law Group, P.C., we offer flat-fee divorce services so clients can keep expenses down and know from the start how much the process will cost. This approach allows you to have the benefit of an attorney, but gives you the chance to do some of the work yourself so you can control legal fees.
Straight Answers to Your Questions About Flat-Fee Divorce
Even if you are confident you can complete the process without hiring an attorney, it is good common sense to have your questions answered by a knowledgeable, experienced lawyer. It is worth arranging a consultation with an attorney at Pollack Law Group, P.C. We won't try to talk you into hiring us. We'll give you straight answers to any questions you may have
Contact Us for Information on Uncontested and Flat-Fee Divorce
If you need assistance filing for an uncontested divorce, our attorneys can help you through this process quickly and efficiently. Our Massachusetts law firm serves clients throughout the state, from Cape Cod to Pittsfield. Contact us at 800-299-DIVORCE (800-299-3486) to learn how we can help you with any family law matter such as divorce, child custody or spousal support. We offer a free, no-obligation consultation with an experienced flat-fee divorce attorney.


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by Laura Hutson
Scott Schuman — the photographer responsible for making an antiquated word like "sartorial" sound cool somehow — visited Nashville on his recent book tour, and we had a suspicion that he had something besides just signing autographs up his finely tailored sleeve. A handful of street style shots from Nashville have been popping up on The Sartorialist since his visit, and we hope there will be more to come. If these shots say anything about what stands out to a sophisticated eye like Schuman's in our city, it's this: Style is uncomplicated, lived-in, confident.


text:
By Mark Hayes
SATB choir, piano accompaniment (with optional orchestration)
Composed by Mark Hayes. Concert. Octavo. Published by Heritage Music Press (LO.15-2239H).
Item Number: LO.15-2239H
Originally written for the International Children's Choir Festival in Canterbury, England, this piece is perfect for all ages. The text speaks of imagination, creativity and possibility. It encourages the singer to live life to the fullest with declarative statements such as I am hope, I am love, I am a servant, I am peace. Its lightly rhythmic melody flows and soars, and the piece ends quietly with the reflective affirmation, I am peace.


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In their ignorance some think they do not desire God unless they are always calling him with the words of their mouth or else by words of desire in their hearts, as if I were to say, 'Ah, Lord, bring me to your bliss', 'Lord save me', or something of this kind. These words are good whether sounded in the mouth or formed in the heart, for they stir a man's heart to the desire of God. Nevertheless, a pure but wordless thought of God or of any spiritual thing — virtues, the manhood of Christ, the joys of heaven, or the understanding of holy scripture — may, with love, be better than any such words. For a pure thought of God is a true desire for him, and the more spiritual your thought is, the greater your desire; therefore when you pray or think about God or do any outward deed for your fellow Christian, be in no doubt or perplexity as to whether you desire God or not, for the action shows it.
— Walter Hilton (1340-1396), The Mixed Life


text: David L. Grange is a retired United States Army Major General. He served with the 101st Airborne during the Vietnam War. He was later assigned to Delta Force, commanding a squadron during the invasion of Grenada and was deputy commander during the Gulf War. His last command was of 1st Infantry Division before he retired in 1999.


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Originally written on That NBA Lottery Pick | Last updated 9/21/13
A couple of hours ago, Brooklyn Nets forward Paul Pierce sent out a Twitter message that might have been meant to be a text message. Check out the below tweet where Pierce asks an unknown individual to stop texting him at a certain number: Stop texting this number — Paul Pierce (@paulpierce34) September 21, 2013 So, who was this text meant for? Unless Pierce tells us, I guess we'll never know. *** Paul Piece image courtesy of Getty Images
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44 year old woman | Whittier, CA, USA | Seeking men 37-45 within 50 miles
I'm ready.
It doesn't take much to make me happy. I take pleasure in the simple things in life, like a beautiful sunset, good conversation, great food, spending time with my daughter and friends. I am a multifaceted person that likes to live life passionately. While I love to engage in stimulating conversations and political discussions, I can't forget about my goofy side. In short, I am not too much of anything but a little of everything.
