The invention relates to a method and system for generating droplets of an aqueous solution on a microfluidic chip with an air continuous phase. Specifically, the droplet generator according to the present invention is integrated into a microfluidic chip to generate and introduce droplets of an aqueous solution into the microfluidic chip. The droplets travelling in a network of chip channels may be captured in on-chip traps in a manner defined by hydrodynamic resistances of chip channels. A biological reaction may be performed on a droplet trapped on the microfluidic chip.

Field of the Invention
The invention relates to a droplet generator incorporated into a microfluidic chip. Specifically, the droplet generator generates droplets of an aqueous solution on a microfluidic chip with an air continuous phase.
Discussion of the Background
The detection of nucleic acids and the ability to perform biochemical assays and the like is central to medicine, forensic science, industrial processing, crop and animal breeding, and many other fields. The ability to detect disease conditions (e.g., cancer), infectious organisms (e.g., HIV), genetic lineage, genetic markers, and the like, is ubiquitous technology for disease diagnosis and prognosis, marker assisted selection, correct identification of crime scene features, the ability to propagate industrial organisms and many other techniques. Determination of the integrity of a nucleic acid of interest can be relevant to the pathology of an infection or cancer. Other biochemical assays, including be detection of proteins or other markers in a sample are relevant both to disease and disorder detection as well as environmental safety.
One of the most powerful and basic technologies to detect small quantities of nucleic acids is to replicate some or all of a nucleic acid sequence many times, and then analyze the amplification products. Polymerase Chain Reaction ("PCR") is perhaps the most well-known of a number of different amplification techniques.
PCR is a powerful technique for amplifying short sections of DNA. With PCR, one can quickly produce millions of copies of DNA starting from a single template DNA molecule. PCR includes a three phase temperature cycle of denaturation of DNA into single strands, annealing of primers to the denatured strands, and extension of the primers by a thermostable DNA polymerase enzyme. This cycle is repeated so that there are enough copies of the amplified DNA to be detected and analyzed. For general details concerning PCR, see Sambrook and Russell, Molecular Cloning—A Laboratory Manual (3rd Ed.), Vols. 1-3, Cold Spring Harbor Laboratory, Cold Spring Harbor, N.Y. (2000); Current Protocols in Molecular Biology, F. M. Ausubel et al., eds., Current Protocols, a joint venture between Greene Publishing Associates, Inc. and John Wiley & Sons, Inc., (supplemented through 2005) and PCR Protocols A Guide to Methods and Applications, M. A. Innis et at, eds., Academic Press Inc. San Diego, Calif. (1990),
Microfluidic chips are being developed for "lab-on-chip" devices to perform biochemical assays including in vitro diagnostic testing. The largest growth area is in molecular biology where DNA amplification is performed in the sealed channels of the chip. Optical detection devices are commonly used to measure the increasing amplicon product over time (Real Time PCR) and/or to perform a thermal melt to identify the presence of a specific genotype (High Resolution Thermal Melt).
Droplet PCR is well known in the art, and has previously taken the form of an aqueous droplet surrounded by an immiscible fluid, such as an oil, a fluorinated liquid, or any other non-aqueous or hydrophobic solvent. However, droplet PCR using an oil phase has some drawbacks. Use of a water-in-oil droplet requires additional materials in comparison to standard PCR (i.e., oils, surfactants, etc.), and proteins can be denatured at the oil-water interface due to their contact with the oil, which can lead to irreversible protein adsorption onto the surface of a microfluidic channel. Further, the viscosity of oil requires slower flowrates than can be achieved with other materials.
Droplet PCR has particularly been used in lab-on-chip applications, both in flow-through microfluidic channels (biochemical reactions may be performed on the samples either while stationary or while flowing through the channel) and in microfluidic systems incorporating traps in which the droplets can be contained in the microfluidic system. For instance, hydrodynamic traps are described in Bithi and Vanapaili ("Behavior of a train of droplets in a fluidic network with hydrodynamic traps", Biomicrofluidies 4, 044110 (2010)).
Bithi and Vanapalli describe the use of both passive and active methods for trapping and storing droplets in microfluidic systems. In some instances, passive trapping is preferred as it is more scalable to allow multiplexing than active trapping may be. Bithi and Vanapalli describe two methods of passive trapping, direct and indirect trapping, which are based on the hydrodynamic resistance of an upper and lower branch of a microfluidic system containing a repetitive series of loops, as is shown in FIG. 1. As noted in FIG. 1, this system of trapping droplets is designed to work with a water-in-oil system, as described above. The effectiveness of trapping droplets in such a system is dependent on droplet size and droplet spacing, requiring precise control of the water-in-oil droplet formation Oil flow rate is a key factor in the performance of such a system, and system paramaters would need to be optimized for the specific oil or other surfactant used in creating the droplets.
Accordingly, a need exists in the art for alternate systems and methods of preparing droplets for use on microfluidic chips that overcome these drawbacks.

Generation and trapping of aqueous droplets in a microfluidic chip with an air continuous phase


A wiring arrangement of a wiring harness 41 at an underfloor 34 is finished by arranging a connecting member 43 to a position of a through-hole 35, by extending a sheath 48 on the underfloor 34 parallel to the underfloor 34 while the sheath 48 is received in a wire protect member 44, and by fixing a terminal fixing member 45 and the wire protecting member 44 to the underfloor 34. After such a wiring arrangement, the wiring harness 41 is electrically connected to a junction block 31 around the through-hole 35 by mounting a battery 25 or the like.

1. Field of the Invention
The present invention relates to a wiring harness arranged on an underfloor at a ground side of a floor panel of a vehicle, and to a wiring structure of the wiring harness.
2. Description of the Related Art
A later-described Patent Document 1 discloses a wiring structure of a wiring harness used in a hybrid vehicle or an electric vehicle. Hereinafter an embodiment of the conventional wiring harness will be explained with reference to FIG. 4.
In FIG. 4, a hybrid vehicle 1 includes a cabin 6 having a driver's seat 3, an assistant driver's seat 4, and a rear seat 5 behind an engine room 2. An engine 7, a motor, 8, and an inverter 9 are mounted on an engine room 2. A motor cable 10 connects the motor 8 with the inverter 9. One end of a wiring harness 11 is connected to the inverter 9. The other end of the wiring harness 11 is connected to a battery 12 (battery pack) interposed between the driver's seat 3 and the assistant driver's seat 4 in the cabin 6.
The wiring harness 11 is composed of two high-voltage cables 13, and a terminal 14 is provided at an end of each high-voltage cable 13. The terminal 14 is fixed to a terminal block 15 provided at a rear of the battery 12 (or a junction block interposed between the terminal 14 and the battery 12) with a bolt 16. The wiring harness 11 is arranged on an underfloor at a ground side of a floor panel 17, and guided into the cabin 6 from a through-hole 18 of the floor panel 17. The through-hole 18 is open at a rear of the battery, and the wiring harness 11 guided into the cabin 6 is bent forward.
[Patent Document 1] JP, A, 2007-290616
According to the conventional technique, there is a problem that the workability of arranging the wiring harness 11 is decreased because it is necessary to sequentially operate to insert the other end of the wiring harness 11 into the through-hole 18 of the floor panel 17 and to bent the wiring harness 11 after the insertion of the wiring harness 11. Further, according to the conventional technique, because the high-voltage cable 13 composing the wiring harness 11 is thick, there is a problem that the bending operation is not easy.
Further, according to the conventional technique, because the wiring harness 11 is guided into the cabin 6, there is a problem that the whole length of the wiring harness 11 becomes long, and a cost of the wiring harness 11 is increased. Further, according to the conventional technique, because the wiring harness 11 is guided into the cabin 6, then bended forward, there is a problem that a space S1 for receiving the bending part is needed. To save the space S1 makes a problem that a foot space of a crew member sitting on the rear seat 5 becomes narrower.
Further, according to the conventional technique, when the thick wiring harness 11 which is hard to be bent is bent from the underfloor to the through-hole 18, the wiring harness 11 is separated away from the floor panel 17 at least near the through-hole 18, and a space S2 is generated at the underfloor side. Therefore, there is a problem that damage may occur because the wiring harness 11 is disposed close to the ground.
Further, according to the conventional technique, when the space S2 is made smaller, because the wiring harness 11 should be bent, the through-hole 18 of the floor panel 17 should be relatively larger. Therefore, there is a problem that a waterproof structure should be larger, and there is a problem that a cost of the larger waterproof structure is increased.
Accordingly, an object of the present invention is to provide a wiring harness and a method of providing a wiring structure of the wiring harness which is able to increase workability, save space, and reduce cost, and able to provide a low-profile arrangement.

Wiring harness and a method of providing wiring structure of the same


A method and system for extracting rib centerlines in a 3D volume, such as a 3D computed tomography (CT) volume, is disclosed. Rib centerline voxels are detected in the 3D volume using a learning based detector. Rib centerlines or the whole rib cage are then extracted by matching a template of rib centerlines for the whole rib cage to the 3D volume based on the detected rib centerline voxels. Each of the extracted rib centerlines are then individually refined using an active contour model.

