Elevator, exhibiting an elevator shaft (34) and a car (32) which is movably provided inside the elevator shaft (34), and a safety installation (2), which is designed in such a way that it can take the elevator out of service in a dangerous situation, characterized by the fact that the safety installation (2) is equipped with a shaft monitoring device.

The invention pertains to an elevator exhibiting an elevator shaft, an elevator car which is movable inside the elevator shaft, and a safety installation which is designed in such a way that it can take the elevator out of service in a dangerous situation.
Everyday life, especially, in cosmopolitan areas, is no longer imaginable without elevators. Elevators are being employed for very diverse applications, e.g., for use in buildings with only relatively few floors (3 to 5 floors) and in relatively tall buildings of, sometimes, substantially more than 50 floors. Elevators are equipped with extremely diverse drive systems. There are those with a friction-driven hoisting motor, which, for instance, may be provided in the upper area of the elevator shaft. These types of elevators frequently are equipped with a counterweight unit that is suspended on the same hoisting cable as the elevator car, which runs in the opposite direction to the elevator car. In addition, there are those elevators, in particular, which are used to service only relatively few floors, so-called hydraulic elevators, with or without a counterweight, in which the elevator car is moved by a hydraulically moved pressure piston. Sporadically, there are also elevators in which the driver is provided on the elevator car directly and which is, for example, designed as a rack and pinion drive, or wheel and disk drive.
In all of these different elevator types, assuring that only maintenance staff or other authorized individuals enter the elevator shaft presents a fundamental problem. In order to solve this problem, elevators typically have a safety installation which is equipped with various sensors and which, upon detecting a dangerous situationxe2x80x94which is defined in accordance with specific prerequisitesxe2x80x94will take the elevator out of service. The acuteness of this problem which, in the past, essentially, only affected elevator operators or maintenance personnel has, most recently, skyrocketed due to the presence of xe2x80x9celevator surfers,xe2x80x9d and, more specifically, due to the determination with which these elevator surfers seek to bypass the safety installation. As a result of this development, safety installations which, until recently, were still deemed satisfactory, have turned out to be inadequate.
A typical safety device is equipped with hatch door contacts on each hatch door which are frequently electronically connected in series, whereby the opening of one single hatch door contact breaks the connection between the power supply and the drive motor. Besides that, additional safety switches exist in the elevator shaft in maintenance-relevant locations, or in locations which pose particular safety problems, namely, specifically, the so-called PES (pit emergency stop), or the pit emergency switch, as well as the TCI (top of car inspection) which is provided on the top of the car and is operated by a mechanic who climbs on top of the car for maintenance purposes. These two switches are frequently also provided in series with the door contact switches. If one of these switches of the safety chain is opened, the connection between the power supply and the drive motor is broken and the elevator car stops in the position it has assumed. Normally, this safety chain is directly connected to the elevator control system. In addition, the PES and the TCI are separately connected to the elevator control system and, apart from that, additional information concerning the current position of the car, etc., is fed to it. The elevator control system software differentiates between the safety chain""s signals in their evaluation. Thus, it is quite obvious that, each time the car makes a normal stop on any floor and with every associated opening of the door, the appropriate door safety contact is opened for a short period and the connection between the power supply and the driver is broken. After the door contact has closed, the safety chain is also closed again as a whole, the power supply to the driver is restored, and the elevator can, quite routinely, start on its way to the next destination stop. If, however, the hatch door, e.g., is opened manually when the car is not in a position that is in flush alignment with an opening on a floor, the car, depending upon software control of the equipment, can be taken out of service permanently, and the elevator operator, or a mechanic who might be called, must inspect the equipment and restart its operation.
Although, over the years, this type of safety installation has proved to be reliable, serious and, in some cases, also fatal, accidents have repeatedly occurred, e.g., either when trained personnel did not correctly adhere to the safety instructions because of time pressures or established routine or when unauthorized individuals forced their way into the elevator shaft. For instance, due to the design of the safety chain with series-connected door contact switches, it is possible for elevator surfers manually to open the door one floor above the regular stop location of the elevator car while the subjacent door is open, so that passengers can exit and board, and to close the door again within the same time period. The elevator surfer then stands on top of the elevator car and the elevator safety installation has failed to acknowledge the fact that a second door was opened manually.
An additional typical accident scenario is the following: one of the passengers has dropped a key into the shaft pit through the gap between the car and the landing floor, and the building""s elevator operator is called for assistance. He sends the car off from the bottommost landing floor and opens the door on the landing floor with the appropriate unlocking key. Then, he blocks the door on the landing floor with an inappropriate tool (for example, a screwdriver) and climbs into the shaft pit without operating the pit emergency switch that is mounted there. If the screwdriver, which is to serve to secure the door on the landing floor, slips out now, it may happen it will close and the car will begin to move. In such a situation, the typical result is a correction run, i.e., the car will run to one of the end points of its path of movement, that is, all the way to the bottom.
Another situation may occur if a maintenance mechanic wishes to step on the elevator top for maintenance purposes. For this purpose, he calls the car to his landing floor and ensures that there are no passengers inside the car. He then sends the car down far enough that he can easily reach the elevator top, and he opens the door on the landing floor with the corresponding unlocking tool. He then enters the top of the car and, even before he is able operates the top of car emergency switch, he stumbles. In this case, the door on the landing floor also closes and the elevator continues its operation in the usual manner because the safety installation is unable to recognize this dangerous situation.
In this context, it is the objective of the present invention to configure the safety installation of an elevator in such a way that, as a general rule, the elevator will be taken out of service when unauthorized people enter the elevator shaft.
In accordance with the invention, this objective is realized by means of the fact that the safety installation is equipped with a shaft monitoring device.
It is not mandatory that the shaft monitoring device monitor the entire elevator shaft. For instance, essential partial areas of the elevator shaft to be monitored are the top of the car, on the one hand, and the shaft pit, on the other hand. The shaft monitoring device may, especially preferably, but need not be designed in combination with the mentioned safety installation in the way of a safety chain. Specifically, this type of shaft monitoring device is able to detect an unauthorized entry into the shaft even without the added safety chain, and can take the elevator out of service. Preferably, the shaft monitoring device is equipped with at least one motion sensor. This may either be an ultrasound or an infrared motion sensor. As a rule, these types of motion sensors are manufactured in large lots for the most diverse applications and can, accordingly, be purchased inexpensively. Naturally, other types of automated motion sensors are conceivable, as well; for instance, video cameras which are connected to an image analyzer. Alternatively, or in addition to motion sensors, a load-sensitive mat may also be provided on top of the car and/or in the shaft pit, which, under load, will transmit a signal to the safety control system or open a switch in the safety chain.
The shaft monitoring device preferably monitors the shaft in the vicinity of the shaft pit and/or in the area of the top of the car. As a rule, these are the only areas in the elevator shaft in which a human being can spend time relatively easily. In the case in which the horizontal surface of the counterweight is large enough, it is also conceivable that a shaft monitoring device could be provided for this area.
