text:
|Publication number
|Publication type
|Application number
|Publication date
|Oct 10, 2000
|Filing date
|Apr 5, 1999
|Priority date
|Apr 16, 1998
|Fee status
|Publication number
|Ronald L. Andrus, George H. Beall, Linda R. Pinckney, Christine C. Wolcott
|Original Assignee
|Corning Incorporated
|Export Citation
|BiBTeX, EndNote, RefMan
|Patent Citations (10), Non-Patent Citations (6), Referenced by (19), Classifications (7), Legal Events (5)
|External Links: USPTO, USPTO Assignment, Espacenet
This application is a provision of Ser. No. 60/082,127 filed Apr. 16, 1998.
1. Field of Invention
The present invention relates to strong glass-ceramics materials containing miserite crystals as the predominant crystalline phase.
2. Description of the Related Art
Glass-ceramics are polycrystalline materials formed by a controlled crystallization of a precursor glass article. A glass-ceramic may be prepared by exposing a glass monolith to a thermal treatment for conversion to a crystalline state. This is referred to as a "bulk or monolith forming process". Monolith glass-ceramic forming technology is founded in U.S. Pat. No. 2,920,971 (Stookey). In general, raw materials usually containing a nucleating agent are melted and simultaneously cooled to form a glass monolith of desired geometry. Thereafter the glass monolith is exposed to a crystallizing thermal treatment referred to as "ceramming". The appropriate thermal treatment typically includes a low temperature hold at a temperature somewhere above the transformation range to induce nucleation, followed by one or more higher temperature holds at temperatures somewhere above the softening point to promote crystal growth. In the monolith forming process nucleation transpires internally. The manufacture of glass-ceramics by bulk forming processes is compatible with high-speed, automated manufacturing processes employed in the formation of glass articles. Furthermore, internal nucleation can provide a wide range of potential crystalline microstructures.
U.S. Pat. Nos. 4,386,162 and 4,397,670 (Beall) discloses the preparation of glass-ceramic articles demonstrating high mechanical strength and toughness wherein crystals of canasite and/or agrellite and/or fedorite having a chain silicate structure constitute the predominant crystal phase. Those articles have a composition expressed in terms of weight percent on the oxide basis, comprising
______________________________________SiO2 45-75 Na2 O 3-15 B2 O3 0-6CaO 8-30 K2 O 0-20 Al2 O3 0-7F 3.5-12 Na2 O + K2 O 5-25 ZrO2 0-12.______________________________________
Compositions resulting in glass-ceramics exhibiting the greatest mechanical strength and toughness containing canasite as essentially the sole crystal phase have a composition expressed in terms of weight percent on the oxide basis, comprising
______________________________________SiO2 50-65 Na2 O 3-13 B2 O3 0-3CaO 15-24 K2 O 3-15 Al2 O3 0-3F 5-9 Na2 O + K2 O 11-22 ZrO2 0-8.______________________________________
Fluorite crystals (CaF2) provide the nuclei upon which the canasite crystals [Ca5 Na4 K2 (Si12 O30)F4 ] grow. Where canasite comprises essentially the sole crystal phase, there is an interlocking blade-like crystalline morphology, which structure has conferred modulus of rupture values to the crystallized articles in excess of 50,000 psi (345 MPa).
U.S. Pat. No. 4,467,039 (Beall et al.) discloses the formation of glass-ceramic articles exhibiting high strength and toughness containing potassium fluorrichterite (KNaCaMg5 Si8 O22 F2) having a chain silicate structure as the predominant crystal phase.
The precursor glasses demonstrate the capability of ceramming very rapidly upon heat treatment and have a composition expressed in terms of weight percent on the oxide basis, comprising
______________________________________SiO2 50-70 F 3-8 Li2 O 0-3CaO 4-15 Na2 O 2-9 Al2 O3 0-7MgO 8-25 K2 O 2-12.______________________________________
Whereas the crystalline articles may also contain potassium-rich canasite (K3 Na3 Ca3 Si12 O30 F4), the preferred products contain potassium fluorrichterite as essentially the sole crystal phase, and have a composition expressed in terms of weight percent on the oxide basis, comprising
______________________________________SiO2 57-68 CaF2 7-12 K2 O 3-7Al2 O3 0-4 Na2 O 2.5-5 MgO 14-18CaO 0-3.______________________________________
A glass-ceramic may also be prepared by firing glass frits in what is referred to as powder processing methods. A glass is reduced to a powder state, formed to a desired shape, fired and crystallized to a glass-ceramic state. Instead of using internal nucleation, the relict surfaces of the glass grains serve as nucleating sites for the crystal phases. The glass composition, particle size, and processing conditions are chosen such that the glass softens prior to crystallization and undergoes viscous sintering to maximum density just before the crystallization process is completed. Shape forming methods may include but are not limited to extrusion, slip-casting, tape casting, spray drying and isostatic pressing.