Book club , Camping , Coffee and conversation , Cooking , Dining out , Fishing/Hunting , Gardening/Landscaping , Hobbies and crafts , Movies/Videos , Museums and art , Music and concerts , Exploring new areas , Nightclubs/Dancing , Performing arts , Political interests , Shopping/Antiques , Travel/Sightseeing , Volunteering , Wine tasting
Basketball, Billiards / Pool, Dancing, Running, Soccer, Walking / Hiking
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I have Dogs
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University of California, Santa Barbara, Santa Barbara, CA
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I like to spend time with friends either traveling or finding a local hang out. I have a pretty eclectic taste in music, (anything except country). :)
I am currently reading Law of Success by Napoleon Hill, I am enjoying it so far
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text:
Brixham Sailing Trawlers
The story of the development of the legendary Brixham sailing trawler
SAILING TRAWLERS A DEVON FISHING VILLAGE, THE CREATION OF A LEGENDARY WORKING VESSEL AND THE BIRTH OF A GLOBAL INDUSTRY In the beginning there was the Wondyrchoum Trawling is a method of fishing by towing a net, suspended from a crossbar, across the sea bed. It had its origins in medieval times, and was a development of the dredge used to catch oysters. In its original form the trawl was called the wondyrchoum. It was a net in The first reference to it is in 1376, when in the reign of Edward III a petition the form of a bag 18 feet long and 10 feet wide, nailed to a cross beam, and with frames at either end which kept the beam above the level of the sea bed. it was causing to fish stocks. was presented to Parliament calling for it to be banned because of the damage were using so fine a mesh that "no manner of fish, however small, entering The problem was that the fishermen who were using this new development within it can pass out" so that the fishermen "take so great abundance of small of the fisheries." the great damage of the whole commons of the kingdom and the destruction wondyrchoum was used only in "creeks and havens" (i.e. natural harbours), not in deep waters, and the damage was being done to spawn and young fish, and endangering the breeding grounds. But because the sailing vessels of the time were not very powerful the fish that they know not what to do with them but feed them to their pigs, to H A M A ND T HE LEG ENDRY SA N ILI G TRAWLER S SAILING TRAWLERS IX BR Introduction Around 200 years ago a revolution began in the small South Devon fishing village of Brixham at the southern end of Tor Bay. "Sailing trawlers and Gullsâ€? by Arthur Briscoe It was a revolution that was to bring profound changes to seagoing communities around the coast of Britain. It spread to Europe and over time became global. It would create an immense new industry, employing hundreds of thousands of people directly and indirectly; one that still exists today was trawling. many other places are still centred. That industry and around which communities in Brixham and method of fishing that for centuries had been carried out in estuaries, creeks and harbours to be deployed in deep waters, far offshore. That vessel was the sailing trawler - the Brixham sailing trawler. It began with the development of a type of sailing vessel which enabled a Sailing trawlers once existed in their thousands. Now only a handful remain. Brixham...Trawling... the Sailing Trawler - this is their story SAILING TRAWLERS 1 The birth of an industry Nobody knows for certain just when deep-sea trawling began, but certainly by the late 18th century the fishermen of Brixham, keen to overcome the problem of limited fish stocks in South Devon waters, had begun to develop a new design of fishing vessel. Its sleek underwater lines and very tall gaff rig gave it the speed to make long passages to and from the fishing grounds in relatively short times. The power that gave them that speed also enabled them to tow large trawls, in deep water and in all kinds of weather. described as a quantum leap forward. The result was a great increase in the size of the catch, and a corresponding decrease in the time taken to make that catch. Nowadays it would be knew that what they had developed gave them a major advantage and they were sufficiently entrepreneurial by nature to exploit it. limited. It was not long before they began to go further and further afield to fish. Smith, said he had been fishing off Dover since before the French Revolution of 1789 "the first from Tor Bay to go so far east". However he also said that by and Hartlepool and all round the coast." the 1830's he "had fished from Sunderland, Durham Channel and the Irish Sea. From there they could Meanwhile others had gone west, to the Bristol Giving evidence to a parliamentary enquiry in 1833 one of them, Walter Fishing stocks in the English Channel were now more accessible, but were still The men from Tor Bay did not describe it in terms of that kind, but they make a fast run home with their catch, using the prevailing westerlies. The fastest of them all, Ibex, once made the 140 miles passage from the Bristol BM346 "Guess Again" under full sail Channel to Brixham between 5 o'clock one afternoon and 8 o'clock the following morning, at an average speed of almost ten knots. SAILING TRAWLERS 2 part of the year but in due course inevitably led to some settling there permanently. However, fishing in more distant waters meant living locally, initially for only Two of these pioneers were Robert Hellyer and his son Charles, who left Brixham in 1854 and settled in Hull. Like nearby Grimsby, and other ports such of the North Sea led to a Klondike-like stampede of Brixham men. comprised of some of the largest sailing trawlers ever built. the new fishing ports that had sprung up as fresh grounds Fleetwood and Dublin. were discovered and opened up: places like Ramsgate, as Lowestoft and Great Yarmouth, Hull had no