Preferably, a motion sensor is provided in such a way that the movement of the hatch doors will not be detected by the motion sensor. This arrangement will facilitate the avoidance of a disturbance or an erroneous signal transmission due to a movement of the hatch doors. In general, motion sensors have a specific, well-defined horizontal and vertical angular field which they are capable of covering. Therefore, essentially, it may be more advantageous to arrange the individual motion sensors on the shaft wall on which the hatch doors are located and to have the xe2x80x9ccritical peripheryxe2x80x9d of the angular field graze past it linearly, essentially parallel to the hatch door opening. Thus, on the one hand, it is ensured that the entry of a person through the hatch door opening will always be detected. Yet, on the other hand, specifically, the movement of the hatch door will no longer be monitored by the sensor.
The shaft monitoring device is preferably connected to a safety control system, which is designed in such a way that after it takes the elevator out of service due to a dangerous situation, it will automatically reset the elevator to its normal operating state, if the shaft monitoring device was unable to detect anything in the shaft over a predetermined extended period and the rest of the sensors of the safety installation also do not display any irregularities over the same period. The advantage of this design shall be described by means of a brief example: because he has heard some noise in the elevator shaft, the elevator operator opens the hatch door and looks into the elevator shaft. The shaft monitor detects that the head has entered the shaft and, thereupon, stops the operation of the elevator. Because the elevator operator could not find anything, he shuts the door again. If, after that, the shaft monitoring device does not detect anything peculiar over a specific extended period, the safety control system assumes that no one is in the elevator shaft any more and automatically resets the elevator to its normal operating state. The predetermined extended period is normally set, so that it can be presumed that a person who is in the elevator shaft would have moved in the meantime, or would have been detected by the shaft monitoring device otherwise. Typical time periods are approximately 5-10 minutes. This time period may appear lengthy from the viewpoint of passengers waiting in front of the elevator doors. However, it is relatively short compared to the time which would elapse if the elevator was manually reset to its normal operating state.
Preferably, the shaft monitoring device is connected to a safety control system that only uses the signals of the shaft monitor while the car is stopped in order to detect dangerous situations. An examination of a motion sensor on top of the car shows that with the elevator in motion, the shaft wall moving past it will be detected as a moving object. If the safety control system were also to use the signals of this sensor in order to detect a dangerous situation while the elevator car is in motion, it would take the elevator out of service each time the car starts up. This similarly applies to other sensors provided in the shaft and the shaft pit which, e.g., may erroneously identify the moving elevator car or the counterweight, the compensating ropes, or other moving parts, as unauthorized objects or people in the elevator shaft. Theoretically, it is true that this problem could also be avoided through an appropriate adjustment of the sensors, but in order to prevent faulty responses with a relatively high degree of reliability, and in order to utilize the entire angular field of the sensors, it is preferable to use the signals of a motion sensor for the detection of dangerous situations only while the car is halted. However, especially in the shaft pit, it might make sense continuously to use the signals of the shaft monitor which is mounted there in order to detect a dangerous situation. On the one hand, only a relatively limited number of moving parts are located there that can, for instance, be covered with screens, or made undetectable by appropriately positioning the sensors of the shaft monitoring device. Generally, in the vicinity of the shaft pit, the probability that a person will enter this area while the car is moving is relatively high. It is true that, normally, the shaft pit is secured due to the fact that the bottommost hatch door is secured by a hatch door contact or that a separate shaft pit hatch is also secured by a separate contact. However, here, the shaft monitoring device provides an additional safety network in the event that this safety contact should fail.
Preferably, the signals of the shaft monitoring device will be used while the car is moving, in order to check the functions of the shaft monitoring device. The fact that while the car is moving the shaft monitoring device typically transmits motion signals to the safety control system can be used for a function check of the individual sensors of the shaft monitoring device either at intervals or continuously. If the safety control system detects that one or more motion sensors of the shaft monitoring device does or do not transmit any motion signals while the car is moving, it can be assumed that a defect is present. The function control option of the shaft monitoring device, as a side effect of a continuous operation, so to speak, should not be underestimated as an additional safety feature.
Moreover, the present invention pertains to a process for the retrofitting of a shaft monitoring device in an existing elevator with a safety installation which is designed in such a way that in a dangerous situation which has been recognized as such by the safety installation, it can take the elevator out of service, which is characterized by the fact that a shaft monitoring device is provided; the shaft monitoring device is installed in the elevator shaft; the shaft monitoring device is connected to the safety installation, and a function check is performed.
The present invention turns out to be particularly valuable due to the fact that it is possible relatively easily to retrofit already existing elevator facilities with safety installations due to the relatively simple installation of the shaft monitoring device, and to update them to the latest state of the art safety technology. Especially in view of the extremely long operating times of typical elevators in buildings, some of which are 50 years or more, the retrofitting of existing facilities to the latest state of the art is always an important issue. The conspicuously simple solution of the present invention facilitates this retrofitting especially easily.
Specifically, this retrofitting is also possible in cases in which the safety control system of the elevator itself is still basically designed to also process the additional signals of the shaft monitoring device. In this case, an internal safety control system may be provided for the shaft monitoring device which, for instance, can receive control signal information to the driver concerning whether the car is presently at a landing floor or is moving between two landing floors. The signals of the individual sensors of the shaft monitoring device are fed to the safety control system of the shaft monitoring device and the latter determines whether a relay, which is present in the safety chain of the elevator in the way of a hatch door contact, will be opened or remain closed. In this manner, the retrofitted shaft monitoring device can, in principle, essentially be used to completely retrofit any elevator regardless of the conditions present in the facility. Preferably, the step of installing the shaft monitoring device includes the mounting of the shaft monitoring device in such a way that it will at least survey either the shaft pit or the top of the car.


A gene transfection particle includes a polymer, a support particle conjugated with the dendritic polymer, and genetic material conjugated with the dendritic polymer. The gene transfection particles are highly efficient and are capable of delivering higher quantities of genetic materials to cells, with reduced cell damage. A gene transfection method involves bombarding cells with conjugates of polymers and genetic material, with or without a support particle.

This invention relates to compositions of matter and methods which are useful in delivering genetic materials to the interior of plant and animal cells, and more particularly to gene transfection particles and particle bombardment methods for gene transfection.
Particle bombardment, also know as the gene gun method, provides a potentially effective method for introducing genetic materials into plant and animal cells in the treatment and control of a variety of genetic, neoplastic and infectious diseases, and for creating transgenic species. Particle bombardment methods of introducing genetic materials into plant and animal cells involves accelerating microscopic particles coated with a genetic material through the wall of the cell to deliver the genetic material to the interior of the cell. The motive force used to accelerate the particles can be generated by high-voltage electric discharge, helium pressure discharge or other means. The microscopic projectile transfection particles generally comprise a gold particle having a diameter of from about 1 to 15 micrometers, and genetic materials attached thereto. Gold particles are preferred because they are chemically inert, have no cytotoxic effects in the cells, and have a high density which permits greater momentum and penetration into cells. Binding agents such as spermidine (N-3-aminopropyl-1-4-butanediamine) have been used to attach genetic materials to gold particles.