Examples of powder processing glass-forming technology can be found in U.S. Pat. Nos. 3,839,001 (Adams et al.), 4,464,475 (Beall et al.), and 5,001,086 (Carrier et al.), herein incorporated by reference.
The manufacture of sintered glass-ceramics is compatible with glass-ceramic compositions for which no nucleating agents exist and is particularly suitable for the production of highly complex and intricately-shaped articles.
It is somewhat uncommon for any one glass-ceramic composition to be compatible with both the monolith and powder forming processes. Surface crystallization and poor internal nucleation in a monolith leads to very weak, deformed articles, while internal nucleation and poor surface crystallization in a powder compact may result in total crystallization prior to sintering, yielding at best a weak, porous, poorly sintered article and at worst a pile of crystallized powder.
It is an object of the present invention to provide a glass-ceramic composition compatible with both forming processes. It is another object of the present invention to provide a glass-ceramic having superior mechanical strength and fracture toughness.
The present invention resides in a single or multiple phase glass-ceramic material having a predominant crystal phase of the chain silicate miserite, a bending strength greater than 25,000 psi (175 MPa), a fracture toughness greater than 3.5 MPa√m, and a composition calculated in weight percent on an oxide basis comprising 40-68% SiO2, 12-35% CaO, 8-20% CaF2, 4-10.5% K2 O, 0-5% Al2 O3, 0-5% B2 O3, 0-15% P2 O5, 0-4% R2 O3, where R represents Y3+ and rare earth metals in the lanthanide series. Up to 5% of optional ingredients may be added from the group consisting of MgO, SrO, BaO, Na2 O, Nb2 O5, ZrO2 and ZnO and up to 10% from the group consisting of Nb2 O5 and TiO2. Additionally, 0-2% of Li2 O as an optional ingredient may also be added.
The inventive glass-ceramic composition is compatible with both the monolith and powder forming processes.
FIG. 1 is a photomicrograph showing the representative microstructure of the miserite glass-ceramic of the present invention.
The present invention is based on the discovery of a family of glass-ceramic compositions that can produce glasses of excellent stability which can be cerammed to produce strong glass-ceramics.
The inventive glass-ceramic is based on a composition comprising as expressed in weight percent on the oxide basis, 40-68% SiO2, 12-35% CaO, 8-20% CaF2, 4-10.5% K2 O, 0-5% Al2 O3, 0-5% B2 O3, 0-15% P2 O5, 0-4% R2 O3, where R represents Y3+ and rare earth metals in the lanthanide series. In addition the composition may comprise 0-5% of optional constituents selected from the group consisting of MgO, SrO, BaO, Na2 O, Nb2 O5, ZrO2, and ZnO, and 0-10% of optional constituents selected from the group consisting of Nb2 O5 and TiO2, and may also comprise 0-2% Li2 O as another optional constituent.
X-ray diffraction analyses on the inventive-glass ceramics indicate a predominant crystal phase of miserite. Miserite is described and structurally analyzed by J. D. Scott in "Crystal Structure of Miserite, A Zoltai Type 5 Structure", Canadian Mineralogist, No. 14, 515-528 (1976).
The miserite mineral is a multiple chain silicate exhibiting an anisotropic, lath or rod-like crystal habit. Structurally, miserite crystals are composed of three-member subchains of SiO4 tetrahedra which are linked to produced a closed quadruple Si12 O30 chain composite, pipe-like in shape and parallel to the c-axis. The formula for miserite is KCa5 □(Si2 O7)(Si6 O15)(OH)F, where □represents a vacant octahedral site in the crystal structure. This octahedral site is defined by slabs of Ca polyhedra and acts as a selective structural trap for minor atomic species which are present in the rocks in which the miserite mineral naturally occurs and provide the necessary charge balance in the formula. Examples of minor atomic species include Ce4+ and Y3+, Nb5+, and other rare earth metals in the lanthanide series.
The most preferred composition range to obtain glass-ceramic materials exhibiting very high mechanical strength and fracture toughness, comprises in weight percent on the oxide basis 42-65% SiO2, 12-25% CaO, 12-16% CaF2, 5-9% K2 O, 0-2% Al2 O3, 0-4% B2 O3, 0-8% P2 O5, 0-3% R2 O3, where R represents Y3+ and rare earth metals in the lanthanide series.
X-ray diffraction patterns of the inventive glass-ceramic reveal that the miserite crystal phase is often accompanied by crystals of cristobalite (SiO2), fluorite (CaF2), xonotlite (Ca6 Si6 O17 F2), and fluorapatite (Ca5 (PO4)3 F), and small amounts of other calcium silicate phases such as wollastonite (CaSiO3). Cristobalite is particularly common in the powder processed glass-ceramic materials, as this crystal phase is easily surface nucleated. The inventive glass-ceramic materials are highly crystalline with less than 20% residual glass.