previous history of deep sea The Hellyers, and many others, had their boats built back home in Devon. fishing, but the discovery of astonishingly rich fishing grounds in the central part They became two of the most successful fishing entrepreneurs, owning a fleet But over time many vessels began being built locally to the Brixham lines in Lowestoft, Great Yarmouth, Hull, Grimsby, Scarborough, 19th century there were more than 3,000 sailing trawlers Numbers grew steadily, and by the latter years of the in commission in UK waters. At the end of the 19th century, there were more than 3,000 sailing trawlers in UK waters Brixham harbour, 1870s SAILING TRAWLERS 3 but 375 at Lowestoft, 450 at Hull, 625 at Great Yarmouth and numbers at other places. Fleet drying out, Brixham 1868 There were 200 at Brixham, 840 at Grimsby, with smaller eagerly snapped up secondhand Northern Europe, from Holland to Scandinavia and the Faroe Islands. The Germans ordered twelve as the nucleus for a home-built fleet. A major new industry had been born. by fishermen along the coast of British-built trawlers were which were able to transport fish from landing place to markets in distant towns in a matter of hours. That also coincided with a population explosion, which in turn led to a major increase in the demand for fish. ubiquitous fish and chip shop. Fishmongers now appeared in every High Street - as did the now The rise of the sailing trawler coincided with the coming of steam railways, Lowestoft harbour 4 SAILING TRAWLERS Long-lining Like fishermen elsewhere the men of Tor Bay originally used a technique known as long-lining for deep sea fishing. As its name suggests, long-lining involved towing a long line through By the 19th century in the North Sea a complete set or "string" the water, with baited hooks suspended from it at regular intervals. consisted of 180 lines (each 240 feet long) daisy-chained together, with carried 4,680 hooks, each of which had to be baited with a whelk. used up annually. hooks every nine feet. That meant the string was eight miles long and Whelks were big business. Around 150,000 baskets of them were This was a laborious and inefficient way to farm the sea and make a living. But help was at hand.The sailing trawler had arrived and the days of hooks and whelks were numbered. BM321 "Terminist" being launched, 1912 SAILING TRAWLERS 5 The Sailing Trawler There were several important features that combined to make the sailing trawler ideal for the role. G Strength Of these three were pre-eminent: G Seaworthiness G Power and speed strong double-skinned hull planking. A typical large trawler would have pairs of frames. The strength came from the marrying of solid oak framing to massively six-inch oak frames (also known as futtocks) bolted together, then a gap of one foot before the next pair. In other words, half of the length of the hull was Trawler under construction on Breakwater Beach, 1899 the planking. On the biggest trawlers that was three inches thick on the outside and two inches thick on the inside. the bow (trading ships had keels that were parallel to the deck, so they could 6 SAILING TRAWLERS Yet it was said that the shape came from the frames but the strength from Seaworthiness came from a straight stem and long keel, deeper aft than at if necessary settle on the ground to load and unload). The draught was deep careful ballasting produced a comfortable motion that resulted in a safe working platform and helped prolong the life of gear. what has been described as "cod's head and mackerel tail", bulbous forward act between a dry boat (lines not too fine) and excessive pitching in bad by the streamlined underwater shape that also gave directional stability. great advantage the sailing trawler had was the flexibility of conditions. Speed came from a shape that was derived from earlier fishing craft with to reduce leeway. A comparatively narrow hull in relation to its length plus and narrowing aft. The sailing trawler had finer sections forward - a balancing weather (not too full).That was allied to a tall and powerful gaff rig, and assisted The greatest power came from the mainsail, but one sail plan, which allowed the amount of sail set to be adjusted by just two or three people to fit changing The flexible sail plan could be adjusted by two or three people to meet changing conditions about 65 feet length on deck. The advent of steam donkey engines around 1860, enabling even larger trawls to be towed and larger mainsails to be set, aft of the time a mizzen mast was added boats three were led to an increase to around 80 feet in length for the largest boats. At the same The first sailing trawlers were cutter-rigged, with a single mast, and up to mainmast, and so these rigged. ketch They could set up to headsails mainsail, mizzen, topsail, mizzen topsail and even, all. when not fishing, a mizzen staysail ... eight in plus "Leader" on slipway, present day, revealing underwater lines. SAILING TRAWLERS 7 tow a heavy trawl over the sea bed in a wide range of weather and sea the boat when towing it under extreme load. The hull shape and rig gave the sailing trawler the ability to stay at work and conditions. A buoyant stern counteracted the tendency of the trawl to swamp wings with which to get her catch to market in prime condition. Those same factors, once the catch was on board, gave the trawler the So successful was the design, and so financially economical the method, that although steam power had been around for a hundred years, trawling under sail continued in Britain up to the outbreak of World War II. The last sailing trawler was built in Brixham in 1926. The photograph on this page and page The Brixham fleet in the 1930s 35 bear witness to the survival of a sizeable fleet at Brixham in those days. proximity to the coalfields of Yorkshire and the North-East. In the North Sea the transition to steam came earlier because of the Spars 1 Mainmast 2 Mizzen mast 3 Topmast 4 Booms 5 Gaffs 6 Bowsprit Sails 7 