A disadvantage with known particle bombardment methods is that they may not provide a sufficient quantity of genetic material to achieve a desired therapeutic effect without causing unacceptably high levels of cell damage. Ning-Sun Yong et al., in Gene Therapeutics: Methods and Applications of Direct Gene Transfer, have reported that for confluent monolayer cell cultures with cells 15-20 micrometers in size, a particle bombardment density of 0.1 particles per square centimeter of 0.9 micrometer particles, which delivers about two particles per cell, results in more than 90% of monolayer cells and 75% of suspension cells being viable and healthy after particle bombardment, but that for most tissue samples, higher particle bombardment densities cause excessive cell and tissue damage. Because of the relatively low binding capacity of the linear polyamines used to attach genetic materials to gold particles, and the relatively low levels of particle bombardment which can be tolerated without excessive cell damage, known transfection particles may not be capable of introducing sufficient quantities of genetic materials to cells to achieve a desired therapeutic or other effect while avoiding excessive cell damage.
Accordingly, there is a need for transfection particles which are capable of delivering higher amounts of genetic materials into cells using particle bombardment methods while minimizing cell damage.
The invention provides highly efficient transfection particles and bombardment methods which are capable of delivering higher amounts of genetic materials to cells while minimizing cell damage. The gene transfection particles of this invention comprise a composite material including a polymer, a support particle conjugated with the polymer, and genetic material conjugated with the polymer.
The bombardment method of this invention involves the steps of forming a gene transfection particle including a polymer, and genetic material conjugate, with or without a support particle, and accelerating the gene transfection particle toward a cell with sufficient motive force to cause the gene transfection particle to penetrate and enter the cell.
An advantage of the invention is that it provides a method whereby the density of the gene transfection particles can be adjusted as required depending on the robustness of the cell membrane which must be penetrated.
The gene transfection particles of the preferred embodiment of the invention preferably include genetic material which is conjugated to polymer, and a metal, in the form of one or more atoms, one or more ion complexes, clusters, or particles, or other support which is also conjugated to the polymer. The metal component provides the gene transfection particles with the density needed to achieve the momentum which is necessary to penetrate the cell wall and/or membrane when the particles are accelerated toward the cell so that the carried genetic material can be delivered to the interior of the cell. The metal used in preparing the gene transfection particles must be chemically inert in the cell environment, have essentially no, or at least very low, cytotoxic effects in the cells, and be capable of being conjugated to a dendritic polymer. The metal preferably has a relatively high density to allow greater momentum and, hence, adequate penetration of the cell wall and/or membrane. Gold is presently preferred because of its established acceptance for use in gene therapy. However, other metals may be employed in certain applications. Examples of metals which may be suitable for use in particle bombardment gene therapy methods include gold, tungsten, silver, copper, magnesium, calcium and combinations thereof.
The metal component may be conjugated to the dendritic polymer in the form of an individual atom, ion, or complex, or in the form of clusters of atoms or microscopic size particles. In addition to metal particles, other suitable supports includes silica particles, alumina particles, and other solid supports having Lewis acid surface functionality. Also, it has been determined that dendritic polymers conjugated to genetic materials, without any metals or other support materials conjugated thereto may also be usefully employed as gene transfection particles in particle bombardment methods.
The gene transfection particles prepared by contacting a dendritic polymer with a metal atom or a metal atom-containing entity, and a genetic material may have a diameter or maximum dimension of from about 1 nm to about 15 nm. Particles comprised of dendritic clusters or aggregates can have a maximum dimension of from about 2 nm up to at least several micrometers. However, the gene transfection particles of this invention preferably have a particle size of from about 1 nm to about 1000 nm, and more preferably from about 1 nm to about 100 nm.
The genetic materials which may be used in preparing the gene transfection particles of this invention include biological response modifiers, such as interleukins, interferons, and viruses, viral fragments and other genetic materials. The term xe2x80x9cgenetic materialxe2x80x9d as used herein refers to nucleotide based materials, including without limitation, viruses and viral fragments, deoxyribonucleic acid (DNA), plasmids, ribonucleic acid (RNA), messenger RNA (mRNA), transfer RNA (tRNA), ribosomal RNA (rRNA), catalytic RNA (cRNA), smaller nuclear RNA (snRNA), exons, introns, codons, and anti-sense oligonucleotides. Genetic material, especially viruses and viral fragments, may incidentally include some protein.
The polymers are preferably dendritic, but linear and other non-dendritic polymers may be suitable. The dendritic polymers used in preparing the gene transfection particles of the preferred embodiment include generally any dendritic polymers which include functional groups, on the interior and/or exterior, which are capable of binding or conjugating the metal with the dendritic polymer. The dendritic polymers used to coat the metal particles have surface functional groups which have an affinity for (i.e., will stick to) the surface of the support particles, with the preferred dendritic polymers being those having amine functional groups e.g., such as PAMAM, POPAM and PEI dendritic polymers. The support particles and the dendritic polymers are contacted under conditions sufficient to cause the dendritic polymer molecules to adhere to the surface of the support particles. Thereafter, the dendritic polymer-support particle conjugate is contacted with genetic material to form a highly efficient gene transfection particle which is capable of delivering larger quantities of genetic materials to a cell, as compared with known gene transfection particles. This result can be achieved even with particles which are substantially smaller than known gene transfection particles, resulting in improved therapeutic effect and reduced cell damage.
Dendritic polymers which may be used include generally any of the known dendritic architectures including dendrimers, regular dendrons, controlled hyperbranched polymers, dendrigrafts, and random hyperbranched polymers. Dendritic polymers are polymers with densely branched structures having a large number of reactive groups. A dendritic polymer includes several layers or generations of repeating units which all contain one or more branch points. Dendritic polymers, including dendrimers and hyperbranched polymers, are prepared by condensation reactions of monomeric units having at least two reactive groups. The dendrimers which can be used include those comprised of a plurality of dendrons that emanate from a common core which can be a single atom or a group of atoms. Each dendron generally consists of terminal surface groups, interior branch junctures having branching functionalities greater than or equal to two, and divalent connectors that covalently connect neighboring branching junctures.
Dendrons and dendrimers can be prepared by convergent or divergent synthesis.
Divergent synthesis of dendrons and dendrimers involves a molecular growth process which occurs through a consecutive series of geometrically progressive step-wise additions of branches upon branches in a radially outward molecular direction to produce an ordered arrangement of layered branched cells. Each dendritic macromolecule includes a core cell, one or more layers of internal cells, and an outer layer of surface cells, wherein each of the cells includes a single branch juncture. The cells can be the same or different in chemical structure and branching functionality. The surface branch cells may contain either chemically reactive or passive functional groups. Chemically reactive surface groups can be used for further extension of dendritic growth or for modification of dendritic molecular surfaces. The chemically passive groups may be used to physically modified dendritic surfaces, such as to adjust the ratio of hydrophobic to hydrophilic terminals, and/or to improve the solubility of the dendritic polymer for a particular solvent
Convergent synthesis of dendrimers and dendrons involves a growth process which begins from what will become the surface of the dendron or dendrimer and progresses radially in a molecular direction toward a focal point or core. The dendritic polymers may be ideal or non-ideal, i.e., imperfect or defective. Imperfections are normally a consequence of either incomplete chemical reactions, or unavoidable competing side reactions. In practice, real dendritic polymers are generally nonideal, i.e., contain certain amounts of structural imperfections.