In the present invention, mixed miserite and fluorapatite glass-ceramic materials may be particularly useful as potential biomaterials. The secondary fluorapatite crystal phase may confer a degree of bioactivity to the inventive glass-ceramics, while at the same time the relatively simple chemistry of the glass-ceramic materials may be indicative of probable biocompatibility. Fluorapatite crystal growth is observed in the inventive glass-ceramics at levels of over 4 wt. % P2 O5 in the bulk composition. The most preferred composition range to obtain a secondary fluorapatite crystal phase comprises in weight percent on the oxide basis, 40-55% SiO2, 20-35% CaO, 10-15% CaF2, 4-8% K2 O, 0-2% Al2 O3, 0-3% B2 O3, 4-15% P2 O5. Up to 2 wt. % Y2 O3 is allowed, but CeO2 suppresses the crystallization of fluorapatite. Although potential biocompatibility has not been rigorously established in the inventive mixed miserite and apatite glass-ceramic materials, because of the apparent potential bioactivity from apatite crystals and potential biocompatibility from the materials' simple chemistry, these glass-ceramics may likely find application as bone implant materials.
Table I sets forth a number of glass compositions, expressed in terms of parts by weight on the oxide basis, illustrating the parameters of the present invention. Table I also presents test forming processes, crystal phases observed, modulus of rupture values as measured in Kpsi, and fracture toughness values as measured in MPa√m.
TABLE I______________________________________ MXO MXQ MXR MXV 1 2 3 4______________________________________SiO2 59.4 57.4 58.0 50.3Al2 O3 0.6 0.6 -- 0.2CaO 18.0 18.0 18.0 29.7CaF2 13.0 13.0 13.0 10.5K2 O 7.6 7.6 7.6 7.0Y2 O3 1.4 1.4 1.4 1.3B2 O3 -- 2.0 2.0 1.0Process Proc. A Proc. A Proc. A Proc. ACrystal miserite miserite miserite miseritePhases xonotliteMOR 28.5 31.7 24.7 14.8(Kpsi)______________________________________ MYB MYE MYG MYH MYI 5 6 7 8 9______________________________________SiO2 59.0 56.4 54.5 54.0 55.6Al2 O3 0.6 0.6 0.6 0.6 0.6CaO 18.0 18.0 19.6 19.6 19.6CaF2 13.0 13.0 12.8 12.8 13.0K2 O 7.6 7.6 7.2 7.2 7.2Y2 O3 0.8 1.4 1.3 -- --B2 O3 1.0 1.0 1.9 1.9 1.9MgO -- 2.0 -- -- --P2 O5 -- -- 2.1 2.1 2.1CeO2 -- -- -- 1.8 --Process Proc. B Proc. B Proc. B Proc. B Proc. BCrystal miserite miserite miserite miserite miseritePhases xonotliteMOR 24.8 25.7 28.5 33.6 28.3(Kpsi)KIc -- -- 3.6 -- --(MPavm)______________________________________ MYJ MYK MYM MYR MYT 10 11 12 13 14______________________________________SiO2 51.7 48.8 45.9 52.2 51.1Al2 O3 0.5 0.5 0.5 0.6 0.5CaO 21.2 22.8 24.0 19.6 21.2CaF2 12.5 12.3 12.0 12.8 12.5K2 O 6.8 6.5 6.1 9.5 6.8Y2 O3 1.2 1.2 1.1 -- --B2 O3 1.8 1.7 1.6 1.8 1.8P2 O5 4.2 6.3 8.5 2.0 4.2CeO2 -- -- -- 1.5 1.5Process Proc. B Proc. B Proc. B Proc. A Proc. ACrystal miserite miserite miserite miserite miseritePhases minor- apatite xonotlite apatiteMOR 30.1 25.8 16.0 30.1 31.5(Kpsi)KIc 36 -- -- --(MPavm)______________________________________ MYV MYW MYX MZA MZD MZG 15 16 17 18 19 20______________________________________SiO2 45.9 45.5 45.0 58.9 58.9 62.4Al2 O3 0.5 0.5 2.0 0.6 0.6 0.6CaO 24.0 23.5 23.5 19.0 19.0 15.0CaF2 12.0 12.0 12.0 13.0 13.0 13.0K2 O 6.0 6.0 6.0 7.5 5.5 6.0B2 O3 1.6 2.5 1.5 -- 1.0 --P2 O5 8.5 8.5 8.5 1.0 2.0 3.0CeO2 1.5 1.5 1.5 -- -- --Process Proc. A Proc. A Proc. A Proc. A Proc. A Proc. ACrystal miserite miserite miserite miserite miserite miseritePhases minor- xonotlite apatiteMOR 29.5 33.3 29.8 18.5 21.0 18.2(Kpsi)KIc -- -- -- 3.9 -- 2.7(MPavm)______________________________________
The exemplary glasses in Table I were powder processed in the following manner. The batch materials, which include but are not limited to standard oxides known to persons skilled in the art such as potassium carbonate and fluorspar (a source of CaF2), were ballmilled together to secure a homogeneous melt, and subsequently deposited in lid-covered platinum crucibles. The filled crucibles were placed into a furnace and the glass batch was melted at temperature ranging from 1475-1500� C. for times ranging from about 4-6 hours. Thereafter a glass frit was prepared; the melt was simultaneously cooled and shaped, by passing the glass through water-cooled rollers to form thin sheets or ribbons, 1-2 mm thick; the ribbons were not annealed to facilitate the fragmentation of the glass; the glass fragments were ballmilled with alumina cylinders and methanol to a powder having an average particle size of about 10 microns. As used herein the term "glass frit" refers to a glass that has undergone pulverization. It is to be understood that the above described method for making glass frit is preferred, but other methods well known in the art are also suitable in the present invention.