Mainsail 8 Mizzen 9 Staysail 10 Jib 11 Flying jib 12 Topsail The rig 8 SAILING TRAWLERS Construction details 4 2 7 5 9 10 1 3 4 10 15 20 Original layout 6 8 10 0 5 1 2 3 Spare rope and gear Crew cabin Galley 4 5 6 Fish hold Ice box Trawl gear 7 8 9 10 Spares bridles and blocks Spare net Sails Small sails SAILING TRAWLERS 9 Fishing Under Sail Trawler skippers used to make their way to fishing grounds by a mixture of: G Pilotage i.e. using landmarks G Course steered and distance run type of bottom (sand, mud etc) G Soundings, with lead line armed with tallow, that gave depth of water and G Colour of sea and type of waves a straight course, which was easier to accomplish with the wind abaft the beam.They would shoot the trawl shortly after the turn of the tide and fish for 5-6 hours until the tide turned again. each end that kept the upper side of the net off the ground.The net was a bag double the beam in length, plus a narrow section at its end, called the 'cod', in which the fish collected. The trawl would be laid along the port side of the boat with the net The trawl beam might be up to 50 feet in length, with an iron trawl head at Once on station they would aim to fish down-tide over smooth ground on inboard. Then the net would the streamed, the trawl squared away and Smacks getting under way and outward bound at Brixham 1868 10 SAILING TRAWLERS lowered. The warp to which it was attached would be up to long. 150 fathoms (300 metres) downwind and downtide, but open. It had to maintain a around two knots with the the trawl. The trawler would fish faster than the tide in order to keep the mouth of the net speed over the ground of trawl down, equivalent to seven or eight knots without tide changed, the trawl would a reciprocal course. 25-30 mph). After six hours, when the A rare photograph of a sailing trawler at work. The drag from the trawl is pulling her stern down. be hauled, the vessel would go about and then fish for a further six hours on The ideal wind was about Force 6 on the Beaufort scale (22-27 knots or The upper side of the net, attached to the beam, formed a roof over the lower part so that fish, when disturbed, would not escape but would be channelled into the net. hoisted up the mast so that the fish slipped out onto the deck to be sorted, When the net was recovered the cod end would be fixed to a line that was cleaned, gutted and packed. SAILING TRAWLERS 11 Trawling Stage 1 the hull, with the net gathered ready for The trawl beam is along the port side of downwind. The mainsail is not set and the or less stationery in the water. streaming. The boat is facing downtide and Trawling mizzen has been 'scandalised' to take the power out of it.The boat is therefore more 12 SAILING TRAWLERS Stage 2 water and the process of allowing the The trawl net has been lowered into the forward (outer) end of the beam to come ('throat') end of the main gaff has been scandalised. The mizzen gaff has been set but the foot of the sail brailled up and the boom sheeted right in to reduce its power. square with the hull has begun.The forward hoisted up the mast, but the 'peak' is still Trawling SAILING TRAWLERS 13 Stage 3 to be lowered away. Both main and mizzen sails and the trawler gathers speed. Stage 4 The beam is set square to the hull, ready in and the mizzen let out.The wind fills the and are fully set.The main has been sheeted Trawling 14 SAILING TRAWLERS bed and fishing is under way. The trawler the tide changes.The upper side of the net is fixed to the beam, while the lower side up they cannot escape. will maintain course for up to six hours until The trawl has been lowered to the sea drags behind. As fish are disturbed and rise Trawling SAILING TRAWLERS 15 A self-assured group of fishermen on the quay with New Pier in background in the 1920s. From the left they are Bill Hellyer, Alf Twyman, Jim Roberts, Jack Fowler, Pricey Holland, Alf Pitman, Jim Clark and Walter Barnes. Around the Harbour Harboursides in fishing ports a century or more ago were crowded, bustling places. With 200 sailing trawlers, plus trading vessels and many small craft, Brixham was as busy as most. Both the inner and outer harbours were full of vessels of one kind or another, landing catches, taking on stores and ice, or mending nets and sails before heading out to sea once more. Here crews exchanged news and told yarns in the brief leisure time they had between trips, and old salts spent their time reminiscing. On New Pier, early 1900s. Fish laid out for sale at the old fishmarket. 16 SAILING TRAWLERS Upham's shipyard, on the East side of the harbour, between Custom House Quay and Grenville House. The yard finally closed in the 1960s. Sails being "barkedâ€? at Overgang Yard, opposite where the yacht club now stands. Barking was carried out with mixture of tallow, tree bark and ochre mixed together and boiled; it was then spread over the sails. SAILING TRAWLERS 17 Life at Sea "Sailing Trawler" by Arthur Briscoe The local fishing grounds for Brixham men lay some three to eight miles off Start Point, running for 20 miles in a north-north-easterly direction and ending opposite Babbacombe on the eastern side of Torquay. Most trawlermen were devout Methodists, and took the view that "it was a crime to be at sea on Sunday, but sacrilege to shoot a trawl." They either fished five or six days, enabling them to be back home in time to observe the Lord's Day. However, as vessels got bigger and faster, and rich new fishing grounds were the local waters and came in at night, or made limited journeys lasting around discovered in the Bristol Channel, others were tempted to spend longer at sea. it was common for trawlers to spend eight weeks at sea, followed by one in port. Carrier boats brought out ice and provisions, and took back the catches of fish. 18 In the North Sea, things were very different. By the end of the 19th century SAILING TRAWLERS Bible but medical supplies, books, magazines and stocks of woollen garments knitted by righteous ladies all over