The present invention relates to rib centerline line extraction in 3D medical image data, such as 3D computed tomography (CT) scans, and more particularly to automatic rib centerline extraction using learning based deformable template matching.
Locating rib metastases and fractures in chest CT scans typically involves reading hundreds of axial CT slices to visually track changes in rib cross-section area. Accordingly, manual reading of CT scans is rather time consuming and rib anomalies are frequently missed in practice due to human error. Automatic extraction of rib anatomical centerlines can be used to enhance the visualization of an unfolded rib cage, which can make routine bone reading tasks more efficient and effective for the radiologists. Extracted and labeled rib centerlines can also serve as a reference to localize organs, register pathologies, and guide correspondence between serial thoracic CT scans for interval change analysis. In addition, the derived information of the rib geometry can assist with the rib cage fracture fixation surgeries.
Despite the above described clinical importance, automatic detection and labeling of ribs in CT scans remains a challenging task. Most conventional methods model the ribs as elongated tubular structures and employ Hessian or structure tensor eigen-system analysis for ridge voxel detection. However, these algorithms are typically computationally expensive and may not achieve consistent results in all patients. FIG. 1 illustrates examples of different rib cross sections in different patients. As shown in FIG. 1, image (b) shows rib cross sections 104 having more clear dark marrow than the rib cross-sections 102 shown in image (a). In many cases, the rib marrow may be darker than the rib boundary; thus the rib center points may not be consistently detected as ridge voxels. To construct a rib centerline, tracking based methods, such as Kalman filtering, are typically used to trace detected rib center points from one slice to the next. However, some conventional tracking based methods require manual initial seed points, and such point to point tracking methods are highly sensitive to local ambiguities or discontinuities posed by rib pathologies like fractures, which may be of the most interest to radiologists. FIG. 2 illustrates examples of different rib pathologies, which can lead to inaccurate rib centerlines in tracing bade methods. As illustrated in FIG. 2, image (a) shows ribs with missing rib segments 202 and image (b) shows ribs with rib metastases 204. Furthermore, in convention rib tracing algorithms, each rib is individually detected and traced; hence rib labeling requires a separate heuristic method.

Method and system for automatic rib centerline extraction using learning based deformable template matching


The present invention provides a process for the preparation of peptides which have or side-chains containing an alkyl- or dialkyl-substituted guanidinyl group or a imidazinylamino or tetrahydropyrimidinylamino group. The process provides higher overall yields of peptide product by permitting the synthesis of the entire peptide chain prior to modification of the side-chain to introduce the groups.

Peptides having alkyl- and dialkylguanidinyl-containing side chains or imidazolinylamino- or tetrahydropyrimidinylamino-containing side chains are frequently useful as pharmaceutical agents. Typically these peptides have been produced by first synthesizing the individual amino acids containing the desired side-chain modification, protecting the reactive side-chain groups in the various amino acids, and subsequently linking the individual modified amino acids to a resin form a peptide using conventional methods. This conventional method is the solid phase method set forth in Merrifield, R. B. J. Am Chem. Soc. 1963, 85, 2149. This process of first synthesizing the protected amino acids containing the desired side chain modification and then synthesizing the peptide is typically a difficult and expensive one, often yielding relatively small amounts of the desired peptide. There is thus a need in the an for a process whereby peptides containing imidazolinylamino- or tetrahydropyrimidinylamino-containing side chains or alkylguanidinyl or dialkylguanidinyl-containing side chains can be more readily introduced into peptides using solid phase peptide synthesis techniques.

Process for producing peptides with side chains containing imidazolinylamino, tetrahydropyrimidinylamino, or alkylguanidinyl groups


Disclosed is a laminate for non-aqueous secondary battery which includes a functional layer that has superior transferability and may exert high function. The disclosed laminate includes a releasable substrate having a water contact angle of 70° or more, and a functional layer on the releasable substrate. The functional layer includes organic particles and a binder. The organic particles each have a core-shell structure having a core and a shell that partially covers an outer surface of the core. The core is made of polymer having a degree of swelling in electrolysis solution of 5 times or more to 30 times or less. The shell is made of polymer having a degree of swelling in electrolysis solution of greater than 1 time to 4 times or less.

Non-aqueous secondary batteries (hereinafter occasionally simply referred to as "secondary batteries") such as lithium ion secondary batteries are small and light, high in energy density, and capable of repeated cycles of charge and discharge. For such characteristics, secondary batteries are used in a wide variety of applications. A secondary battery generally includes non-aqueous secondary battery members such as a positive electrode, a negative electrode, and a separator for separating the positive electrode and negative electrode from each other to prevent a short-circuit between them.
In recent years, secondary battery members have been used that include a substrate for non-aqueous secondary battery, and a functional layer (e.g., a porous membrane layer for improving heat resistance and strength, or an adhesive layer for improving adhesion between secondary battery members) formed on the substrate using a slurry composition for non-aqueous secondary battery functional layer (hereinafter occasionally simply referred to as a "functional layer composition") containing a binder component and a dispersion medium such as water.
Specific examples of secondary battery members that have been used in the art are electrodes that include an electrode substrate, which has an electrode mixed material layer provided on a current collector, and a functional layer formed on the electrode substrate; and separators that include a separator substrate and a functional layer formed on the separator substrate (see, e.g., PTLS 1 and 2).
PTL 1 discloses a porous membrane layer to be formed on an electrode substrate or separator substrate and reports that a porous membrane layer that comprises a binder (made of polymer particles having heterogeneous phase structure consisting of a core layer composed of a polymer of a vinyl monomer component, and of a shell layer composed of a polymer of a hydrophilic functional group-containing monomer component) and non-conductive particles exhibits superior strength as well as exerts high lithium ion diffusivity in lithium ion secondary batteries.
PTL 2 reports that a separator that includes a separator substrate, a porous membrane layer containing non-conductive particles and binder formed on the separator substrate, and an adhesive layer containing a particulate polymer having a specific glass-transition temperature formed on the porous membrane layer exhibits good adhesion to electrodes allowing a secondary battery to exert superior high-temperature cycle characteristics and rate characteristics.

Laminate for non-aqueous secondary battery, and method for manufacturing non-aqueous secondary battery member


A multilayered reflector structure deposited on the light emitting surface of a semiconductor electroluminescent device and consecutively comprising a layer of low refractive index material, a layer of intermediate refractive index material and a layer of high refractive index material. Ablative means remove and form an aperture in the outer high index layer at the region of optical radiation emission from said device whereby the level of reflectivity is highest at the center of the aperture as compared to structure regions adjacent to the aperture. In this manner, fundamental mode stabilization may be achieved. Also disclosed is a nonablated three layered reflector structure.

The present invention relates to apertured and unapertured structures as applied to at least one light emitting surface of semiconductor electroluminescent devices, such as, injection lasers or light emitting diodes (LEDs).
Heretofore, the suggestion has been made to apply multilayered structures to at least one facet surface of an electroluminescent device to provide a high level of reflectivity. If the reflectivity level is high at one of the facet surfaces, the current threshold of the device is reduced because more of the optical radiation is reflected back into optical radiation cavity of the device. Such a multilayered reflector structures are disclosed in U.S. Pat. Nos. 4,092,659 and 4,147,409.
The drawback in the employment of these types of reflectors is that, although reflectivity at one facet surface may be substantially increased, lowering current thresholds, mode stabilization is not achieved but rather undesirably enhanced toward unstabilization.
Furthermore, conventional gain-guided semiconductor injection lasers with known current confinement means exhibit nonlinearities in the light output power verses laser current characteristics. Abrupt changes in these characteristics are referred to as "kinks". Kinks can occur for contact stripe lasers at lower levels of a few milliwatts with contact stripe widths on the order of 8 um or wider.
The presence of kinks is now understood to result from spatial hole burning in the injected carrier profile which, in turn, causes the laser mode to shift laterally along the p-n junction of the injection laser. In the absence of a built-in mode guiding mechanism, such as, for example, curved or angled stripe geometry or a channeled substrate, the lateral mode shift produces a kink in the optical power output.
By providing a spatially selective reflector on at least one facet surface of the device, albeit an injection laser or LED, a higher central reflective region can be created at the point of light emission from the device to thereby increase mode stability and, as a result, increase the power level at which these output kinks occur.
What is proposed here is a multilayered reflector which, by means of an ablative process, will produce a reflector structure that has relatively high modal reflectivity at the center of optical radiation emission from the device, which reflectivity decreases radially from the center of such emission.
The employment of multilayered ablatable structures on at least one facet of such devices is not new in the art. U.S. Pat. No. 3,843,401 discloses an ablatable multilayered structure for determining the location of the p-n junction of a solid state laser device and causing the optical radiation to be emitted from a restricted region at the junction of the device.

Apertured and unapertured reflector structures for electroluminescent devices


In a method of enhancing the dry grinding efficiency of petcoke including adding additives to the petcoke and dry grinding the petcoke together with the additives. The additives may include a combination of at least one organic additive and at least one inorganic additive.