Three gram samples of each glass powder composition were pressed at 10,000 psi into 0.5 inch diameter pellets. The glass powder pellets were introduced in a furnace and fired from 25� C. to 1000� C. at a rate of 500� C./hour with a hold at 1000� C. for four hours, during which the glass powder pellets underwent sintering and crystallization to a glass-ceramic state. After the firing cycle was complete, power to the furnace was turned off and the pellets were allowed to cool to room temperature at furnace rate.
The glass-ceramic pellets were submitted for X-ray diffraction analysis to determine the crystal phase(s) present in each specimen.
Specimens were also prepared for strength and toughness measurements in the following manner. A slurry was formed of 100 grams of the glass powders mixed with 8 grams of a 50% solution of "20M m.w." polyethylene glycol (Carbowax�) and approximately 40 grams of deionized water. The slurries were hand mixed and allowed to air dry, and thereafter hand passed through a 20 mesh screen (0.84 mm openings) to form granules for subsequent pressing into bars. Two processes were utilized in the formation of testing bars. In the first process (Proc.A), 8 grams of the granules were pressed one at a time under a pressure of 4,670 psi, using a Carver Model C laboratory press, into bars having approximate dimensions of 3.0"�0.5"�0.2". In the second process (Proc.B), 5.25 gram of the granules were pressed six at a time under a pressure of 10,400 psi, using a Dennison 39 ton hydraulic press, into bars having approximate dimensions of 2.5"�0.5"�0.15". Subsequently the bars were heated from 25� C. to 1000� C. at 300� C./hour with a hold at 1000� C. for 4 hours, and were cooled to room temperature at furnace rate, whereby the bars were sintered and crystallized to a glass-ceramic comprising a miserite primary crystal phase.
The glass-ceramic bars were sandblasted to produce consistent surface flaws in order to reduced the variability caused by specimen handling in subsequent abraded modulus of rupture (MOR) testing. MOR values in Table I indicate the highest value obtained in a group of 5 or 6 samples tested for each composition.
MOR or flexural strength is a measure of a material's ability to withstanding failure under a given load. High values of MOR are indicators of a strong material capable of withstanding high pressures before failure.
For fracture toughness (KIc,) samples, 25 grams of glass powder were pressed into bars having approximate dimensions of 3.0"�0.5"�0.6" using Proc.A as described above. The same thermal treatment as per the strength specimens was also employed for the toughness specimens. From these sintered bars, KIc samples were cut and finished with a fine grind to 0.565"�0.375"�0.325", all dimensions�0.001". Typically, three test specimens were obtained from each sintered bar.
KIc is a measure of a material's intrinsic resistance to catastrophic crack propagation. High fracture toughness or KIc values are desired. KIc values for certain compositions are set forth in Table I and indicate the mean value based on three samples.
As can be observed from a study of Table I a MOR value of approximately 34,000 psi (235 MPa) was observed in Example 8. KIc values of 3.6 MPa√m and 3.9 MPa√m were observed in Examples 7 and 10, and Example 18, respectively.
It is noted that all examples in Table I include an accessory cristobalite crystal phase. Internal nucleation is still the dominant force over surface nucleation even in the powder processed samples, nonetheless a strong, properly sintered glass-ceramic article was obtained.
In addition to isostatic pressing, other powder processes may be utilized in the production of the inventive glass-ceramic materials including but not limited to slip casting, tape casting, spray drying and extrusion.
In the present invention it has been observed that the operable glass compositions are also compatible with the monolith process for glass-ceramic formation. Therefore, the inventive glass-ceramic materials can be produced with customary monolith forming processes, as described in U.S. Pat. No. 2,920,971 (Stookey) and herein incorporated by reference. Raw materials are batched, melted into a glass, the glass cooled to a temperature at least below the transformation range, and a desired glass article shaped therefrom. The glass article is thereafter cerammed.