the country. and the like. Later there would be salt beef, treacle and potatoes, all boiled up - fresh from the sea and far better than anything on offer in the fishmonger's. A number of "mission smacksâ€? served those fleets, carrying not only the Heading out from Brixham In the first few days at sea the crew might dine on roast beef, suet pudding together in seawater. For breakfast they had fish, boiled or fried. And what fish! dinner. When the meal was finished it was customary to have half an hour of was then off duty until breakfast time. The boy and fourth hand stayed on deck while the others went below for telling yarns before the third hand went on deck to relieve the fourth hand, who came down for dinner. When he went back up the boy came down, and before having a late supper in the early hours of the morning - usually leftovers from dinner with hard tack biscuits made from flour and water. They might trawl till late in the evening, then pack the catch into boxes things for their wives or sweethearts. Mat-making was a favourite pastime. they cut to a uniform size and then threaded into sacking. While at sea the men would amuse themselves when off duty by making Before going to sea the men would collect off-cuts from tailor's shops which If the wind failed they might raft their boats up together and go aboard each other's craft. Or someone might entertain all other boats in the area by playing the accordion, the music carrying for miles across the water in the still air. scarce on board, so they washed before they went to sea, and again when they appearance and were usually seen in their Sunday best. Bed was a sack of straw, and they slept on it fully dressed. Fresh water was reached land. But when they were home they took great pride in their 19 SAILING TRAWLERS Crew Duties Boy The boy had to cook, provide a constant supply of tea, keep the cabin subordinates could do. On the largest vessels there were five crew. Each crewman had his own duties, in addition to being able to do what his 4th hand The fourth hand had to stand watch and handle the boat in fine weather, and be able to find the right one in the dark. He was responsible for keeping the fish hold and fo'c'sle clean. boat with the trawl gear down, know the Rules of the Road, understand tides, clean, stow small gear, mend nets and get rid of the "brashâ€? brought up in the trawl. In fine weather he might also take the helm when the trawl was shot. do splices and whippings, take soundings, keep the sails in their proper places 3rd hand The third hand had to keep a watch of up to eight hours, manage the Mate The Mate had to set up and shoot the trawl gear, handle the boat in rough Master The Master was on duty 24 hours a day and had to come on deck and weather, have wide knowledge of the various fishing grounds, be responsible for the ship's stores and take charge in the absence of the Master. use his superior knowledge in any emergency. When going to sea he had to navigate the vessel himself until clear of all dangers, check that the trawl warp was securely fastened to the mast before shooting, and that all the lights were used with the greatest care, that no provisions were wasted, the boat was kept seaworthy, and ALWAYS KEEP A GOOD LOOK-OUT. After 1883 he also had to be able to read a chart and take sun sights, be lit at sundown. Above all it was his duty to ensure the owner's property was prepare the catch for market. prepare the trawl for shooting, attend to the rigging and help the fourth hand proficient in navigation, pilotage and tidal theory and be fully conversant with shape of the waves, depth of water and the character of the sea bed as revealed by the lead line. 20 the collision regulations. Until then he relied on course steered, distance run, SAILING TRAWLERS Trinity Sailing Foundation The Trinity Sailing Foundation is a registered charity, founded in 1999 with two aims: 1. The preservation of the historic sailing vessels it owns and operates, as important examples of our maritime and industrial heritage. To increase appreciation of maritime heritage and give as many people as possible the opportunity to learn about it and experience life under traditional sail. 2. To assist the personal development of young people, especially the disadvantaged, using offshore sail training as a means of teaching a range of life skills, building confidence and self esteem and using that to motivate them to take positive steps to improve their chances of making a success of adult life. bringing together Trinity was established by Trinity assists the personal development of young people to improve their chances in life organisations with shared three interests in the fields of maritime heritage and sail training. The three vessels that gave Trinity its name were: largest of her type. She is 105 feet in length overall, displaces 110 tonnes and carries 3,150 square feet of sail on her gaff ketch rig. feet of sail, also on a gaff ketch rig. 'Leader'. Built in 1892. The oldest surviving sailing trawler and one of the 'Provident'. Built in 1924, is an example of the medium-sized 'Mule' class. 