The hyperbranched polymers which may be used represent a class of dendritic polymers which contain high levels of nonideal irregular branching as compared with the more nearly perfect regular structure of dendrons and dendrimers. Specifically, hyperbranched polymers contain a relatively high number of irregular branching areas in which not every repeat unit contains a branch juncture. The preparation and characterization of dendrimers, dendrons, random hyperbranched polymers, controlled hyperbranched polymers, and dendrigrafts is well known. Examples of dendimers and dendrons, and methods of synthesizing the same are set forth in U.S. Pat. Nos. 4,507,466; 4,558,120; 4,568,737; 4,587,329; 4,631,337; 4,694,064; 4,713,975; 4,737,550; 4,871,779 and 4,857,599. Examples of hyperbranched polymers and methods of preparing the same are set forth, for example in U.S. Pat. No. 5,418,301.
The dendritic polymers or macromolecules useful in the practice of this invention are characterized by a relatively high degree of branching, which is defined as the number average fraction of branching groups per molecule, i.e., the ratio of terminal groups plus branch groups to the total number of terminal groups, branched groups and linear groups. For ideal dendrons and dendrimers, the degree of branching is 1. For linear polymers, the degree of branching is 0. Hyperbranched polymers have a degree of branching which is intermediate that of linear polymers and ideal dendrimers, a degree of branching of at least about 0.5 or higher is preferred. The degree of branching is expressed as follows:       f          b                    xe2x80x83                  τ        =                    N        t            +              N        b                            N        t            +              N        b            +              N        1
where Nx is the number of type x units in the structure. Both terminal (type t) and branched (type b) units contribute to the fully branched structure whilst linear (type 1) units reduce the branching factor; hence
  0  ≤      f          b                    xe2x80x83                  τ        ≤  1
where ƒbr=0 represents the case of a linear polymer and ƒbr=1 represents the case of a fully branched macromolecule.
Dendritic polymers suitable for use with the invention also include macromolecules commonly referred to as cascade molecules, arborols, arborescent grafted molecules, and the like. Suitable dendritic polymers also include bridged dendritic polymers, i.e., dendritic macromolecules linked together either through surface functional groups or through a linking molecule connecting surface functional groups together, and dendritic polymer aggregates held together by physical forces. Also included are spherical-shaped dendritic polymers and rod-shaped dendritic polymers grown from a polymeric core.
The dendritic polymers used in the practice of this invention can be generationally monodisperse or generationally polydisperse. Dendritic polymers in a monodisperse solution are substantially all of the same generation, and hence of uniform size and shape. The dendritic polymers in the polydisperse solution comprise a distribution of different generation polymers. The dendritic polymer molecules which may be used in the practice of this invention include mixtures of different interior and exterior compositions or functionalities.
Dendritic polymers which are useful in the practice of this invention include those that have symmetrical branch cells (arms of equal length, e.g., PAMAM dendrimers) and those having unsymmetrical branch cells (arms of unequal length, e.g. lysine-branched dendrimers) branched dendrimers, cascade molecules, arborols, and the like.
The term xe2x80x9cdendritic polymerxe2x80x9d also includes so-called xe2x80x9chyper comb-branchedxe2x80x9d polymers. These comprise non-crosslinked poly-branched polymers prepared by (1) forming a first set of linear polymer branches by initiating the polymerization of a first set of monomers which are either protected against or non-reactive to branching and grafting, during polymerization, each of the branches having a reactive end unit upon completion of polymerization, the reactive end units being incapable of reacting with each other; (2) grafting the branches to a core molecule or core polymer having a plurality of reactive sites capable of reacting, with the reactive end groups on the branches; (3) either deprotecting or activating a plurality of monomeric units on each of the branches to create reactive sites; (4) separately forming a second set of linear polymer branches by repeating step (1) with a second set of monomers; (5) attaching the second set of branches to the first set of branches by reacting the reactive end groups of the second set of branches with the reactive sites on the first set of branches, and then repeating steps (3), (4) and (5) above to add one or more subsequent sets of branches. Such hyper comb-branched polymers are disclosed in European Patent Publication 0473088A2. A representative formula for such hyper comb-branched polymer is:
wherein C is a core molecule; each R is the residual moiety of an initiator selected from a group consisting of free radical initiators, cationic initiators, anionic initiators, coordination polymerization initiators and group transfer initiators; A and B are polymerizable monomers or comonomers capable of withstanding the conditions required for branching therefrom or grafting thereto, at least during the polymerization of the {(A)xe2x88x92(B)} linear polymer chain and during its grafting to a prior {(A)xe2x88x92(B)} branch of the {(A)xe2x88x92(B)} core branch; each G is a grafting component, and the designation
{(A)(1xe2x88x92y)xe2x88x92(B)y} indicates that G can attach to either an (A) unit or a (B) unit; n is the degree of polymerization of the indicated generation comb-branches; y is the fraction of B units in the indicated generation branch, and has a value of 0.01 to 1; the superscripts 0, 1 and i designate the comb-branch generation level, with i beginning at xe2x80x9c2xe2x80x9d and continuing for the number of reiterative branch set generations in the polymer; and at least n0 and nxe2x80x2 are xe2x89xa72.
For purposes of clarifying terminology, it should be noted that dense star dendrimers are built by reiterative terminal branching, while hyper comb-branched dendrimers are built by reiterative comb-branching. In dense star dendrimers, subsequent generation branches are attached to the terminal moieties of a previous generation, thus limiting the degree of branching to the functionality of the previous generation terminal moiety, which would typically be two or three. In contrast, by branching oligomers upon prior generation oligomer branches in accordance with hyper comb-branched dendrimer, one can dramatically increase the degree of branching from generation to generation, and indeed can vary the degree of branching from generation to generation.
Dendritic polymers which are particularly well suited for use in preparing the gene transfection particles of this invention include various dendritic polymers containing exterior and/or interior primary or secondary amine groups, amide groups, or combination thereof. Examples include polyamidoamine (PAMAM) dendritic polymers, polypropylamine (POPAM) dendritic polymers, and polyethyleneimine (PEI) dendritic polymers. Dendritic polymers having amide and/or amine groups have a very high affinity and binding capacity for both metals and genetic materials.
In accordance with a preferred aspect of the invention, a support particle, preferably of metal is first conjugated with a dendritic polymer to form a metal/dendrimer composite which is subsequently contacted with a genetic material to form gene transfection particles. Conjugation, as used herein, refers to any of various interactions between the dendritic polymer and the support, in which the support is bonded to the dendritic polymer or otherwise localized with respect to the dendritic polymer so that the density of the support can be utilized to impart sufficient momentum to the gene transfection particle during particle bombardment to achieve cell penetration and introduction of the genetic material to the cell interior. Thus, conjugation, as used herein, encompasses chemical bonding, such as complexation, hydrogen bonding, dipole-dipole interactions, London dispersion forces, Van der Waals interactions, as well as physical entrapment or diffusion controlled retention of the support within the interior of a dendritic polymer.
The metal which is conjugated with the dendritic polymer can be in the form of individual metal atoms or metal atom-containing moieties which are bonded to functionally reactive sites within the interior or on the exterior of a dendritic polymer molecule, or physically entrapped or retained within the interior of the dendritic polymer molecule. The metal which is conjugated with the dendritic polymer may also be in the form of a cluster of metal atoms or a metal particle to which the dendritic polymer(s) is bonded.