More specifically the method for monolith forming the inventive glass-ceramic article comprises four general steps:
(a) melting a batch for glass having a composition comprising in weight percent: 40-68% SiO2, 12-35% CaO, 8-20% CaF2, 4-10.5% K2 O, 0-5% Al2 O3, 0-5% B2 O3, 0-15% P2 O5, 0-4% R2 O3, where R represents Y3+ and rare earth metals in the lanthanide series, and 0-5% of optional constituents selected from the group consisting of MgO, SrO, BaO, Na2 O, Nb2 O5, ZrO2, and ZnO, 0-10% of optional constituents selected from the group consisting of Nb2 O5 and TiO2 and 0-2% Li2 O as another optional constituent;
(b) cooling the glass to a temperature at least below the transformation range thereof and simultaneously forming a glass article therefrom of a desired configuration;
(c) exposing the glass article to a temperature between about 900-1000� C. for a period of time sufficient to cause development of the miserite crystals as the predominant crystal phase to form a glass-ceramic;
(d) cooling the glass-ceramic to room temperature.
Step (c) will customarily be divided in two stages. First the glass article will be exposed to a temperature within the range of about 600-800� C. for a period of time sufficient to generate the development of nuclei therein. The period of time will generally be about 2 hrs. Second, the nucleated glass will be exposed to a temperature within the range of about 900-1000� C. for a period of time sufficient to effect the growth of crystals on the nuclei. The period of time will generally be about 4 hrs. The inventive glass-ceramic material is internally nucleated with CaF2.
Most often the resulting phase assemblage in the inventive glass-ceramic materials may be slightly different between the two forming processes. Nonetheless, the sequence of crystallization from fluorite to xonotlite to miserite is the same in both processes, and miserite is always the predominant crystal phase.
Table II reports a comparison between powder and monolith processing in crystal phase assemblage and MOR values in Examples 2, 5, 6 and 7.
TABLE II______________________________________ MXQ MYB MYE MYG 2 5 6 7______________________________________SiO2 57.4 59.0 56.4 54.5Al2 O3 0.6 0.6 0.6 0.6CaO 18.0 18.0 18.0 19.6CaF2 13.0 13.0 13.0 12.8K2 O 7.6 7.6 7.6 7.2Y2 O3 1.4 0.8 1.4 1.3B2 O3 2.0 1.0 2.0 1.9MgO -- -- 2.0 --P2 O5 -- -- -- 2.1Powder Proc. A Proc. B Proc. B Proc. BFormingProcessMOR (Kpsi) 31.7 24.8 25.7 28.5Crystal miserite miserite miserite miseritePhases minor- minor- xonotlite minor- cristobalite cristobalite cristobaliteMonolith 800� C.- 800� C.- 800� C.- 800� C.-Forming 2 hrs 2 hrs 2 hrs 2 hrsProcess 1000� C.- 1000� C.- 1000� C.- 1000� C.- 4 hrs 4 hrs 4 hrs 4 hrsCrystal miserite miserite miserite miseritePhases minor- xonotlite fluoriteMOR (Kpsi) 24.1 20.4 17.1 24.9______________________________________
Monolith processed samples were prepared in the following manner. The glass compositions of examples 2, 5, 6, and 7 were melted to a glass, and thereafter poured into 0.5" thick patties and annealed at 600� C. Test pieces were sawcut to approximate dimensions of 2.5"�2.0"�0.5". The two-step thermal treatment included a nucleating step at 800� C. for 2 hours, followed by a 4 hour crystallization at 1000� C. The rate of heating was 300� C./hour. Cooling to room temperature was at furnace rate. The cerammed test samples were cut and fine ground into sample MOR bars having the dimensions of 2.0"�0.25"�0.13". The samples were sandblast abraded and MOR tested similarly to the aforementioned powder processed samples.
As can be observed from a study of Table II, cristobalite was not a secondary phase in the monolith processed samples. Furthermore, in all four examples, the powder processed samples had higher mechanical strengths than the monolith processed counterparts.
It should be recognized that although laboratory practice was employed, production of the inventive glass-ceramics can be transferred to commercial scale manufacturing.
Moreover, it should also be noted that various heat-treatment cycles may be used to produce unique microstructures tailored to provide different mechanical properties.
FIG. 1 is a scanning electron micrograph of the fracture surface of Example 3, wherein miserite comprises essentially the sole crystal phase present, taken at a magnification of 2000 times. The bar at the bottom of the micrograph represents a distance of 10 microns. The glass-ceramic was white-opaque in appearance. As can be observed in the micrograph the randomly-oriented, rod-like crystals represent the miserite crystal phase. The miserite crystals are about 10 microns in length and about 1 micron in diameter. The representative interlocking, rod-like crystal morphology is assumed to account for the high mechanical properties in the final product. It is believed that for a fracture to propagate through the resulting microstructure it has to follow a tortuous path around each miserite crystal, and therefore catastrophic failure is less likely to result.