'Golden Vanity'. Built in 1908, at 53 feet in length overall she is the baby She is 95 feet in length overall, displaces 80 tonnes and carries 2,750 square of the fleet and built on the lines of the small 'Mumble Bee' class. She displaces SAILING TRAWLERS 21 20 tonnes and carries 1,250 square feet of sail on a gaff cutter rig. parish of Brixham. They all are judged to be of "pre-eminent regional and Historic Fleet. In 2008 a fourth vessel was acquired - 'Spirit of Britannia' is a former Boston All three were built in the same yard at Galmpton on the River Dart in the national significanceâ€? and as such among the 200 vessels that form the National smack, built at King's Lynn in 1915. She is 75 feet overall, displaces 50 tonnes and carries 2,250 square feet of sail on her gaff cutter rig. She is on the National Register of Historic Ships, though not part of the Historic Fleet. of October. The boats normally sail for up to 30 weeks each year, from April to the end More than two-thirds of Trinity's activities are related to sail training, and each year several hundred young people from across the country benefit from carefully-structured courses, run in conjunction with a range of partner afford the full cost. organisations. Trinity raises funds through grants, donations and events to subsidise deserving young people whose sponsoring organisations cannot Trinity offers cruising holidays and charter, which gives the general interest in heritage an opportunity to sail on these classic former working vessels. The income from Trinity believes that its twin aims, combining heritage and social welfare, help The advent of Trinity brought three historic vessels to Brixham, forming the restoration. For the remainder of the time public and those with a special that helps with maintenance and preserve the vessels by providing them with a worthwhile modern role. nucleus of the heritage fleet now based in the port. It led directly to the return trawlers, bringing about a revival in the history and heritage of the community. 22 SAILING TRAWLERS of Vigilance and in due course of Pilgrim, two of the other surviving sailing Leader Leader was built in 1892 in the shipyard of W A Gibbs at Galmpton Creek on the River Dart. She was built for William Robbens, and in order to finance her he raised a mortgage of ÂŁ1,100 from Robert Hellyer, a Brixham man who had moved to Yorkshire in the 1850's and become among the greatest fishing magnates of the 19th century. the largest class of sailing trawler. She is also the oldest, and largest, to survive. including all her spars, rig, sails and fishing gear - within 12 weeks of an order being placed. At the time the yard was able to deliver a completed sailing trawler - At 80 feet on deck and displacing more than 100 tonnes, she was one of the skipper and first hand sailed for a share of the profits.The second hand was mother. The ship's papers show that when she went to sea on her first fishing trip to get 17 shillings (85 pence), a week paid to his wife; the third hand 13 shillings (65 pence), paid to himself, and the boy 10 shillings (50 pence), paid to his 23 SAILING TRAWLERS "Leader" as a sail training vessel, followed by "Gratitude", Sweden 1970s Provisions while at sea were to be "sufficient without waste". especially Scandinavia, and in 1907 Leader was sold to Swedish owners. She was based at Tjarno on the West coast close to the Norwegian border, and Second World War. In the mid-1950s she was de-rigged and used as a coastal cargo vessel. then moved further south to Sannas. She fished under sail until after the In 1969 she was acquired by the Swedish Cruising Association. They spent Secondhand British sailing trawlers were always in great demand in Europe, four years restoring her and used her as a sail training vessel, based at their sailing school in Gothenburg, until 1984. cruising the West Coast of Scotland, Lorne. and spent 10 years as Lorne Leader In 1985 she returned to UK waters based at Craobh Haven on the Firth of In 1996 she was acquired by one of Trinity's founders and brought her back As "Lorne Leader" Scotland 1980s to her original home waters. Three years later she became part of the newly-formed Trinity Sailing Foundation. SAILING TRAWLERS 24 Off the Devon Coast, present day "Leader" as a cargo vessel, Sweden, 1950s SAILING TRAWLERS 25 Provident Provident was built in the yard at Galmpton on the River Dart where Leader had been built, but which by then had passed to Mr Gibbs' son-in-law John Sanders. Gibbs ran the yard until his death in 1905. It then passed to Sanders, a shipwright who had married the boss s daughter Bessie. She is one of the medium-sized 'Mule' type of sailing trawler. by gunfire from a German U-boat during World War I. She was built in 1924 for William Pillar, to replace of the same name, sunk Skipper Pillar and the crew of the first 'Provident' had famously rescued survivors from the torpedoed battleship HMS Formidable in a Channel gale in Buckingham Palace to meet the King and receive medals for bravery, and at the request of Winston Churchill - then First Lord of the Admiralty - were the early hours of the morning of New Year's Day 1915.They were invited to awarded a grant from the public purse. replacement, the current 'Provident'. After the war a government grant enabled William Pillar to build a 'Provident' fished until 1933, when American, and for four years flew the Atlantic before returning to Devon. she was converted to a yacht for an Stars and Stripes. Her new owner took In 1937 'Provident' was sold again, her to the Mediterranean and across the and spent World War II laid up in "Provident" entering harbour, 1920s Cornwall. She changed hands twice more after the war was over, before in SAILING TRAWLERS 26 1951 becoming the flagship of the Island Cruising Club at Salcombe. She remained there for 46 years, but in 1997 the club Dartmouth, and then Brixham, under the Trinity flag. decided they could no longer maintain her, and she moved along the coast to Over the past half century and more Providnet has been a familiar and wellloved sight along the shores of both the UK and Brittany. SAILING TRAWLERS 27 Golden Vanity Like her two bigger sisters, Leader and Provident, Golden Vanity was also built at Galmpton. Constructed in 1908 to the lines of the smallest type of sailing trawler, a He painted sailing trawlers at work, the last of the commercial trading ships Briscoe sailed Golden Vanity extensively around Britain's south and east 'Mumble Bee', she was in fact a private yacht, a floating studio for her owner, the noted marine artist Arthur Briscoe. to operate under sail, and other working craft. coasts, and to the neighbouring coastlines of continental Europe. One of his thriller "Riddle of the Sandsâ€?. After Briscoe sold Golden Vanity she changed hands several times. occasional companions was Erskine