Metal-dendritic polymer conjugates or composites in which the metal is in the form of a metal atom or metal atom-containing moiety bound to, trapped within, or retained within a dendritic polymer molecule can be prepared by localizing a metal atom-containing entity (such as a metal atom, a metal ion, or metal-containing complex or molecule) with respect to a dendritic polymer. Localization, as used herein, involves contacting the dendritic polymer with a metal atom-containing entity under suitable conditions for a suitable period to allow the metal atom-containing entity to become chemically conjugated with interior or exterior reactive sites, or both, and/or disposed within the interior of the dendritic polymer molecule. Physical restraint may range from relatively transient containment of the reactant or reactants within the interior of the dendritic polymer to relatively permanent entrapment of the reactant or reactants in the interior or exterior of the dendritic polymer. Bonding of the reactant or reactants with the interior or exterior of the dendritic polymer includes ionic bonding, donor acceptor interactions (coordination bonding), hydrogen bonding, Van der Waal interactions, and London dispersion interactions. Metal atom-containing entities can become physically entrapped within the interior of a dendritic polymer by contacting a metal atom-containing entity with a dendritic polymer having an interior which is accessible to the metal atom-containing entity, under conditions and for a period sufficient to allow the metal atom-containing entities to become disposed within the interior of the dendritic polymer molecule, and thereafter reacting the metal atom-containing entity to form a compound or ion which is physically trapped within the interior of the dendritic polymer molecule, and/or modifying the surface of the dendritic polymer molecule so that the dendrimer is no longer permeable to the metal atom-containing entity. For example, metal ions can generally enter the interior defined by generation 4 through 6 PAMAM dendrimers, and subsequently react with a complexing agent which is also capable of permeating the dendrimer surface to form a complex which is incapable of leaving the interior of the dendrimer on account of its physical size and/or shape. Methods for trapping metal atom-containing entities within the interior of a dendritic polymer by modifying the surface groups are disclosed, for example, in European Patent Application 95 201373.8 (Publication No. 0,684,044 A2).
The metal-dendritic polymer conjugates in which the metal is distributed on and/or within the dendritic polymer in the form of individual atoms or moieties containing a single metal atom can be contacted with genetic material to form gene transfection particles. All genetic materials contain an acid functionality which will readily and tenaciously bond with various surface functionally reactive sites on dendritic polymers, especially with amine and amide functional groups. Because of the very high surface density of functional groups on dendritic polymers (for example, a fifth generation PAMAM dendrimer has 128 amine bonding sites) relatively high amounts of genetic material can be conjugated to a dendritic polymer to form gene transfection particles having a much higher level of genetic material to particle mass and size than the known gene transfection particles. As a result, effective amounts of genetic material can be delivered to the interior of a cell using fewer particles, and using smaller particles. Each of these factors may contribute to lower levels of cell damage during particle bombardment, and, therefore, higher levels of cell and tissue viability after particle bombardment.
The metal-dendritic polymer conjugates described above may be combined or conjugated, to each other or to dendritic polymers which do not include any metal, to form dendritic polymer clusters or aggregates having a larger diameter or maximum dimension than a single dendritic polymer molecule. Conjugation of dendritic polymers into clusters or aggregates can be achieved by coordination bonding of at least two different dendritic polymer molecules to a single metal atom, or by use of divalent, trivalent or other polyvalent crosslinking agents, which may be linear or branched polymers or other macromolecules, including dendritic polymers having surface functional groups which will bond directly with the surface functional groups of other dendritic polymers. When two or more different types of dendritic polymers having different types of surface functional groups are used to form metal-dendritic polymer clusters by direct reaction of the different types of surface functional groups with each other, the different types of dendrimers may be first reacted with each other to form clusters or aggregates, and subsequently contacted with a metal atom-containing entity, or one or more different types of dendritic polymers may be contacted with a metal atom-containing entity to form one, or more, metal-dendritic polymer conjugate(s) which is, or are, subsequently reacted with the other dendritic polymer(s) and/or metal-dendritic polymer conjugate(s) to form dendritic polymer cluster or aggregates containing metal.
The genetic material may be contacted with the dendritic polymer, or polymers, before, during, or after the dendritic polymer, or polymers, have been contacted with the metal atom-containing entity, or entities, or a combination thereof.
The metal and genetic material loading can be controlled as desired, such as by carefully controlling the quantities of materials which are contacted with each other, by the selection of the dendritic polymer or polymers with respect to type, size, generation and surface functionality, by controlling the conditions under which the components are contacted, etc.
By suitable selection of the dendritic polymer or polymers, crosslinkers, if any, the type and amount of the metal atom-containing entity or entities, the loading level of metal and genetic material, the manner in which and the conditions under which the components are combined, any of various particle sizes, particle densities and therapeutic activities can be achieved to meet specific requirements relating to the type of cell being treated and the type of disease which is being treated.
In accordance with another aspect of the invention, the gene transfection particles can be prepared by coating dendritic polymer molecules onto the surface of a metal particle. Suitable gold particles, provided in the form of gold sols, are commercially available from a variety of different suppliers.
Preferred metal particles in accordance with this invention have a diameter or maximum dimension below 1 micrometer, and more preferably from about 1 nm to about 100 nm.
In addition to the tremendous advantages relating to improved effectiveness and reduced cell damage associated with this invention, the particles of this invention have been found to provide better protection of the genetic material against nuclease degradation, and can therefore extend the period of therapeutic effectiveness.
The method of this invention involves accelerating any of the gene transfection particles disclosed herein toward a plant or animal cell with sufficient force to cause the gene transfection particle to penetrate and enter the cell. The method can be performed in vivo on cells which are normally exposed, such as epidermal cells, in vivo on cells which are exposed by surgical methods, such as tissue or cells of various internal organs, ex vivo on tissue or cell explants which are transplanted into a host plant or animal after particle bombardment, or in vitro, such as in gene amplification techniques or in the mass production of certain gene products. Particle bombardment using the gene transfection particles of this invention can be achieved using any of various gene guns which are now well known in the art and the literature, including high-voltage electric discharge apparatus, pressure discharge apparatus, and other suitable means which have or will be developed. The gas used in the pressure discharge apparatus should be essentially inert to the support, genetic material and polymer. Suitable inert gases include, for example, helium and argon.

Method and articles for transfection of genetic material


The invention provides a composite, laminated armor panel (10) for absorbing and dissipating kinetic energy from projectiles (12), the panel (10) comprising a first outwardly-positioned layer (14) made of a hard material selected from a ceramic material and a metal having a Rockwell-C hardness of at least 27, an intermediate layer (16) softer than the first layer (14), made of a material selected from aluminium and metals having a Rockwell-C hardness of less than 27 and a third backing layer (18) of tough woven textile material, wherein the three layers (14,16,18) are laminated together and wrapped on at least four sides in a further tough woven textile material (20) which is bonded to the outer surfaces of the composite, laminated armor panel (10).

The invention provides a composite, laminated armor panel for absorbing and dissipating kinetic energy from projectiles, and resists delamination in use. The panel comprises a lamination of at least three layers. A first outwardly positioned layer is made of a hard material such as a ceramic material or a metal having a Rockwell-C hardness of at least 27. An intermediate layer is softer than the first layer, being made of aluminium or other metals having a Rockwell-C hardness of less than 27. A third backing layer comprises tough woven textile material. All layers are laminated together and wrapped on at least four sides in a further tough woven textile material, which is bonded to the outer surfaces of the composite armor panel. The woven textile material wrapping the panel is preferably made of aramide synthetic fibers or polyethylene fibers.