Petroleum coke (petcoke) is a carbonaceous solid derived from oil refinery coker units or other cracking processes. It is a by-product from oil refineries and is mainly composed of carbon. Fuel grade petcoke also contains high levels of sulphur. There has been considerable interest in petcoke for many years, as it is normally cheaper than coal and has a very high calorific value. There are three types of petcoke, which are been produced depending on the process of production. There exist delayed, fluid and flexi coking with delayed coking constituting over 90% of the total production. All three types of petcoke have higher calorific values than coal and contain less volatile matter and ash.
The main uses of petcoke are as energy source for cement production, power generation and iron and steel production. There are many constraints for effective utilization of petcoke as a fuel in cement industry. One of these constraints is the hardness of petcoke, its hardness is greater than coal and hence the power consumption of the grinding systems is increased. Due to its low content of volatile matter, petcoke has poor ignition and burnout characteristics. Therefore, petcoke has to be ground to a much higher fineness than conventional fuels in order to allow its use as fuel in cement kilns or calciners. However, petcoke is difficult to grind, primarily because of its high carbon content that has a lubricating effect, so that petcoke shows a lesser tendency towards comminution by attrition and abrasion in the grinding systems.
A further problem associated with the firing of petcoke in cement kilns or calciners is its high sulphur content. Due to the high levels of excess air required for petcoke combustion the SO2 emissions are relatively high. In the course of the clinkering process SO2 is absorbed into the cement clinker as sulphates. Due to the high sulphur content operational issues also can arise during petcoke firing in cement kilns, such as blockage at kiln inlets and in preheater and precalciner cyclones.
U.S. Pat. No. 4,162,044 discloses a process for grinding of coal or ores in a liquid medium with use of a grinding aid comprising an anionic polyelectrolyte derived from polyacrylic acid in order to increase the grinding efficiency.
U.S. Pat. No. 4,136,830 discloses a process for grinding coal or ores containing metal values comprising carrying out said grinding in a liquid medium and with a grinding aid comprising copolymers or salts of copolymers of styrene with maleic anhydride, in order to increase the grinding efficiency.

Method of enhancing the dry grinding efficiency of petcoke


A planter for retaining gravel and landscaping effects in underwater settings such as an aquarium is disclosed. The invention comprises a plurality of retaining walls disposed in an upstanding spaced apart relationship for forming a plurality of landscaping sections with each section having a different height from every other section for defining a terrace relationship with the adjacent retaining walls. A plurality of elongated spacers are disposed in paired releasable communication with the retaining walls for maintaining the spaced apart relationship between the adjacent retaining walls. Each retaining wall further has a plurality of apertures adapted for urging water flow from one landscaping section to the next lowermost adjacent landscaping section, and a second plurality of apertures adapted for urging cooperative engagement between adjacent elongated spacers. A base wall is disposed in an upstanding orientation and in a spaced apart relationship with the lowermost landscaping section retaining wall and a pump is provided for pumping the water from the aquarium to the highestmost landscaping section.

1. Field of the Invention
The present invention relates to a new and improved underwater planter and more particularly, pertains to an underwater planter having a plurality of retaining walls in a terraced relationship for maintaining the three dimensional landscaping vistas that the hobbyist creates by restricting animal access to the planter.
2. Description of the Prior Art
The use of underwater stabilization systems using rocks, driftwood and plants is known in the prior art. More specifically, underwater stabilization systems using rocks, driftwood and plants heretofore devised having many parts and being difficult to operate and maintain in conditions typically found in aquatic situations requiring the stabilization of visual aesthetic landscaping effects and in particular, maintaining the visual aesthetic landscaping effects in spite of the constant movement of the landscaping by the semi-aquatic animals when they move across the landscaping, or when they dig into the landscaping in search of food are known to consist basically of familiar, expected, and obvious structural configurations, notwithstanding the myriad of designs encompassed by the crowded prior art which has been developed for the fulfillment of countless objectives and requirements.
The prior art discloses a large number of underwater stabilization systems using rocks, driftwood and plants. By way of example, U.S. Pat. No. Des. 268,607 issued to Malik appears to disclose an aquarium filter.
U.S. Pat. No. Des. 317,966 issued to Willinger appears to disclose an aquarium filter.
U.S. Pat. No. 5,006,230 issued to Votive, III et al. discloses a dual action aquarium filtration system having intake means for aquarium water, pre-filter means, and water transfer means.
U.S. Pat. No. 5,167,607 issued to Thiemer et al. discloses a filter for an aquarium having a bottom chamber and a filter compartment for a filter material located above the bottom chamber. Water is supplied from above so as to pass through the filter compartment to the bottom of the chamber.
U.S. Pat. No. 5,171,438 issued to Korcz discloses an aquarium filtration system using biological and mechanical means. The system has the capability to also include chemical filtration.
U.S. Pat. No. 5,171,437 issued to Fletcher, Sr. discloses an intake aquarium filter medium for immersion within the aquarium tank and having a permeable synthetic filter material for urging movement of water therethrough for causing air bubbles to collect within the filter.
In this respect, the underwater planter according to the present invention substantially departs from the conventional concepts and designs of the prior art, and in doing so provides an apparatus primarily developed for the purpose of an underwater planter having a plurality of retaining walls in a terraced relationship for maintaining the three dimensional landscaping vistas that the hobbyist creates by restricting animal access to the planter.
It is therefore an object of the present invention to provide a new and improved underwater planter which has all the advantages of the prior art underwater stabilization systems using rocks, driftwood and plants and none of the disadvantages.
It is another object of the present invention to provide a new and improved underwater planter which may be easily and efficiently manufactured and marketed.
It is a further object of the present invention to provide a new and improved underwater planter which is of a durable and reliable construction.
An even further object of the present invention is to provide a new and improved underwater planter which is susceptible of a low cost of manufacture with regard to both materials and labor, and which accordingly is then susceptible of low prices of sale to the consuming public, thereby making such a underwater planter economically available to the buying public.
Still yet another object of the present invention is to provide a new and improved underwater planter which provides in the apparatuses and methods of the prior art some of the advantages thereof, while simultaneously overcoming some of the disadvantages normally associated therewith.
Even still another object of the present invention is to provide an underwater planter having a plurality of retaining walls in a terraced relationship for maintaining the three dimensional landscaping vistas that the hobbyist creates by restricting animal access to the planter.
Lastly, it is an object of the present invention to provide a planter for retaining gravel and landscaping effects in underwater settings comprising a plurality of retaining walls disposed in an upstanding spaced apart relationship for forming a plurality of landscaping sections. A plurality of elongated spacers are disposed in paired releasable communication with the retaining walls for maintaining the spaced apart relationship between the adjacent retaining walls. A base wall is disposed in an upstanding orientation and in a spaced apart relationship with the lowermost landscaping section retaining wall. Means are provided for pumping the water from the aquarium to the highestmost landscaping section.
These together with other objects of the invention, along with the various features of novelty which characterize the invention, are pointed out with particularity in the claims annexed to and forming a part of this disclosure. For a better understanding of the invention, its operating advantages and the specific objects attained by its uses, reference should be had to the accompanying drawings and descriptive matter in which there is illustrated preferred embodiments of the invention.
Therefore, it can be appreciated that there exists a continuing need for a new and improved underwater planter which can be used for and more particular, an underwater planter having a plurality of retaining walls in a terraced relationship for maintaining the three dimensional landscaping vistas that the hobbyist creates by restricting animal access to the planter In this regard, the present invention substantially fulfills this need.


A method and apparatus for depositing a layer of aggregate material over a large area of land, for example, in preparing a new land fill waste-disposal site. An elongated, endless-belt conveyor is positioned across the width of the site and is supported upon a plurality of longitudinally spaced tractor units which are adapted to move the entire conveyor laterally across the length of the site. Aggregate material is supplied to one end of the conveyor and is conveyed toward the opposite end thereof. A mobile discharge unit through which the endless-belt passes, is moveable longitudinally along the conveyor to discharge the aggregate from the endless belt continuously as the discharge unit travels between the ends of the conveyor. The discharged material is continuously conveyed laterally away from the conveyor, deposited upon a portion of the site and spread along a strip of the land area laterally adjacent to the conveyor. After the strip has been covered with aggregate adjacent the conveyor along the entire width of the site, the tractor units move the entire conveyor laterally over the finished strip, and the process is repeated until the entire site is covered.