Childers, author of the classic yachting In 1972 her then owner, Peter Crowther, entered her in the first Observer Singlehanded Transatlantic Race (OSTAR). It took her 88 days to make the 28 SAILING TRAWLERS crossing - still a record for the longest in the history of the race. Peter, who also entered the race junk-rigged Galway Blazer, always took part for the experience... winning was not on his mind. on several other occasions in the Vanity had become derelict and By the mid 1980s Golden was lying in Brixham harbour. She was rescued by a group of local Vanity Trust and restored her carried out sail training under joined Trinity. over a period of years. She their flag until 1999, when she people who set up the Golden SAILING TRAWLERS 29 People in the Story William Allan Gibbs and John Sanders founded the shipyard in Galmpton in 1836. In 1859 William adventure centre), which for 125 years provided accommodation, education and training for the orphaned sons of seamen. 1905. It was in his time that 'Leader' was built. W A Gibbs was the son of William Gibbs who had Gibbs senior started the Brixham Seamen's Boys Home (now known as Grenville House and an outdoor The younger William inherited the yard in 1886 ran it until his death in The yard then passed to his son-in-law John Sanders, a shipwright who had married the boss's daughter Bessie. He built both 'Golden Vanity' and 'Provident'. trawlers - of the highest quality, and for delivering them on time and at the many destined for owners as far away as Hull and Grimsby. The Hellyers Gibbs and Saunders had a reputation for building boats - particularly sailing promised price. Over the years some 300 sailing trawlers were built there, owners in Brixham in the first half of the 19th century, who reportedly left the town in 1854 and moved to Hull in order to benefit from the big catches the of their day. Most of their vessels were built back 'home' in Brixham. the money that enabled William Robbens to have 'Leader' built. North Sea had to offer.They went on to become the greatest fishing magnates Robert plays a particularly important part in our story, because he put up In 1910 Charles Hellyer moved back to Brixham and spent the then Robert and Charles Hellyer were father and son who were successful trawler enormous sum of ÂŁ50,000 having an imposing mansion built overlooking the most imposing building in the town. 30 SAILING TRAWLERS harbour. It could have been to make sure everyone knew for certain that the local boys had made good! Wolborough House stands there to this day, still the William Pillar trawler 'Provident', which had been fishing in the Channel south of Berry Head, was running for home in a full gale torpedoed battleship 'Formidable' was sighted. It was overloaded and in danger of being swamped. come alongside the boat and transfer the survivors to 'Provident'. All were survivors, 23 died before the remainder reached shore. £500, and the others lesser amounts. build a replacement. Arthur Briscoe Born in 1843 At considerable risk, and after several attempts, Skipper Pillar managed to when a small open boat loaded with 71 survivors from the In the early hours of New Year's Day 1915 the sailing returned safely to land. Of the occupants of another similar boatload of Medal by King George V at Buckingham Palace. Pillar received a cash award of Pillar and his crew of two men and a boy were each awarded the Albert Later in the war 'Provident' was herself sunk by gunfire from a U-boat, and when the war was over the Government awarded Pillar money with which to and educated at studied School, Shrewsbury at Briscoe the Slade School of Fine Art in London and in Paris. A noted marine artist whose work still commands five-figure sums today, he was also a keen sailor. lived aboard with his wife and young son, but he also sailed in square riggers and documented the last days of sail in oils, watercolours and etchings . "Riddle of the Sands" and the two sailed together on a number of occasions. He commissioned the building of 'Golden Vanity'. For a number of years he One of his friends was Erskine Childers, author of the classic sailing yarn "Brixham Trawlers" by Arthur Briscoe SAILING TRAWLERS 31 Brixham Brixham in 1791. The village is clustered tightly round the harbour and has not yet spread up the surrounding hills. A pipe leads "sweet water" from the reservoir on the left to Deer Rock. Tor Bay, facing east, has always provided ships and sailors with protection from the prevailing westerly winds, and Brixham's position at the southern end of the bay meant it was the most sheltered spot of all. It was the natural site for the development of the local fishing and shipbuilding industries. During the 18th century the sheltered bay became increasingly important to the Admiralty and the availability of "sweet water" at a spring. Wooden conduits carried water to Kings Quay, built in 1690 for the purpose of watering the Kings ships. 1804. Brixham led to the construction of a Navy reservoir fed by The New Quay and fishmarket were completed by Plans for a breakwater to protect the harbour from The availablity of "sweet water" at Brixham led to the construction of a Navy reservoir easterly winds can be traced back 1781 but it was not until 1843 that due to lack of funds. construction started. Only 1400 feet had been built when work was halted and emphasised the need for protection. It was not until 1909 that with 32 SAILING TRAWLERS Severe gales in 1859 and 1866 caused damage to the incomplete structure financial help from the government another 600 feet could Brixham quay, 1910 constructed. Work began again in 1912 and the final 1000 feet added the First World War. by 1916, despite the outbreak of be Three retired trawlermen Tom May, Tom Bray and Tom Perrett. markets for fish landed at Brixham. The development of transport had an enormous impact on the available In early days there was no requirement for the upkeep of roads and consequently they were in a very poor state. It was