The present invention relates to armor for protection against projectiles.
More particularly, the invention provides a lightweight multi-layer armor plate resistant to delamination.
The aim of armor systems is to prevent the penetration of projectiles into a protected area by using protective panels of acceptable weight, volume and cost. There are additional considerations such as durability, ease of fabrication and ease of repair if needed that will impinge on the selection of suitable armor.
A further feature of a satisfactory armor system is that it is not degraded by a first projectile to such extent that a following projectile will penetrate the panel. Generally, weight is the overriding consideration in aircraft, volume and weight are important in land vehicles, and cost is the main criteria in naval vessels and stationary applications.
The traditional method of armoring vehicles has long been the use of thick steel plates. Such armor is still used today in applications where weight is not of vital concern, for example in large naval vessels and in stationary applications.
The main use of such armor in land vehicles has been in tanks. However contradictory requirements that the tank be fast and mobile, yet survive being hit by a shell from an opposing tank have posed a dilemma to tank designers. Much thought and experiment was devoted to the problem before and during the Second World War. The dilemma is well illustrated by a tank of German design, which was in use at the end of the war. The athe PzKpfw VI Ausf E Tiger tank was provided with steel armor varying in thickness between 26 and 110 mm. The tank weighed 57 ton, and a 694 hp engine was needed to drive this vehicle at its modest maximum speed of 37 km/h.
With the development of the HEAT (High Explosive Anti-Tank) shell, armor designers were faced with a warhead having a shaped copper-lined hollow in the forward edge of the explosive filling which detonated a short distance from the target armor. The explosive charge adopted a shape that created a jet of vaporized copper which burned through the armor. The warhead includes a mass of plastic explosive that is plastered by impact to the outer face of the steel armor and is then detonated.
Threats of this type led to the development during the past 40 years of more complex armor systems, thinner versions of which were later adapted for use in the protection of medium-weight road vehicles from rifle and machine-gun fire. Multi-layer armor was developed and proved in many decades as having an improved penetration resistance/weight ratio relative to steel. Further innovations effected concern the use of ceramics, artificial fibers, and various arrangements designed to deflect the projectile sideways in an outer layer so that an inner layer of the armor could contain the projectile fragments. Such armor systems weigh significantly less than a solid steel panel providing equivalent protection.
Reduced weight has enabled armor manufacturers to also meet the demand for protection of lighter road vehicles, mainly for military use, but increasingly also for civilian buses, vans and cars. Due to the large size of this market, much effort has been invested in developing armor that meets the difficult weight-volume-cost constraints for light vehicles. As has been explained in our previous Patent (U.S. Pat. No. 6,112,635), armor for light vehicles is expected to prevent penetration of rifle bullets of any type, even when close-range fire is absorbed at velocities in the range 700 to 1000 meters per second. At present it is impracticable to protect light vehicles against high caliber armor-piercing projectiles, e.g. 12.7 and 14.5 mm, because the weight of suitable armor would impede the mobility and performance of such vehicles, and because room is not available for armor of the requisite thickness.
With regard to military aircraft, armor has been provided for the area where the pilot and navigator sit. No method of armoring a complete aircraft is known.
A large volume of patents has been issued for composite armor. The following are believed to be representative of the state of the art.
King in British Patent No. 1,142,689 discloses an armor plate including a non-metallic matrix, which rigidly holds bodies of a hard shatter-resistant material. When such body is shattered by a projectile, the projectile is also fragmented, the fragments being absorbed by the matrix.
A more complex arrangement is disclosed by Poole in U.S. Pat. No. 4,061,815. He proposes sandwiching at least one layer of polyurethane between rigid impact-resistant sheets of material such as aluminium armor plate or fiberglass and a thin retaining sheet on the far side. An optional ceramic or metallic filler is embedded in the polyurethane. The lightweight armor is claimed to be suitable for aircraft. However as the lamination is between 2-5 inches thick, it is difficult to imagine how such a high volume armor could be fitted into existing airplanes.
In British patent No. 1,352,418 to the German company Feldmuhle Anlagen-und Produktions, the claimed innovation is high temperature bonding of adjacent layers. A first layer comprises at least 90% by weight of sintered alumina. At least one intermediate layer is metallic and has a greater coefficient of thermal expansion. The layers are bonded together at above 500xc2x0 C.
The present inventor has disclosed a composite armor panel in U.S. Pat. No. 6,112,635, which patent makes reference to a substantial number of prior-art patents for armor plate. An internal layer of Al2O3 pellets, preferably round, flat cylindrical or spherical, having an axis of at least 12 mm is bound in a solidified material. Most pellets are in direct contact with at least 6 other pellets. Outer layers of synthetic fibers or aluminium can be added. The panel resists several high-speed projectiles even if all rounds successively impact the same small area.
A weakness of prior-art composite armor, which has not been accorded adequate consideration, concerns the problem of local delamination, which can occur as a result of impact, typically with a high-speed projectile. Following such delamination, the effected area loses much of its protective properties, resulting in a following round penetrating the armor plate in the delaminated area.
It is therefore one of the objects of the present invention to obviate the disadvantages of prior art armor systems and to provide a composite armor panel that has improved resistance to delamination.
The present invention achieves the above objects by providing a composite, laminated armor panel for absorbing and dissipating kinetic energy from projectiles, said panel comprising:
a) a first outwardly-positioned layer made of a hard material selected from a ceramic material and a metal having a Rockwell-C hardness of at least 27;
b) an intermediate layer softer than said first layer, made of a material selected from aluminium and metals having a Rockwell-C hardness of less than 27; and
c) a third backing layer of tough woven textile material;
wherein said three layers are laminated together and wrapped on at least four sides in a further tough woven textile material which is bonded to the outer surfaces of said composite, laminated armor panel.
In a preferred embodiment of the present invention there is provided a composite, laminated armor panel wherein the first layer is formed of titanium, hard carbon steel or ceramics.
In a most preferred embodiment of the present invention there is provided a composite, laminated armor panel wherein the intermediate layer is formed of low carbon steel, medium carbon steel or aluminium.
Yet further embodiments of the invention will be described hereinafter.
The believed cause of delamination of multi-layer armor panels when impacted by a projectile is the dissipation of kinetic energy by a projectile, which does not penetrate the panel. Such energy is dissipated in several ways, among them the application of shock vibration to an intermediate layer, which shock waves propagate laterally and horizontally to adjoining areas. In the present invention, the tightly wrapped outer layer absorbs a part of such energy and prevents loosening or separation of the armor panel layers.
It will thus be realized that the novel armor of the present invention, by resisting delamination provides improved protection from the second, third and following rounds to impact the panel, and not merely from the first. Furthermore, additional and unexpected benefits are derived from wrapping the panel in an impregnated tough woven textile material such as Kevlar(copyright).
The wrapping prevents the ingress of toxic chemicals used in chemical warfare. Vehicle contamination is thus reduced and decontamination by conventional flushing equipment is readily performed.
The hard materials used for the outer layer are naturally brittle, but are advantageous in effecting projectile velocity reduction and in particular in deforming the projectile, thereby easing the task of inner layers of the armor. The wrapping bonded to the hard outer steel plate reduces crack propagation in the hard material when hit by a projectile. This brings about a further improvement in the capacity of the composite armor plate of the present invention to resist multiple impacts in a small defined area of the panel.