The invention relates to a method and apparatus for depositing a layer of aggregate material of approximately consistent depth over a large area of land. While the invention may be utilized in laying down a layer of sand or gravel for constructing a large parking lot or other large construction site in an economical manner, the invention has particular utility and provides particular advantages in preparing a new land fill waste-disposal site economically and in an environmentally responsible manner. Other applications for the present invention may be found in any task where aggregate material is to be deposited over a site containing areas which must not be subjected to heavy loads or where features of the terrain such as deep ditches or the like must be spanned or otherwise dealt with. Another possible application is surface mine reclamation where large quantities of aggregate material such as soil materials must be spread over a large area economically.
In the case of preparing a large area of land for a new land fill waste-disposal site, it is common to deposit over the entire site a first layer of sealing clay, then a layer of sand, another layer of clay and over these deposited layers the entire site is covered with a plastic liner of, for example, high-density polyethylene to prevent as much as possible liquids from the waste from leaching into the land and possibly contaminating underground water. Over the plastic liner a leachate collection system is located consisting of perforated plastic pipe immediately surrounded by a filter fabric and rock. The land is graded so that liquid will flow over the plastic liner to the leachate collection system where it is collected and properly disposed of. It is then conventional to deposit a layer of sand of about twelve to about eighteen inches in depth over the entire plastic liner and leachate collection system and thus over the entire land fill site. Conventional methods of laying down a layer of aggregate such as the sand are not well suited to this job. For example, a loaded dump truck moving across the plastic while depositing a trailing stream of sand can be quite destructive to the plastic liner. Even if the dump truck were to back over the sand as it is deposited from the rear of the truck, the massive weight of the truck may present problems to the integrity of the plastic liner and a slight detour from the proper path would lead the truck directly onto the liner.
Another conventional method is to dump the sand at the edge of the site and have a bull dozer spread the sand over the liner such that the dozer always tracks over sand which it has pushed ahead and spread. This method is disadvantageous in that it is very difficult to economically produce a layer of sand of consistent depth and the heavy equipment required, and the number of passes required, increase the probability of plastic liner and leachate collection system degradation. Also the great weight of the sand piles initially being shifted across areas of the liner may cause tearing of the liner. A great degree of operator skill would also be necessary. Further, in order to perform the conventional methods using large dump trucks and bulldozers, large numbers of expensive man-hours must be expended as well as the use of large numbers of very expensive heavy machinery. Due to the large number of men and machines used in conventional methods scheduling of truck arrivals and equipment usage can be an extremely important part of the job causing heightened probabilities of down time and wasted machine-hours and man-hours. As compared to the present invention, conventional methods may also use a greater amount of fuel.

Method and apparatus for depositing a layer of aggregate material


A positive displacement rotary pump is provided for use in circulating a viscous product at high pressures. The pump includes a housing having a product inlet and a product outlet communicating with an interior cavity. One wall of the cavity is defined by a removable cover. A pair of spaced substantially parallel shafts extends through a wall of the cavity opposite the cover wall. One end of each shaft is supported by the cover. A pair of meshing rotors is locked on the shafts and disposed uniformly within the cavity. The endface of each rotor adjacent the removable cover has a substantial countersunk portion. Bearing means, substantially isolated from the product, is disposed within each rotor endface countersunk portion and supportingly engages a segment of the rotor shaft one end. At least a portion of each bearing means is located between planes defined by the surfaces of the cover and the wall opposite thereto which coacts to form the cavity. Means for supporting the bearing means is removably mounted on the cover.

Various positive displacement rotary pumps have heretofore been provided for circulating various viscosity products; however, such pumps have been ineffective in handling such products at pressures within the range of 200-350 psi. When operating within such a pressure range, such pumps have been beset with one or more of the following shortcomings: (a) serious shaft deflection occurs; (b) an inordinate amount of bearing wear results; (c) serious galling between the rotors and the cavity surfaces; (d) the rotors are higly susceptible to product corrosion and product abrasiveness; (e) the shafts are not effectively isolated from the product thereby causing the potential for serious contamination problems; and (f) makes disassembly of the pump for cleaning and maintenance a difficult and time-consuming operation.

Positive displacement rotary pump with bearings in countersunk portions of the rotors


The disclosure relates to a selective printing apparatus adapted to be used in a hand held labeler. The apparatus includes selectively settable printing members driven by wheels coupled by gearing with read wheels for indicating the selected data to be printed. The read and print wheels are driven by a manually movable, shiftable and rotatable selector shaft. The print wheels are detented and the selector shaft is detented within holes in the print wheels. An indicator slidably mounted by a stationary frame is coupled to the selector shaft through a lost-motion connection to enable the print head to move between printing and non-printing positions.

1. Field of the Invention
This invention relates to the art of selective printing apparatus.
2. Brief Description of the Prior Art
Various prior art U.S. Pat. Nos. 3,330,207 to De Man dated July 11, 1967; 3,886,862 to Hamisch, Jr. dated June 3, 1975; 3,908,543 to Wirth dated Sept. 30, 1975; 3,968,745 to Hamisch, Jr. dated July 13, 1976; 3,972,281 to Sams dated Aug. 3, 1976; and 4,055,118 to Yo Sato dated Oct. 25, 1977; and West German Offenlegungsschrift No. 2,350,537 are made of record.


The presently disclosed and/or claimed inventive concept(s) relates generally to oxidative oxidized reaction products made from the mechanocatalytic oxidative depolymerization of lignin. More particularly, but without limitation, the mechanocatalytic oxidative depolymerization of lignin is performed in a non-aqueous/non-solvent based and solvent-free process, i.e., via a solid-solid mechanocatalytic oxidative reaction methodology. In one particular embodiment, the process of making such oxidative oxidized reaction products includes, without limitation, the step of mechanocatalytically reacting an oxidation catalyst with lignin or a lignin-containing material. The oxidative reaction products obtained from the process include, for example, at least one of vanillin, and syringealdehyde, vanillic acid, and syringic acid.