Although the now preferred embodiments of the invention have been set forth, it will be apparent to those skilled in the art that various changes and modifications may be made thereto without departing from the spirit and scope of the invention as set forth in the following claims.
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|U.S. Classification
|501/3, 501/5, 65/33.3, 501/4
|International Classification
|Cooperative Classification
|European Classification
|Apr 5, 1999
Owner name: CORNING INCORPORATED, NEW YORK
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|Mar 29, 2004
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text:
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- Zoning: RES
- Acreage: 5.1
- Lot description: Secluded, Sloping, Trail/Near Trail
- State: NH
- Street: Eastern Corner Road
- Building Number:
- Development/Subdivision: 0
- Zip Code: 03223
- County: NH-Grafton
- Town: Campton
- Area Description: Mountain, Near Golf Course, Near Skiing
- Elementary School: Campton Elementary
- Junior High:
- High School: Plymouth Regional High School
- Water: None
- Sewer: None
- Electric: At Street
- Services:
- Land Restrictions:
- Taxes: $862
The New England Real Estate Network provides Multiple Listing Services (MLS) in the States of New Hampshire, Vermont, Massachusetts and Maine.
Copyright© 2016 The New England Real Estate Network. All rights reserved. This information is deemed reliable but not guaranteed. The data relating to real estate displayed on this Site comes in part from the IDX Program of NEREN. The information being provided is for consumers personal, non-commercial use and may not be used for any purpose other than to identify prospective properties consumers may be interested in purchasing. Data last updated on 12/10/2016.

subset: commoncrawl


text:
Watch this space
Something exciting is brewing
Welcome to
Asia Dive Academy
As with many dive operations, Asia Dive Academy started with a few passionate divers with the drive to share their love of the underwater world. We are all about education – passing on the knowledge and love for everything related to diving and this philosophy, is reflected in every aspect of our operations, from our friendly dive staff, to the convenient locations of our dive centres. Sustainability, growth and discovery through education.
Since 1996, we have collectively certified over 12,000 recreational divers and hundreds of dive professionals from over 100 countries have experienced the wonders of the underwater world with us.
What we offer
A complete range of recreational and dive professional courses.
Dive logistic support, including procurement, rental and maintenance for existing operators
Dive operation, business insights and industry training
Dive Management Associate Program
The DMA Program is our offering to non-divers and divers alike, an intensive on-the-job training program, where you will go through Dive Business training. This includes Dive Operations, Marketing Application, Retail Operations, Customer Service Training and Facility & Inventory Management Training, as well as Dive Training – going from a Non-diver to a Scuba Diving Professional!
It is very much like a Full Time Scuba Internship where you will work in a scuba shop, become familiar with dive operations, and will also be trained to become a dive professional! It is a great introduction to having a career in the scuba diving industry.
Instructor Training Course
From the time man had the urge to explore the underwater world, the pleasures were denied to the vast majority until scuba training and equipment were developed in its present form. Now that diving is accessible to anyone, there is a high demand for people who have a passion for diving and want to share that experience with others.
The Instructor Training Course is a unique program that has stood the test of time. In order to stay competitive in today's diving industry, the program has been updated to ensure that all Dive Professionals are equipped with the latest retail business training and industry knowledge. A newly certified Open Water Instructor can be absolutely sure to have all necessary skills and knowledge to work successfully.
From our latest post
Have any questions?
Call us
+65 6533 5944
Come and visit


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Soft Amethyst Mica
Used in CP soap - I love this color! I bought a sample pack. I was in the middle of making a soap using a lavender colorant from a different company that I had pre-mixed & turned my soap a light gray. I was desperate for colorant so I grabbed the sample of Soft Amethyst Mica and put a teaspoon directly into my soap batter. I had already put some TD in my soap trying to get rid of the other colorant. I stick blended in the Soft Amethyst Mica and it was GORGEOUS! It was the perfect soft, creamy, light lavender color. Unfortunately in my rush I spilled the rest of my sample of the floor but I'm order more now. I can't wait to see what it looks like when not mixed with TD.
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Nov 8, 2015
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Ooey Gooey Caramel Flavor Oil
Yummy, yummy and more yummy! I mix this with the butterscotch flavor to make my own unique balm. My customers love it :)
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Agriculture: Small Scale Farming
March 3 @ 6:00pm - May 12 @ 8:00pm| $130
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This is an introductory course for the backyard homesteader with an entrepreneurial spirit. Learn how to plan, design, and modify your garden landscape (no matter what size) to become more self-reliant through home food production. This course will help beginning growers understand effective farming methods and what is required to produce healthy produce using sustainable inputs. You will also learn how to develop multiple revenue streams through business planning, as well as how to create synergy with existing networks and local resources. Land ownership is not a requirement; you will be connected to one of many community gardening efforts in Wilmington. Knowledge gleaned from this course can even help you develop a business proposal to gain land access in your own neighborhood. No textbook required. $130
The CFCC Continuing Education division is currently offering this course at the Wilmington Campus. You can register online through WebAdvisor at www.cfcc.edu or register in person at the Community Enrichment department located in the G-building at 402 N. Front Street, Wilmington, NC.