While during ballistic tests the bullets are fired directly at 90 degrees to the armor panel, armor used in the field will receive the vast majority of projectiles at some angle to the armor other than perpendicular. As the bullet punches through the hard outer skin, part of the bullet is already in contact with the softer intermediate layer. Because the plane common to the outer and intermediate armor layer will rarely be precisely perpendicular to the bullet axis, the bullet will be fragmented or at least deflected from its course in a manner analogous to the refraction of light waves on a plane surface bounding two different transparent media. The third armor layer is then able to prevent penetration of the deflected bullet or its fragments.
Ballistic tests were performed to validate the design. Test results obtained and listed herein fully validated expectations from the specified armor panel.
The invention will now be described in connection with certain preferred embodiments with reference to the following illustrative figures so that it may be more fully understood.
With specific reference now to the figures in detail, it is stressed that the particulars shown are by way of example and for purposes of illustrative discussion of the preferred embodiments of the present invention only and are presented in the cause of providing what is believed to be the most useful and readily understood description of the principles and conceptual aspects of the invention. In this regard, no attempt is made to show structural details of the invention in more detail than is necessary for a fundamental understanding of the invention, the description taken with the drawings making apparent to those skilled in the art how the several forms of the invention may be embodied in practice.


A toy figure with a changeable face comprising: a head; a facial area located on the head; a torso attached to the head; a pair of arms attached to the torso; a pair of legs attached to the torso; changeable markings located on the facial area, the changeable markings will change when the changeable markings receive a stimuli. A toy figure backpack comprising: a container, the container comprising a front side configured to abut against a toy figure, and a rear side; attachment means located on the container, and configured to removeably attach to the toy figure; a pair of electrically conductive contacts located on the front side; a pc board in communication with the pair of electrically conductive contacts, the pc board located within the container; a power supply located within the container and in communication with the pc board.

Children's toys are often popular for a short period of time. Toys that have a long-lasting popularity tend to key on specific creative aspects of the player. One of these is the snap together product known today as Lego's.
The Lego Group began in the carpentry workshop of Ole Kirk Christiansen, in Billund, Denmark. In 1916, Christiansen purchased a woodworking shop in Billund which had been in business since 1895. The shop mostly helped construct houses and furniture, and had a small staff of apprentices. The workshop burned down in 1924 when a fire ignited some wood shavings. Ole Kirk constructed a larger workshop, and worked towards expanding his business even further. When the Great Depression hit, Ole Kirk had fewer customers and had to focus on smaller projects. He began producing miniature versions of his products as design aids. It was these miniature models of stepladders and ironing boards that inspired him to begin producing toys.
In 1932, Ole Kirk's shop started making wooden toys such as piggy banks, pull toys, cars and trucks and houses. The business was not profitable because of the Great Depression. Farmers in the area sometimes traded food in exchange for his toys; Ole Kirk continued producing practical furniture in addition to toys to stay in business. In the mid-1930s, the yo-yo toy fad gave him a brief period of increased activity until it suddenly collapsed. Ole Kirk used the leftover yo-yo parts as wheels for toy trucks, to reduce waste. His son Godtfred began working for him, taking an active role in the company.
In 1934, Ole Kirk held a contest among his staff to name the company, offering a bottle of homemade wine as a prize. Christiansen was considering two names himself, "Legio" (with the implication of a "Legion of toys") and "Lego", a self-made contraction from the Danish phrase "leg godt", meaning "play well." Later the Lego Group discovered that "Lego" can be loosely interpreted as "I put together" or "I assemble" in Latin. Ole Kirk selected his own name, Lego, and the company began using it on their products.
Following World War II, plastics became available in Denmark, and Lego purchased a plastic injection molding machine in 1947. One of the first modular toys to be produced was a truck that could be taken apart and re-assembled. In 1947, Ole Kirk and Godtfred obtained samples of interlocking plastic bricks produced by the company Kiddicraft. These "Kiddicraft Self-Locking Building Bricks" were designed by Hilary Page. In 1939, Page had applied for a patent on hollow plastic cubes with four studs on top (British Patent N° 0.529,580) that allowed their positioning atop one another without lateral movement. In 1944, Page applied an "Improvement to Toy Building Blocks" as an addition to the previous patent, in which he describes a building system based on rectangular hollow blocks with 2×4 studs on top enabling the construction of walls with staggered rows and window openings. The addition was granted in 1947 as British Patent N° 587,206. In 1949, the Lego Group began producing similar bricks, calling them "Automatic Binding Bricks." Lego bricks, then manufactured from cellulose acetate, were developed in the spirit of traditional wooden blocks that could be stacked upon one another but could be "locked" together. They had several round "studs" on top, and a hollow rectangular bottom. They would stick together, but not so tightly that they could not be pulled apart. In 1953, the bricks were given a new name: "Lego Mursten", or "Lego Bricks."
Plastic products were not well received by customers initially, who preferred wooden or metal toys. Many of Lego's shipments were returned, following poor sales. In 1954, Godtfred had become the junior managing director of the Lego Group. Godtfred's conversation with an overseas buyer struck the idea of a toy "system", with many toys in a line of related products. Godtfred evaluated their available products, and saw the plastic bricks as the best candidate for such a "system". In 1955, Lego released the "Town Plan" as such a system, using the building bricks.
The building bricks were moderately received, but had some problems from a technical standpoint: their "locking" ability was limited, and they were not versatile. In 1958 the bricks were improved with hollow tubes in the underside of the brick. This added support in the base, enabling much better locking ability and improved versatility. The company patented the new design, as well as several similar designs to avoid competition. Ole Kirk Christiansen died that same year, and Godtfred inherited leadership of the company.
Another warehouse fire struck the Lego Group in 1960, consuming most of the company's inventory of wooden toys. Godtfred decided that the plastic line was strong enough to abandon production of wooden toys. As a result, Godtfred's brothers Gerhardt (then head of wooden toys) and Karl Georg left the Lego Company and began a separate company "Bilofix". By the end of the year, the Lego Group was employing more than 450 people.
In 1961, Lego wished to expand sales to North America, but did not have the logistical capabilities to do so. Lego made an arrangement allowing Samsonite to begin producing and selling Lego products in the United States and Canada.
1961 and 1962 saw the introduction of the first Lego wheels, an addition that expanded the potential for building cars, trucks, buses and other vehicles from Lego bricks. Also during this time, the Lego Group introduced toys specifically targeted towards the pre-school market.
In 1963, cellulose acetate, the material used to create Lego bricks, was replaced by the more stable acrylonitrile butadiene styrene (ABS plastic), which is still used today. ABS is non-toxic, is less prone to discoloration and warping, and is more resistant to heat, acids, salt, and other chemicals. Samsonite manufacturing in North America did not switch at the same time, and still used some degree of cellulose acetate in its Lego products.
1964 was the first year that instruction manuals were included in Lego sets. One of the LEGO Group's most successful series,[citation needed] the Lego train system, was released in 1966. The original train sets included a 4.5-volt motor, battery box and rails; two years later, a 12-volt motor was introduced.