1. Field of the Inventive Concept(s)
The presently disclosed and/or claimed inventive concept(s) relates generally to oxidized reaction products made from the mechanocatalytic oxidative depolymerization of lignin. More particularly, but without limitation, the mechanocatalytic oxidative depolymerization of lignin is performed in a non-aqueous and solvent-free process, i.e., via a solid-solid mechanocatalytic oxidative reaction methodology. In one particular embodiment, the process of making such oxidized reaction products includes, without limitation, the step of mechanocatalytically reacting an oxidation catalyst with lignin or a lignin-containing material. The oxidized reaction products obtained from the process include, for example, at least one of vanillin, syringealdehyde, vanillic acid, and syringic acid.
2. Background of the Inventive Concept(s)
The conversion of lignocellulosic biomass represents a potentially rich source of aromatic compounds and complete depolymerization of lignin within the lignocellulosic biomass can produce salable products such as vanillin, syringealdehyde, vanillic acid, syringic acid, and specialty chemicals that use these compounds as precursor molecules. Markets for these biomass-based materials will expand as demand grows for non-petroleum sourced materials, for example. Current production methods for the extraction of vanillin from Kraft liquor, for example, produce 160 kg of caustic waste for every kilogram of vanillin produced. Profitability can be increased and environmental concerns can be lessened by the development of a scalable process that foregoes such traditional caustic processes for the conversion of biomass materials.
Lignin is a complex chemical compound (shown in FIG. 1) commonly derived from wood as a byproduct of the pulp industry and is an integral part of the secondary cell walls of plants and some algae. It is one of the most abundant organic polymers on Earth, exceeded only by cellulose, embodying approximately 30% of non-fossil organic carbon, and constituting from a quarter to a third of the dry mass of wood. As a biopolymer, lignin is unusual because of its heterogeneity and lack of a defined primary structure. Its most commonly noted function is the support through strengthening of wood (xylem cells) in trees. Global production of lignin is around 1.1 million metric tons per year and is used in a wide range of low volume, niche applications where the form of lignin, but not its quality, is important.
Lignin is a cross-linked racemic macromolecule with molecular masses in excess of 10,000. It is relatively hydrophobic and aromatic in nature. The degree of polymerization in nature is difficult to measure since it is fragmented during extraction, and the molecule consists of various types of substructures that appear to repeat in a haphazard manner (as shown in FIG. 1). There are three monolignol monomers that are methoxylated to various degrees: p-coumaryl alcohol, coniferyl alcohol, and sinapyl alcohol. These lignols are incorporated into lignin in the form of the phenylpropanoids p-hydroxyphenyl (H), guaiacyl (G), and syringyl (S), respectively. Gymnosperms have a lignin content that consists almost entirely of G with small quantities of H, the lignin content of dicotyledonous angiosperms is mostly a mixture of G and S (with very little H), and monocotyledonous lignin is a mixture of all three. Many grasses have mostly G type lignin structures, while some palms have mainly S type lignin structures. The type and amount of lignin depolymerization products (e.g., oxidized reaction products) are dependent on the type and/or amount of a particular type of lignin in the biomass (i.e., H, G, and/or S). That is, the available percentage of precursors in the lignin structure strictly determines the formation of phenolic compounds such as vanillin or syringealdehyde. Lignin is especially useful in producing phenolic aldehydes as it requires fewer transformations or chemical treatments. For example, Sun et al., (2000) found that a yield of about 50 to 59.7% syringaldehyde and vanillin in equal proportions of the total phenolic aldehydes was obtained via nitrobenzene oxidation from lignin extracted from rice straw.
Biodegradation of lignin is a prerequisite for processing biofuel from plant raw materials. Lignin is indigestible by animal enzymes, but some fungi and bacteria are able to secrete ligninases (also named lignases) that are able to inefficiently and non-economically biodegrade the lignin polymer. As such, the presence of lignin within cellulosic or hemicellulosic structures is associated with reduced digestibility of the overall plant biomass.
Vanillin is a phenolic aldehyde having the molecular formula C8H8O3 (shown in FIG. 2). Its functional groups include aldehyde, ether, and phenol. It is the primary component of the extract of the vanilla bean. Synthetic vanillin, instead of natural vanilla extract, is sometimes used as a flavoring agent in foods, beverages, and pharmaceuticals. Natural "vanilla extract" is a mixture of several hundred different compounds in addition to vanillin. Artificial vanilla flavoring, on the other hand, is a solution of pure vanillin, usually of synthetic origin.
Due to the scarcity and expense of natural vanilla extract, there has long been interest in the synthetic preparation of its predominant component vanillin. The first commercial synthesis of vanillin began with the more readily available natural compound eugenol. Typically, artificial vanillin is made either from guaiacol or from lignin. Lignin-based artificial vanilla flavoring is alleged to have a richer flavor profile than oil-based flavoring; the difference is most likely due to the presence of acetovanillone in the lignin-derived product, an impurity not found in vanillin synthesized from guaiacol. Synthetic vanillin became significantly more available in the 1930s, when production began using the lignin-containing waste produced by the sulfite pulping process for preparing wood pulp for the paper industry. While some vanillin is still made from lignin wastes, most synthetic vanillin is today synthesized in a two-step process from the petrochemical precursors guaiacol and glyoxylic acid.
Several routes exist for synthesizing vanillin from guaiacol. At present, the most significant of these is a two-step process practiced by Rhodia since the 1970s, in which guaiacol reacts with glyoxylic acid by electrophilic aromatic substitution. The resulting vanillylmandelic acid is then converted via 4-Hydroxy-3-methoxyphenylglyoxylic acid to vanillin by oxidative decarboxylation.
The largest use of vanillin is as a flavoring, usually in sweet foods. The ice cream and chocolate industries together comprise 75% of the market for vanillin as a flavoring, with smaller amounts being used in confections and baked goods. Vanillin is also used in the fragrance industry, in perfumes, and to mask unpleasant odors or tastes in medicines, livestock fodder, and cleaning products. Vanillin has also been used as a chemical intermediate in the production of pharmaceuticals and other fine chemicals. In 1970, more than half the world's vanillin production was used in the synthesis of other chemicals, but as of 2004 such a use only accounted for 13% of the market for vanillin. Additionally, vanillin can be used as a general purpose stain for developing thin layer chromatography (TLC) plates to aid in visualizing components of a reaction mixture.
Vanillic acid (4-hydroxy-3-methoxybenzoic acid) is an odorless dihydroxybenzoic acid derivative and having the formula C8H8O4 that is used as a flavoring agent. It is an oxidized form of vanillin. It is also an intermediate in the production of vanillin from ferulic acid. The highest amount of vanillic acid in plants known is found in the root of Angelica sinensis, an herb indigenous to China, which is used in traditional Chinese medicine. Açaí oil, obtained from the fruit of the açaí palm (Euterpe oleracea), is rich in vanillic acid (1,616±94 mg/kg), for example. It is also one of the main natural phenols in argan oil and is also commonly found in wine and vinegar. Vanillic acid is one of the main catechins metabolites found in humans after consumption of green tea infusions.
Syringealdehyde (also, "syringaldehyde" or 3,5-dimethoxy-4-hydroxybenzaldehyde) is an organic compound having the formula C9H10O4 (shown in FIG. 3) that occurs in trace amounts throughout nature. Because it may contain many different functional groups, it can be classified in many ways—aromatic, aldehyde, or phenol. It is a colorless solid (impure samples appear yellowish) that is soluble in alcohol and polar organic solvents. Its refractive index is 1.53. Syringealdehyde is very similar in structure to vanillin and has comparable applications. Though not as well-commercialized as vanillin, syringealdehyde chemistry and its manipulation are emerging rather rapidly.
Syringealdehyde is formed in oak barrels and blends into whiskey, giving it a spicy, smoky, hot, and smoldering wood aroma. It is also used in the manufacture of antibacterial drugs including Trimethoprim, Bactrim, and Biseptol where syringealdehyde is an essential intermediate in their production. Bactrim or Biseptol are combinations of Trimethoprim with sulfamethoxazole. Applications for the use of syringealdehyde are diverse: as an antifungal agent for yeast infections and as an antimicrobial for clostridium; as an antimicrobial additive to antiseptic paper (thereby reducing the transmission of staph, pneumonia, and pseudomonas bacteria); and, it has potent antioxidant properties. See, e.g., Ibrahim et al., "A Concise Review of the Natural Existance, Synthesis, Properties, and Applications of Syringaldehyde," BioResources 7(3) (2012), the entire contents of which is hereby incorporated by reference in its entirety. For example, antioxidant activity for syringealdehyde has been recorded to be six times higher than that of protocatechuic aldehyde and the antioxidant activity of syringealdehyde has been found to be significantly greater than that of vanillin. (Boundagidou et al., 2010).
Lignin, as it is a waste of the pulping industry and a major by-product from the biomass-to-ethanol conversion process, offers a continuous, renewable, and economical supply of syringealdehyde. Syringyl (S) units found in lignin are the source from which syringealdehyde can be obtained when lignin-containing materials undergo certain oxidation reactions.
Syringic acid (4-hydroxy-3,5-dimethoxybenzoic acid) is a naturally occurring O-methylated trihydroxybenzoic acid having a formula of C9H10O5. It is an oxidized form of syringealdehyde. Syringic acid (as well as vanillic acid) possesses antimicrobial, anti-cancer, and anti-DNA oxidation properties. Additionally, both compounds act as immunomodulators and provide protective effects in mice with liver injuries. See, e.g., Itoh et al. "Hepatoprotective Effect of Syringic Acid and Vanillic Acid on CCI4-Induced Liver Injury," Biological and Pharmaceutical Bulletin, Vol. 33 (2010) No. 6 P 983-987, the entire contents of which is expressly incorporated by reference herein.
Mechanocatalysis or tribocatalysis is a solid-solid reaction using mechanical force without the addition of solvents, i.e., it is a non-aqueous or solvent-free catalytic reaction. Effective mechanocatalysts are mechanically robust and possess sites that are physically accessible and chemically active. Mechanocatalytic processes also typically do not require external heat. Substantially all of the energy for the reaction comes from the pressures and frictional heating provided by the kinetic energy of milling media moving in a container. In a mechanocatalytic system, it is important that intimate contact between the catalyst and reactant is maintained. Pebble (or rolling) mills, shaker mills, attrition mills, and planetary mills are a few examples of mills that effectively "push" the catalyst into contact with the material to be treated in a mechanocatalytic process. A mechanocatalytic process for converting biomass to soluble sugars is, for example, disclosed in U.S. Ser. No. 11/935,712, the entire contents of which are hereby incorporated by reference in their entirety.
One of the ways to convert lignin to fuels or chemicals is by base catalyzed depolymerization followed by hydrotreating, as shown in U.S. Patent publications 2003/0100807A1 and 2003/0115792A1. This process uses a strong base to partially break up the lignin compounds. One problem of this approach is the high consumption of strong base (such as NaOH) which makes the process less economical and environmentally appropriate. One recent study showed, for example, that pH within this process must be above 12.4 in order to achieve a relatively high lignin conversion.
Processes that avoid such a need for strong bases can shift the recovery of organic precursors from biomass to economically viable processes, as well as lessen the cost of environmental protection for such bio-conversion processes.
As such, disclosed and/or claimed herein are processes and methods for economically, safely, and reliably producing oxidized reaction products made from the mechanocatalytic oxidative depolymerization of lignin. More particularly, but without limitation, the mechanocatalytic oxidative depolymerization of lignin is performed in a non-aqueous/solvent-free based process, i.e., via a solid-solid mechanocatalytic oxidative reaction methodology. In one particular embodiment, the process of making such oxidized reaction products includes, without limitation, the step of mechanocatalytically reacting an oxidation catalyst with lignin or a lignin-containing material. The oxidized reaction products obtained from the process include, for example, at least one of vanillin, syringealdehyde, vanillic acid, and syringic acid.

Catalysts for the mechanocatalytic oxidative depolymerization of polymer-containing materials and methods of making oxidized reaction products using same

University of Central Florida Research Foundation Inc


A sharps collector comprising a container for holding, storing, and disposing syringes. The sharps collector includes a disposable receptacle and a decorative cover. The receptacle preferably has two elongated apertures and chutes associated with each aperture. The chutes are designed to guide syringes into the receptacle once the syringes pass through an aperture. The chutes also obstruct syringes which are already contained in the receptacle from protruding or re-emerging out of the receptacle. The decorative cover is reusable and fits over and attaches to the receptacle. When the cover is attached to the receptacle, it conceals the apertures and chutes of the receptacle. The cover includes an elongated aperture through which a shuttle is accessed. The shuttle directs syringes to the concealed apertures and chutes of the receptacle. The syringes to be disposed are placed in the shuttle and the shuttle is manually shifted such that a syringe is pushed towards an aperture and chute. The syringe then falls through the aperture, is guided by the chute, and ultimately falls into the receptacle and is contained within the receptacle. The cover can be detached from a receptacle when that receptacle is ready to be discarded.