not until the mid 16th Century that each parish was made responsible for its own roadways. This Trusts were set up across the country to create good roads and pay for their upkeep through tolls collected from those who profited from using them. markets. Portsmouth by sea and then by road to reach the London Devon markets in Exeter and Bath were opened up, supplied direct from Brixham. Fish caught by Brixham boats could now be taken to system proved neither effective nor fair. During the 18th Century Turnpike When the turnpike network extended into The 1848 rail link meant that fish could be delivered to London within hours of being landed 33 SAILING TRAWLERS of being landed. Arctic ice was starting to be imported from Norway to keep it fresh on the journey and fish was really on the move. constructed connecting Torquay to Kingswear, having a station known as Brixham Road at Churston. The two mile journey from Brixham to this station was still a great inconvenience and a Mr. Wolston felt strongly that the town determined to build it himself. Mr. Wolston founded the Torbay and Brixham the economy of the town. Access to the railway improved during the 1860s when a new line was In 1848 a rail link from Torquay meant fish could reach London within hours would benefit from having its own connection. So strong was his conviction that he lobbied vigorously for a Brixham link and this being unsuccessful he line which opened in 1868 and proved to be a great success and a boon to France the British fleet was frequently to be seen in Torbay. The French navy them from coming up Channel to invade England. had assembled in Brest and it was essential that the British fleet should prevent Much of the time British ships were stationed out in the western During the long period of the Revolutionary and Napoleonic wars with approaches to the English Channel, blockading the French in port, but they needed shelter to run to from westerly gales, where they could also restock Lord St Vincent strongly favoured Torbay. Lord Howe spent so much time here that he earned the nickname 'Lord Torbay' and other famous Admirals at one time or another. the ships, put their sick and wounded ashore and find more crew if necessary. Hawke, Cornwallis, Hood, Rodney and Nelson all brought their fleets to Torbay Napoleon was Between 1794 and 1804 extensive fortifications were brought to Torbay built on Berry Head to protect the ships at anchor and following his guard against possible French troop landings. defeat at Waterloo Napoleon was brought to Torbay on a man-o-war before his exile to following his defeat at Waterloo and remained at anchor St. Helena became quite a tourist attraction, with many small craft taking passengers around the ship. 34 awaiting the order to take him to exile on St. Helena. He SAILING TRAWLERS fishing port had been steadily progressing and an important ship and boatbuilding industry had built up alongside. Wheaton as the largest shipbuilder Records from 1804 show Waiting for a breese, 1868 Captain Samuel Holland and family. Holland owned three sailing trawlers named "Guess", "Guess Again" - pictured on page 2 - and "Guess On" (to deter nosey neighbours who wondered where he had found the money to build them). Brixham's advancement as a in Brixham.Wood and Furneaux are also mentioned along with four smaller yards. The number and size Furneaux trawlers and trading ships inside the Fishcombe. was building both of the yards increased and by 1850 harbour, Jackman was building on the Breakwater beach, Cottie had a yard at Shoalstone and Osbourne at Dewdney, Munday and Richardson had yards on King Street. Uphams outlived them all. Founded in 1817, by 1890 the site covered three acres and could build ships of up to 400 tons. Uphams also built many trawlers, the best known being 'Ibex', renowned for her unbeatable speed. dozen operating under sail in the 1920's, with new ones being built until 1926, and a handful remained fishing until the outbreak of World War II. The town is still the third largest fishing port in England. 200 vessels in the 1890's. Despite the advent of steam there were still several From the advent of the sailing trawler Brixham's fleet grew to more than Brixham outer harbour, still full of sailing trawlers, 1926 SAILING TRAWLERS 35 Paintings by Toni Knights, marine artist, modern beam trawler skipper and former Trinity skipper. 36 SAILING TRAWLERS H A M A ND T HE LEG ENDRY SA N ILI G TRAWLER S Trinity thanks the following for their assistance Brixham Heritage Museum Brixham Community College Roger Kyle Images, by kind permission Front cover: Sir John and Lady Rose Back Cover: Robert Cann Page 36: Toni Knights IX BR Illustrations Page 9: Norman Young Pages 12-15: Toni Knights 'Leader' and 'Provident' in Tor Bay, 2009 By Martin West Trinity Sailing Foundation The Sail Loft, Pump Street, Brixham TQ5 8ED Tel: 01803 883355 Email: firstname.lastname@example.com Web: www.trinitysailing.co.uk Design: www.designsolutionltd.co.uk


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September 19, 2013
Emergency personnel look over the crash scene following a collision between a Via Rail train and a city bus at a crossing in Ottawa, Ontario, Wednesday, Sept. 18, 2013. An Ottawa Fire spokesman said there are "multiple fatalities" and a number of people injured from the bus. (AP Photo/The Canadian Press, Adrian Wyld)
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6 killed as Canada bus strikes passenger train
Thursday, September 19th, 2013 6:58 a.m.
Passengers screamed "Stop! Stop!" seconds before their bus crashed through a crossing barrier and into a commuter train during morning rush hour in Canada's capital on Wednesday, killing six people and injuring 34.


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- Special invitation to observe a company class by prior arrangement
- Annual name listing in The Nutcracker playbill
- Invitation to Choreographic Workshop
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