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Family and Society in American History
By (author) Joseph M. Hawes Elizabeth Nybakken
Format: Paperback
Normal Price: $62.00
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Family and Society in American History by Joseph M. Hawes
Book DescriptionThe internal dynamics of families have altered dramatically as the family has gradually shifted from a unit of economic production to a collection of individuals in pursuit of different goals. Taking examples from the eighteenth through the twentieth centuries, this eclectic reader illuminates changes in the American family and presents some of the methods and approaches used to study families. Linking family patterns with changing social circumstances, "Family and Society in American History" considers husband-wife and parent-child relationships in light of language usage, gender roles, legal structures, and other contexts. For example, new legal attitudes toward divorce emerged as marriage came to be seen as a site for individual satisfaction. Marital fertility declined as American society modernized and pregnancy and childbirth came to be seen as medical rather than family issues. Schools and other institutions of the state absorbed functions formerly performed by the family, and women's economic contributions to the family disappeared from view as the social values of the early republic divided the male (work) from the female (home) sphere. In the twentieth century, a new domestic role for men - Mr. Do-It-Yourself - developed in the wake of suburbanization. In addition to identifying trends within the dominant culture, contributors consider the experiences of ethnic and immigrant families, reassessing generational conflict in Italian Harlem, comparing the attitudes of male and female Mexican migrant workers in Kansas, and showing how Chinese immigrant women targeted for rescue by Presbyterian mission workers took advantage of the gap between Chinese and American culture to increase their leverage in family and marital relationships. A diverse compendium of family life, "Family and Society in American History" provides an intriguing commentary on the permeability of social structures and interpersonal behavior.
Buy Family and Society in American History book by Joseph M. Hawes from Australia's Online Bookstore, Boomerang Books.
Book DetailsISBN: 9780252068737
(228mm x 152mm x 21mm)
Pages: 360
Imprint: University of Illinois Press
Publisher: University of Illinois Press
Publish Date: 1-Jun-2001
Country of Publication: United States
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Fundraiser draws $600,000 for youth behavioral health services/
Yesterday's Invest in Youth Breakfast raised $600,000 for Youth Eastside Services (YES), an organization that provides mental health counseling, substance abuse treatment, and education and prevention programs for youth and families on Seattle's Eastside.
"We are so moved by this outpouring of support," said YES Executive Director Patti Skelton-McGougan. "This community of committed, caring donors is what makes our work possible."
Speakers included:
· KIRO 7 news anchor and Voice of the Seahawks Steve Raible
· Alaska Air Group Chairman and CEO Brad Tilden and his wife Danielle Tilden, whose career in youth-serving organizations spans over 25 years
· Seattle Seahawk Jermaine Kearse, who made a special appearance in support of YES
· YES Board of Trustees member Dan Faulker, a realtor and former client of YES
· Youth speaker Tallulah Gronseth, who recovered from substance abuse with YES' support
· Youth speaker Robert Santos, who is recovering from substance abuse with YES' support
· Basketball legend and philanthropist Lenny Wilkens
The money raised will support subsidized and free care to struggling families, as well as fund YES' education and prevention programs.
See photos and a wrap-up of the event at www.YouthEastsideServices.org.


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Möchtest du als deine Standardwährung festlegen oder nur für diese Sitzung behalten?
This guest did not leave comments about this hotel.
Location and how close it was to everything My brother inlaw got a room there when we arrived that was a lot bigger at a cheaper price
location. Beach access directly across the street. In the midst of boutiques, and restaurants. Easy access to beach trolley. No
Close to the bridge walk, beach and many souvenirs self-checked in was easy since I arrived after 9 Pm and they left a welcome letter with the gate security who helped me through out my stay I also asked for late check out which was for fee Not accessible to handicap as quoted and my room was in the second floor and there was no elevator
location location and nice big room
perfect room for q weekend get away, full kitchen, location
the people who worked there would bend over backwards for anything I'd need older room, and the door jam of my hotel room was half broken, and the key wouldn't really work, easy for someone to break in if they wanted to. Plus, people directly outside of my room in the patio area were smoking cigars and cigarettes
convenient dark and depressing room. were supposed to serve breakfast from 8:00 to 9:30. By the time I had to leave at 8:20, the breakfast room and office were still locked.
Location, cleanliness and wonderful staff.
Location, location, location plus top staff and a excellent restaurant.