The term "sharps" applies to any sharp device used in medical applications, such as hypodermic needles, lances, and the like. The dangers of disposing of these devices after use have become more prevalent with expanding diseases such as AIDS and hepatitis. Before disposal, the used devices must be contained such that exposure to others is minimized. These disposal problems are present in hospitals and doctor's offices, and are also present in home settings. Diabetics, for example, and others must dispose of numerous used needles and syringes. There are presently over two million diabetics in the United States, each of whom use an average of one and one-half syringes per day.
In addition to the problem of providing a receptacle for receiving used syringes, the container itself must be disposable, hold a reasonable number of syringes, insure that the syringes are stacked or packed in some suitable way, be safe to use without a deposited syringe sticking out or reemerging from the receptacle, be secure so that a child or animal cannot reach in and injure themselves on the discarded syringes contained therein, be closeable for disposal, and be puncture resistant, leak resistant, break resistant, as well as be tamper resistant after being closed and tamper evident if opened. The use of nontoxic materials and incineratable materials is important because some receptacles are incinerated and/or disposed of at disposal sites. Also, for use in doctor's offices the receptacles may need to be autoclavable.


A curved, tubular packing casing of unreinforced cellulose having non-uniform wall thickness in cross-section is disclosed. The area of minimum wall thickness lies opposite the area of maximum wall thickness and is situated in the area of the greater, outer radius of curvature. The maximum wall thickness lies in the range from about 50 to 160 .mu.m, and the minimum wall thickness lies in the range from about 10 to 50 .mu.m. The maximum wall thickness is 50 to 800% greater than the minimum wall thickness.

The invention relates to a curved, ring-type or spiral tubular packing casing, in particular to an artificial sausage casing in the form of a so-called round, comprising unreinforced cellulose and to a method for its production in which viscose (cellulose xanthate) is converted into regenerated cellulose. The helically wound tube obtained after drying can be divided into individual curved or annular sections which, when used as artificial sausage casing, are filled with sausage meat and further processed.
Packing casings of this type have been known for a long time. They are produced by the viscose method in which the alkaline viscose solution is extruded through an annular slot die directly into an acid coagulation bath. The coagulated tube is converted into cellulose hydrate gel by treatment with acid regeneration liquid and is thereafter dried in the inflated state.
In order to produce the permanently curved tube form by the viscose method, the coagulated and regenerated tube of cellulose hydrate gel is dried in the inflated and spirally wound state. Thus, DE-C-667,016 (=US-A-2,136,566) describes a drying process in which the tube, spirally wound on a heated drum and inflated with air, is dried in two stages. First, the inner side of the tube in contact with the drum is dried, and thereafter the tube is dried on all sides with air until completely dry. Because of the one-sided drying, the inner side bearing on the drum shrinks to a greater extent than the outer side which is dried later. Due to the cellulose hardening in the heat, the tube assumes the permanently spiral shape. This method requires a high degree of servicing and is suitable only for non-continuous operation. The unfavorable material properties of the tube casing obtained are a further disadvantage.
In a further development the spiral form is produced on the coagulated and not yet completely regenerated tube. In this method, described in DE-C-932,713 (=US-A-2,925,621), the air-inflated, coagulated tube is passed helically over a drum-shaped support through a regeneration bath. The regenerated cellulose tube running off the support is permanently shaped. DE-C-1,163,701 (=US-A-3,155,752) describes a cylindrical support suitable for carrying out this method. According to the information in DE-C-932,713 the cellulose tube casings regenerated in spiral winding should have better dimensional stability and smaller ring diameters compared to those prepared according to DE-C-667,016 which obtain their spiral shape only by the one-sided shrinkage upon drying. However, the method of DE-C-932,713 has the disadvantage that production interruptions are necessary for removal of the reaction gases arising in the tube upon regeneration of the cellulose. The tube casings obtained show widely differing properties, in particular as regards bursting pressure, caliber (casing diameter), ring diameter, expansion behavior and strength. The strength of the casings is, moreover, inadequate. It does not permit the casings to be provided in the watered state with a metal clip. In order to prevent damage to these casings during tying-off, a special thread is required. When used as sausage casing for boiling sausage, undesired wrinkle formation and jelly deposition occur after only a short storage time. Wrinkled sausage casings are not only unattractive, but the wrinkled areas also prevent penetration of smoke upon smoking of the sausage.
It is furthermore known in the prior art to produce curved sausages with tube casings of thermoplastic material. Thus, according to DE-C-2,163,764 (=US-A-3,950,469) the molten plastic (polyethylene terephthalate) is extruded through a tubular die, with an eccentrically designed ring slot, to give a tube which, corresponding to the shape of the ring slot, has a non-uniform thickness over the periphery. The extruded tube is stretched biaxially, and subsequently further stretched monoaxially in the longitudinal direction. The synthetic tube obtained is not yet curved. Only when a sausage mixture is pressed in should the straight synthetic tube be given a curved form by the action of the filling pressure. The thin-walled half of the tube is expanded radially more easily than the thick-walled half of the tube. The result of this is that the tube is radially expanded predominantly in the area of the thin-walled half of the tube, which occurs at the expense of a partial reduction in the length of the tube. This reduction in the length of the thin-walled part of the tube brings about the curvature of the tube when the sausage mixture is pressed in.
DE-C-2,314,767 (=US-A-4,081,562) has disclosed a method for the production of a curved sausage casing of edible materials, in particular animal skin fiber compositions. In the example collagen is extruded through a tubular die with an eccentrically mounted pellet. By this means a tube casing is produced which is of non-uniform thickness over the periphery and which, as a result of the nonuniform width of the die gap, curves on emerging from the die. It is then filled with blown air, led off helically in uniform turns and dried, the thicker areas at all times being subjected to the greatest expansion. Sausage casings of this material are not suitable for a number of types of sausage because of the lack of transparency. Moreover, in order to increase their strength, these casings must be watered in common salt solutions. This leads to pollution of the waste water and to corrosion of the processing machines.


The present invention relates to improved processability of polyolefin films through the addition to the basic isotactic polypropylene (iPP) polymer of a syndiotactic polypropylene (sPP) in an amount within the range of about 2 to 10 weight percent and of a resin or rosin modifier in an amount within the range of 1 to 30 weight percent. Preferably, the composition could contain syndiotactic propylene in an amount within the range of about 2 to 5 weight percent. Preferably, about 3 weight percent of syndiotactic propylene is present in the polyolefin composition. The resin or rosin modifier could, preferably, be present in an amount within the range of 5 to 10 weight percent. Preferably, the composition should contain about 10 weight percent of the modifier. The present invention encompasses both the resulting polyolefin films and the process for producing such films. The improved processability of the film includes fewer webs breaks and drawability at higher line speeds, resulting in fewer shut downs of the processing line and a decrease in manufacturing time. These improvements are measured in terms of variable machine direction orientation draw ratios and transverse direction orientation oven temperatures.

Biaxial orientation of polyolefins, particularly polypropylenes, produces films which have applications in the polyolefin film business, for example snack food packaging, cigarette overwrap, electronic components wrapping, packaging tape, and shrink film. The polymers normally employed in the preparation of biaxially oriented films are isotactic homopolymers with high stereoregularity, although on some occasions the use of syndiotactic polymers has been proposed. Also suitable are co-polymers of isotactic polypropylenes with a small content of ethylene (mini-random co-polymers).
Isotactic polypropylene is one of a number of crystalline polymers which can be characterized in terms of the stereoregularity of the polymer chain. Various stereo specific structural relationships denominated primarily in terms of syndiotacticity and isotacticity may be involved in the formation of stereoregular polymers of various monomers.
Isotactic polypropylene is conventionally used in the production of relatively thin films in which the polypropylene is heated and then extruded through dies and subject to biaxial orientation by stressing the film in both a longitudinal direction (referred to as the machine direction) and lateral direction sometimes referred to as the tenter direction. The structure of isotactic polypropylene is characterized in terms of the methyl group attached to the tertiary carbon atoms of the successive propylene monomer units lying on the same side of the main chain of the polymer. That is, the methyl groups are characterized as being all above or below the polymer chain. Isotactic polypropylene can be illustrated by the following structural formula: ##STR1##
[Bolding for emphasis only]
Stereoregular polymers, such as isotactic and syndiotactic polypropylene can be characterized in terms of the Fisher projection formula. Another way of describing the structure is through the use of NMR. Bovey's NMR nomenclature for an isotactic pentad is . . . mmmm . . . with each "m" representing a "meso" dyad, or successive methyl groups on the same side of the plane of the polymer chain. As is known in the art, any deviation or inversion in the structure of the chain lowers the degree of isotacticity and crystallinity of the polymer.
In contrast to the isotactic structure, syndiotactic propylene polymers are those in which the methyl groups attached to the tertiary carbon atoms of successive monomeric units in the chain lie on alternate sides of the plane of the polymer. Syndiotactic polypropylene can be illustrated by the following structural formula: ##STR2##
[Bolding for emphasis only]
Syndiotactic polymers are semi-crystalline and, like the isotactic polymers, are insoluble in xylene. This crystallinity distinguishes both syndiotactic and isotactic polymers from an atactic polymer, which is non-crystalline and highly soluble in xylene. An atactic polymer exhibits no regular order of repeating unit configurations in the polymer chain and forms essentially a waxy product. In most cases, the preferred polymer configuration will be a predominantly isotactic or syndiotactic polymer with very little atactic polymer.
The isotactic polymers normally employed are typically prepared through the use of conventional Ziegler-Natta catalysts of the type disclosed, for example, in U.S. Pat. Nos. 4,298,718 and 4,544,717, both to Myer et al. U.S. Pat. No. 5,573,723 to Peiffer discloses a process for producing biaxially-oriented polypropylene film based on an isotactic polypropylene homopolymer or propylene ethylene co-polymers. Other co-polymers of propylene and alpha-olefins having from 4-8 carbon atoms also may be employed in the Peiffer process.
Catalysts employed in the polymerization of alpha-olefins may be characterized as supported catalysts or unsupported catalysts, sometimes referred to as homogeneous catalysts. Traditional supported catalysts are the so-called "conventional" Ziegler-Natta catalysts, such as titanium tetrachloride supported on an active magnesium dichloride as disclosed, for example, in the aforementioned patents to Myer et al. A supported catalyst component, as disclosed in the Myer '718 patent, includes titanium tetrachloride supported on an "active" anhydrous magnesium dihalide, such as magnesium dichloride or magnesium dibromide. The supported catalyst component in Myer '718 is employed in conjunction with a co-catalyst such and an alkylaluminum compound, for example, triethylaluminum (TSA1). The Myer '717 patent discloses a similar compound which may also incorporate an electron donor compound which may take the form of various amines, phosphenes, esters, aldehydes, and alcohols. Metallocene catalysts are often employed as unsupported or homogeneous catalysts, although, as described below, they also may be employed in supported catalyst components.
Alternative types of catalysts that produce isotactic polyolefins are disclosed in U.S. Pat. Nos. 4,794,096 and 4,975,403. These patents disclose chiral, stereorigid metallocene catalysts that polymerize olefins to form isotactic polymers and are especially useful in the polymerization of highly isotactic polypropylene. As disclosed, for example, in the aforementioned U.S. Pat. No. 4,794,096, stereorigidity in a metallocene ligand is imparted by means of a structural bridge extending between cyclopentadienyl groups. Specifically disclosed in this patent are stereoregular hafnium metallocenes which may be characterized by the following formula: EQU R"(C.sub.5 (R').sub.4).sub.2 HfQp (3)
In formula (3), (C.sub.5 (R').sub.4) is a cyclopentadienyl or substituted cyclopentadienyl group, R' is independently hydrogen or a hydrocarbyl radical having 1-20 carbon atoms, and R" is a structural bridge extending between the cyclopentadienyl rings. Q is a halogen or a hydrocarbon radical, such as an alkyl, aryl, alkenyl, alkylaryl, or arylalkyl, having 1-20 carbon atoms and p is 2.
The various metallocene structures as described above can be used either as so-called "neutral metallocenes" in which case an alumoxane, such as methylalumoxane, is used as a co-catalyst, or they can be employed as so-called "cationic metallocenes" which incorporate a stable non-coordinating anion and normally do not require the use of an alumoxane. For example, syndiospecific cationic metallocenes are disclosed in U.S. Pat. No. 5,243,002 to Razavi. As disclosed there, the metallocene cation is characterized by the cationic metallocene ligand having sterically dissimilar ring structures which are joined to a positively-charged coordinating transition metal atom. The metallocene cation is associated with a stable non-coordinating counter-anion. Similar relationships can be established for isospecific metallocenes.
While metallocene catalysts are generally proposed for use as homogeneous catalysts, it is also known in the art to provide supported metallocene catalysts. As disclosed in U.S. Pat. Nos. 4,701,432 and 4,808,561, both to Welborn, a metallocene catalyst component may be employed in the form of a supported catalyst. As described in the Welborn '432 patent, the support may be any support such as talc, an inorganic oxide, or a resinous support material such as a polyolefin. Specific inorganic oxides include silica and alumina, used alone or in combination with other inorganic oxides such as magnesia, zirconia and the like. Non-metallocene transition metal compounds, such as titanium tetrachloride, are also incorporated into the supported catalyst component. The Welborn '561 patent discloses a heterogeneous catalyst which is formed by the reaction of a metallocene and an alumoxane in combination with the support material. A catalyst system embodying both a homogeneous metallocene component and a heterogeneous component, which may be a "conventional" supported Ziegler-Natta catalyst, e.g. a supported titanium tetrachloride, is disclosed in U.S. Pat. No. 5,242,876 to Shamsoum et al. Various other catalyst systems involving supported metallocene catalysts are disclosed in U.S. Pat. Nos. 5,308,811 to Suga et al and 5,444,134 to Matsumoto.
Polyolefin compositions which can be oriented at variable process conditions, particularly over a range of machine direction orientation draw ratios and transverse direction orientation oven temperatures, are desirable for a number of reasons. Film manufacturers have the flexibility to vary one or more processing conditions within an acceptable range for a particular film production run. In addition, the possibility of a web break during the orientation process is lessened, resulting in lower processing line start up costs. For example, a standard machine direction orientation draw ratio is about 5 times the original length of the polyolefin film. A standard transverse direction oven temperature is about 166.degree. C. These processing conditions are considered standard in that the occurrence of web breaks in the film are infrequent. The ability to orient film compositions under variable conditions, for example a machine direction draw ratio within the range of its standard up to 9 times the original length, and a transverse direction oven temperature within the range of its standard to about 20.degree. C. less than the standard, gives manufacturers greater latitude in the production of film products. A further processing advantage is the ability to draw the film at higher line speeds thereby decreasing the manufacturing time.
Biaxially-oriented films can have a number of properties to their advantage during and after the machine processing steps. A relatively low coefficient friction is desirable, both during the biaxially orientation procedure and in the use of the ultimately-produced biaxially-oriented film for end use applications. A relatively high stiffness, as indicated by the tensile modulus in both the machine direction and the transverse direction is usually advantageous. Relatively low permeabilities to gas and water are desirable. In addition, a high shrinkage factor of the processed film, while undesirable in some cases, can be advantageous in others, such as where the film is used in stretch wrapping of food products, electrical components, and the like.
Properties of the resulting film product can be dependent to a certain degree on the particular process conditions under which the polyolefin composition was manufactured. For example, a stiffer film with a higher shrinkage factor and better barrier properties would result from an orientation process incorporating a larger machine direction orientation draw ratio. Likewise, the transverse direction orientation oven temperature would affect the properties of the resulting oriented film product, particularly improving the shrinkage factor.
The physical and optical properties of films are important in the film industry and should fall within certain parameters for different film applications. The optical properties include haze, contact clarity (NAS), and gloss. Haze is a phenomena of light scattering and arises from local variations in the refractive index. Haze is defined as the relative fraction of scattered intensity from the dispersed particles in all directions, being detected in a range of wide angle, to the incident light intensity. Contact clarity or NAS is a measure of contact clearness or see-through quality and is different from haze due to the direct transmittance of light. For example, some films may indeed be hazy but appear clear as the film is in contact with the contents of a package. Unlike haze, NAS clarity is distance dependent so that the thinner the film, the better the contact clarity. Gloss is defined as the ratio of the reflected light intensity from the film at a specific angle of incidence light to that of a standard with the ideal smooth surface.

Compositions for improved orientation processing


A method for the manufacture of a circuit board containing a component and circuit board containing a component. The invention is based on first manufacturing an intermediate product, which contains the insulator layer of the circuit board and the components, which are set in place inside the insulator layer in such a way that the contact elements of the components face the surface of the intermediate product. After this, the intermediate product is transferred to the circuit-board manufacturing line, on which a suitable number of conductor-pattern layers and, if necessary, insulator layers are manufactured on one or both sides of the intermediate product, in such a way that, when manufacturing the first conductor-pattern layer, the conductor material forms an electrical contact with the contact elements of the components. Alternatively, stages can also be performed on a single manufacturing line.