Beautiful room - Great location - excellent A+
Located walking distance to everything you need? Friendly staff. We were traveling with another couple and plan on a return visit.
Staff is excellent. Very nice hotel.
The service and the amenities were great.
I liked the amenities and the location of the Resort. The beds sucked.. I stay in 4 and 5 star hotels only and for a Ritz the beds sucked, the sheets were not soft... and I always forget that the rate is inexpensive because they charge you mandatory resort fees per night at check out. Needless to say valet is $24 per day. I feel like I am flying on commercial airlines with the nickel and dimming. Just increase the price and make it all inclusive.
The pool and beach facility at Lido is perfect
Rooms were functional. Staff was well trained. An additional Resort FEE when checking in. It's NOT really a resort. And if it was , I would like to know about additional fee's in advance.
Clean, comfortable rooms, pool area nice I think Breakfast should be included for the price. Music at the bar area would be nice...
Great location for anything you wanted to do. Relax, Swim, Kaysk, paddle board, fish, go to the beach. All inclusive to do the above activities. Great pool bar. Friendly and helpful staff starting from your arrival at the front door until you leave. Close proximity to great restraunts, night life and cultural events. I liked everything. Nothing negative about this Hotel
The staff was very cordial and helpful. The room was quiet and very clean. Lots of activities. Hard to differentiate between those "free" amenities and those for which you are charged. Also not enough complimentary newspapers in the early morning.
Water backed up in the sink in our room. They were quick to repair but the smell remained in the room and was awful.
Staff were friendly and helpful. My room was clean and pleasant. Had a hard time regulating the room temperature.
It was quiet until morning....Do not get the rooms next to the stairway or help linen room unless they give yoy a discount. If you are in the back, no need to open your curtains because the view is unpleasing to the eye and will put you in foul mood.. It was quiet. Got the most...no USB outlets for my devices unacceptable !!!! The place needs to be updated . Checkout was easy... I think what I payed for the room was too much.... The location was good. I give this hotel a left vertical thumb .
We had a bad experience with another hotel the night before we arrived and the Hilton more than made up for the competitions mistakes. Everything was just as we expected it to be.
Great Staff. Bathtub filthy, shower-head from the fifties. Photos taken.


text:
Shaft Seal 5057-301, 9/16" Shaft Size, For use with salt chlorine generators, ozonators and regular pool and spa use, the 5057-30 will replace the item if the customer wants a Viton shaft seal. the 5057-30 is exactly the same seal, but it uses Viton rubber instead of the standard rubber.
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text:
I recently installled a Powernow on the air filtter side of my carb. The OEM part that it replaces had a hose connection that went to the AIS. I capped the hole to that AIS port and also capped the port hole that tee's into the hose line that goes to the port opening that is located between the carb and the engine which also connects to my hot start button. By doing a search in this forum as to disconnecting the AIS there was a number of ways but by plugging the hose that connected to the opening located between the carb and the engine I would not have to change my stock pilot jet so that is what I did.
My question is disconnecting both these lines cause me any potential problems? The bike start and runs well. I noticed that it does not idle as fast as it used to. I also noticed that now when I adjusted my fuel screw which seemed before to idle the fastest at three turns out now idles best when it is turned most all the way in. Closed to 1&1/2 turns out seems to idle about the same.
I have done all the free mods but have stayed with the WR timing. I installed a JD jetting kit and did what was recommended for riding a sea level, (red needle as I remember).
The bike seems to run pretty much the same as before but with better low end responce though it does not seem to rev out as well as it used to.
Any suggestion as to things I need to consider with what I have done?
Want to make sure I did not do something wrong or need to do something more. Thanks for whatever advice you can give.
Question Concerning AIS On 99 WR400.
Started by standup rider , Oct 02, 2006 08:37 AM
3 replies to this topic
Posted October 02, 2006 - 09:09 AM
There is no AIS on a 99 WR 400f, you must be talking about the ACV on the carb
Posted October 02, 2006 - 08:04 PM
The reason you had to turn in the fuel screw is because the hoses you blocked off is causing it to run rich. You need to replace the pilot air jet using the method you chose. The only hose you really need to block to the ACV is the one at the bottom that T's in with the hot start. I took the T out and hooked the hose from the hot start direct to the engine. And plugged the one at the ACV just to keep dirt out of it. That is the hose that actually opperates the device. The ACV is a valve that is normally open connecting the top two hoses, high vaccum from a throttle chop closes the valve to enrichen the mixture to prevent decel popping.
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Product Description
Philips Dry Iron HD1172/01
Super power dry iron that works on 750 w and gives faster ironing. There is a cord winder which keeps the cord wounded easily and packed. The entire cord can be smoothly wound around heel rest. This Dry Iron will provide you safe ironing and easy ironing. This electric home appliance is designed to give perfect ironing and that too just anytime. It is light in weight too.