1. Field of the Invention
The present invention relates to a method for manufacturing a circuit board containing a component, as well as to a circuit board containing a component.
2. Brief Description of the Related Art
Layers containing a component are manufactured, for example, when manufacturing multi-layer circuit boards or other corresponding electronic modules. In particular, the invention relates to a method for manufacturing a layer, which contains one or several components, which are connected electrically to an external circuit, or to each other, with the aid of conductor structures manufactured in the electronic module.
US Publication No. 2005/0001331 discloses a manufacturing method for circuit-board structure, in which first of all a circuit board, which comprises an insulator layer and a conductor pattern on the surface of it, is manufactured. After that, a semiconductor component is then connected to the conductor pattern of the surface of the circuit board, using a suitable flip-chip attachment method. The connection is made with the aid of contact bumps on the surface of the semiconductor component. In the method of the US publication, after attachment of the component, a patterned and unpatterned insulating-material layer is laminated on top of the circuit board and then on their surface a conductor-pattern layer.
U.S. Pat. Nos. 6,038,133 and 6,489,685, as well as US Publication No. 2002/0117743 disclose methods, in which a conductor pattern is made on the surface of a detachable membrane and a semiconductor component is attached to the conductor pattern using a flip-chip attachment method. After this, the component is surrounded with a layer of insulating material and the detachable membrane is removed.
The aforementioned U.S. Pat. No. 6,038,133 and US Publication No. 2002/0117743 also disclose a method, in which a flip-chip method is used to attach the component not to a conductor pattern, but to a unified conductor membrane, from which conductor patterns are formed in a later stage of the process. A corresponding method is also disclosed in, for example, U.S. Pat. No. 5,042,145, WO 2004/077902, WO 2004/077903, and WO 2005/020651.
In addition to the types of method referred to above, many other methods are known, by means of which circuit-board structures containing components can be manufactured. For example, the components can be first of all placed inside an insulating-material layer and connected electrically to the conductor layer only after this, as is disclosed in International Publication No. WO 2004/089048. In the method of WO 2004/089048, the component is glued onto the surface of the conductor layer and after the component has been glued an insulating-material layer is formed on, or attached to the surface of the conductor layer. After the gluing of the component, vias are also made, through which electrical contacts can be formed between the conductor layer and the component. After this, conductor patterns are formed from the conductor layer, to the surface of which the component has been glued. With the aid of the method described by the publication, it is possible to manufacture mechanically durable electronic modules, which contain embedded unpacked components. A good side of the method is also the fact that the contacts to the components can be made by growing metal, in which case the electrical properties of the contacts will be excellent.
However, the method disclosed in WO 2004/089048 differs from the conventional circuit-board manufacturing process to such an extent that its introduction to mass production will in most cases require the construction of a new manufacturing line, or at least alterations to a traditional manufacturing line. Thus the introduction of the method will also demand considerable initial investments.
The invention is intended to improve the method disclosed in WO 2004/089048, so that it can be exploited more easily also in connection with traditional circuit-board manufacturing processes.
The invention is based on first of all manufacturing an intermediate product, which contains the insulator layer of the circuit board and the components, which are attached in place inside the insulator layer, in such a way that the contact elements of the components open onto the surface of the intermediate product, or at least extend into the vicinity of the surface of the intermediate product. After this, the intermediate product is transferred to a circuit-board manufacturing line, on which a suitable number of conductor-pattern layers, and if necessary insulator layers are made on one or both sides of the intermediate product, in such a way that in the manufacture of the first conductor-pattern layer the conductor material forms an electrical contact with the contact elements of the components.
At the same time, according to the invention an alternative method is also created for manufacturing the product described in WO 2004/089048.
Considerable advantages are gained with the aid of the invention.
With the aid according to the invention, the method disclosed in WO 2004/089048 can be more easily utilized also in connection with traditional circuit-board manufacturing processes.
With the aid of the invention, an alternative method is also presented for manufacturing the product described in WO 2004/089048.
Further scope of the applicability of the present invention will become apparent from the detailed description given hereinafter. However, it should be understood that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

Manufacture of a circuit board containing a component


Three collar groups 6A through 6C, each group comprising collars 5a through 5b, 5c through 5e and 5f through 5h which are thin walled and close to each other are provided in a spaced manner in a piston sliding direction. A first group 6A which is provided at the front most end of the piston head 5 comprises two collars 5a and 5b. The front collar 5a which is in contact with the liquid drug has a larger diameter than that of the rear collar 5b. First and third collar groups 6B and 6C which are at the rear of the first collar group 6A comprise three collars 5c to 5e and 5f to 5h, respectively. The intermediate collars 5d and 5g have larger diameters than those of the front and rear collars 5c and 5e; and 5f and 5h, respectively. A support collar 5i is provided at the rear of the collar groups 6B and 6C in such a manner that it is spaced therefrom. The support collar 5i has a thick walled portion x at its base excepting the peripheral edge thereof.

1. Field of the Invention
The present invention relates to a syringe and in particular to a syringe having a piston head which is made of a resin.
2. Related Art
As is well known, prior art syringe mainly comprises a cylinder which accommodates liquid such as drug and a piston which is reciprocally disposed within the cylinder. The piston comprises a piston main body and a piston head (gasket) which is secured to a front end of the piston main body by means of screwing and the like so that it slides along the inner wall of the cylinder while keeping the sealing condition therewith.
Recently, it is known that the cylinder is preferably made of any of cycloolefin resins in view of chemical resistance and heat resistance. On the other hand, the piston head is made of an elastomer such as butyl rubber since it should slide on and along the inner wall of the cylinder while keeping the liquid-tightness therewith.
However, such an elastomer requires a complicated and tedious washing step since plasticizers, cross-linking agents and pigments which are used with the elastomer may be dissolved to the chemical which is contained in the cylinder.
The elastomer (particularly, butyl rubber) has a low sliding ability for the inner surface of the cylinder. In order to make the reciprocal movement of the piston smoother, the inner face of the cylinder is coated with a lubricating agent such as silicone oil.
There is also a problem that it is hard to provide a high stability in size for the reason of the manufacturing process when the piston head is made of an elastomer.
Therefore, it is a main object of the present invention to achieve the simplification of the manufacturing process by omitting the washing step while satisfying the characteristics which are basically required for the syringe, to enable smooth sliding without using any lubricant, to enhance the dimension accuracy and stability and to achieve the reduction in cost by achieving the foregoing.
In view of the above-mentioned object, the present inventors have believed that the piston head is also made of a resin similarly to the cylinder to omit the washing step and to enhance the dimension accuracy and stability and have made efforts to study the manufacturing of the syringe. We have found from our study that if the prior art piston head is made of only a resin, there occur problems in liquid-tightness, sliding characteristics and ability of incorporation of the piston head into the cylinder. We have further made efforts on the research and development of the syringe to solve these latter problems together and made the present invention.
One embodiment of the invention resides in a syringe comprising a cylinder for containing liquid therein and a piston which is reciprocally disposed within the cylinder. The piston including a piston main body and a piston head made of a resin which is secured to a front end of the piston main body and slides along the inner wall of the cylinder while keeping the liquid-tightness therewith. The piston head is formed on the periphery thereof with collar means which contacts with the inner wall of the cylinder, at least the peripheral edge of the collar means being thin walled. The collar means being slidable on and along the inner wall of the cylinder while keeping the liquid-tightness.
An aspect of the invention resides in the collar means comprises collars which are spaced in a direction of sliding of the piston. The collar of at least two adjacent collars, which is on the front side in the sliding direction being supported by the collar which is in the rear side in the sliding direction when the piston slides.
Another aspect of the invention resides in the syringe having a collar means having a base end portion which is thick walled excepting for the peripheral edge.
Another embodiment of the invention resides in a syringe comprising a cylinder for containing liquid therein and a piston which is reciprocally disposed within the cylinder. The piston including a piston main body and a piston head made of a resin which is secured to a front end of the piston main body and slides along the inner wall of the cylinder while keeping the liquid-tightness therewith. The piston head is formed on the periphery thereof with collar groups, each comprising two collars which are close to each other, at least the peripheral edge of each of the collars being thin walled. The collars being slidable on and along the inner wall of the cylinder while keeping the liquid-tightness. The front collar of the collar group having a diameter which is larger than that of the rear collar. The front collar having a larger diameter being supported by the rear collar when the piston is inserted into the cylinder.
Still another embodiment of the invention resides in a syringe comprising a cylinder for containing liquid therein and a piston which is reciprocally disposed within the cylinder. The piston including a piston main body and a piston head made of a resin which is secured to a front end of the piston main body and slides along the inner wall of the cylinder while keeping the liquid-tightness therewith. The piston head is formed on the periphery thereof with collar groups, each comprising three collars which are close to each other, at least the peripheral edge of each of the collars being thin walled. The collars being slidable on and along the inner wall of the cylinder while keeping the liquid-tightness. The intermediate collar of the collar group having a diameter which is larger than that of the front and rear collars. The intermediate collar having a larger diameter being supported by the front and rear collars when the piston is slided in the cylinder.
Yet another embodiment of the invention resides in a syringe comprising a cylinder for containing liquid therein and a piston which is reciprocally disposed within the cylinder. The piston including a piston main body and a piston head made of a resin which is secured to a front end of the piston main body and slides along the inner wall of the cylinder while keeping the liquid-tightness therewith. The piston head is formed on the periphery thereof with at least two collar groups being spaced in a direction of sliding of the piston, each group comprising collars which are close to each other, at least the peripheral edge of each of the collars being thin walled. The collars being slidable on and along the inner wall of the cylinder while keeping the liquid-tightness. The collar group at the distal end comprises two collars. The front collar of the frontmost collar group having a diameter which is larger than that of the rear collar. The front collar having a larger diameter being supported by the rear collar when the piston is inserted into the cylinder. The collar group which is at the rear of the frontmost collar group comprises three collars, the intermediate collar having a diameter which is larger than those of the front and rear collars. The intermediate collar having a larger diameter being supported by the front or rear collar at least when the piston slides, wherein a piston support collar which is thick walled at the base end thereof excepting for the peripheral edge thereof is provided at the rear of these collar groups in a spaced relationship therewith.
An aspect of the invention resides the piston head being formed of a resin which is selected from the group consisting of polypropylene, polyethylene, fluorine, cyclopolyolefin, and polycarbonate resins.