On 7 Jun. 1968, the first Legoland Park was opened in Billund. This theme park featured elaborate models of miniature towns built entirely from Lego bricks. The three acre (12,000 m2) park attracted 625,000 visitors in its first year alone. During the next 20 years, the park grew to more than eight times its original size, and eventually averaged close to a million paying visitors per year. More than eighteen million Lego sets were sold in 1968.
In 1969, the Duplo system went on sale. Duplo bricks are much larger than Lego bricks, making them safer for young children, but the two systems are compatible: Lego bricks can be fitted neatly onto Duplo bricks, making the transition to the Lego system easily made as children outgrow their Duplo bricks. The name Duplo comes from the Latin word duplus, which translates literally as double, meaning that a Duplo brick is exactly twice the dimension of a Lego building brick (2×height by 2×width by 2×depth=8×the volume of a brick).
During the last three decades of the 20th century Lego expanded into new areas of toy making and marketing. In 1971, Lego began to target girls by introducing furniture pieces and dollhouses. In 1972, Lego added boat and ship sets, with floating hull pieces.
During this same period, Godtfred Kirk Christiansen's son, Kjeld Kirk Kristiansen, joined the managerial staff, after earning business degrees in Switzerland and Denmark. One of Kjeld's first achievements with the company was the foundation of manufacturing facilities, as well as a research and development department that would be responsible for keeping the company's manufacturing methods up to date. Human figures with posable arms made an appearance in 1974 in "Lego family" sets, which went on to become the biggest sellers at the time; in the same year, an early version of the "minifigure" miniature Lego person was introduced, but it was not posable and had no face printed on its head. A Lego production plant was opened in Enfield, Conn. in the United States.
In 1975 "Expert Series" sets were introduced, geared towards older, more experienced Lego builders followed by the "Expert Builder" sets in 1977. The technical sets featured moving parts such as gears, differentials, cogs, levers, axles and universal joints, and permitted the construction of realistic models such as automobiles, with functional rack and pinion steering and lifelike engine movements. In 1978 the Lego "minifigure" was added. These small Lego people have posable arms and legs, and a smile. The figure was used in many varieties of Lego sets, allowing construction of towns populated with the smiling minifigure Lego citizens.
In 1979 Lego expanded into space with the creation of Lego Space sets with astronaut minifigures, rockets, lunar rovers and spaceships and the Scala series, featuring jewelry elements marketed towards young girls. Kjeld Kirk Kristiansen became the president of Lego in this year.
Since the 1960s, educators saw Lego bricks' constructive potential as being an invaluable asset in helping children to develop creativity and problem-solving abilities. Teachers had been using Lego bricks in the classroom for a variety of reasons. In 1980, the Lego Group established the Educational Products Department (eventually renamed Lego Dacta, in 1989), to expand the educational possibilities of their toys. A packing and assembly factory opened in Switzerland, followed by another in Jutland, Denmark that manufactured Lego tires.
Between the 1960s and 90s Lego worked with Royal Dutch Shell in allowing Shell branding on certain items. In 1981, the second generation of Lego trains appeared. As before, these were available in either 4.5 V (battery powered) or 12 V (mains powered), but with a much wider variety of accessories, including working lights, remote-controlled points and signals, and decouplers.
The "Expert Builder" series matured in 1982, becoming the "Technic" series. 13 August of that year marked the Lego Group's 50th anniversary; the book 50 Years of Play was published to commemorate the occasion. In the following year, the Duplo system was expanded to include sets for even younger audiences, particularly infants; new sets included baby rattles and figures with adjustable limbs. The year after, Lego minifigure citizens gained a realm of knights and horses, with the introduction of the first Castle sets. Light & Sound sets made their appearance in 1985; these sets included a battery pack with electrical lights, buzzers, and other accessories to add another dimension of realism to Lego creations. Also that year, the Lego Group's educational division produced the Technic Computer Control, which was an educational system whereby Technic robots, trucks, and other motorized models could be controlled with a computer. Manaus, Brazil gained a Lego factory in this year, as well.
In 1984, the Technic line was expanded with the addition of pneumatic components. In August 1988, 38 children from 17 different countries took part in the first Lego World Cup building contest, held in Billund. That same year, Lego Canada was established. The Lego line grew again in 1989 with the release of the Lego Pirates series, which featured a variety of pirate ships, desert islands and treasure; the series was also the first to depart from the standard minifigure smiling face to create an array of piratical characters. The Lego Group's Educational Products Department was renamed Lego Dakta in this year; the name is derived from the Greek word "didactic", which roughly means "the study of the learning process." MIT's Dr. Seymour Papert, from the Laboratory of Computer Learning, was named "Lego Professor of Learning Research," after his ongoing work in linking the Logo programming language with Lego products.
Until 1989 Lego minifigures only came in a yellow skin color with standard smiling face, though early prototypes had a variety of skin colors and facial expressions. Lego Pirates in 1989 expanded the array of facial expressions with beards and eye patches, followed by sun glasses, lipstick, eyelashes, and so on. However, many older collectors resented the new look, saying they looked too "cartoon-ish" or "kiddy", and preferred the simplistic nature of the two eyes and smile.
In 1990 a new series designed for advanced builders was released. Three Model Team sets, including a race car and an off-road vehicle, featured a level of detail and realism not previously seen in any Lego series. Where Technic was mechanically accurate, Model Team was visually and stylistically accurate. The Lego Group became one of the top 10 toy companies in this year; it was the only toy company in Europe to be among the top 10. Legoland Billund had more than one million visitors in this year, for the first time in its history. The first-ever "Lego Professor of Business Dynamics," Xavier Gilbert, was appointed to an endowed chair at the International Institute for Management Development in Lausanne, Switzerland. Lego Malaysia was also established in 1990. In 1991, the Lego Group standardized its electrical components and systems; the Trains and Technic motors were made 9V to bring the systems into line with the rest of the Lego range.
In 1992 two Guinness records were set using Lego products: A castle made from 400,000 Lego bricks, and measuring 4.45 meters by 5.22 meters, was built on Swedish television, and a 545 meters long Lego railway line with three locomotives was constructed. Duplo was augmented with the addition of the Toolo line featuring a screwdriver, wrench, nuts and bolts; the Paradisa line, targeted towards girls, brought a variety of new pastel colors into the Lego system and focused around horses and a beach theme. In 1993 a Duplo train and a parrot-shaped "brickvac" that could scoop Lego pieces up off the floor were released.
In the late 1990s, the Lego Group brought out a series of new and specialized ranges aimed at particular demographics. The Slizers/Throwbots line preceded the Bionicle range, and uses Technic pieces and specialist moldings to create a set of action figures for boys, while Belville is a more conventional line aimed at girls and featuring large posable figures like those in the Technic range. A "Lego 4 Juniors" group features 2-inch (51 mm) tall medium-sized figures ("medi-figure") without jointed arms, and longer legs than the classic Lego minifigure. In 2003, the Lego Group introduced a completely new system, Clikits, aimed at girls and consisting of customizable plastic jewelry and accessories. In 2004, Lego added the QUATRO brick, for ages 1-3. Much like Duplo, a Quatro brick is four times the dimension of a regular Lego brick, and is compatible with the Duplo brick. Also that year, they created the second line of Knights Kingdom themed product.
Despite the popularity of Lego figures and similar competitive products, there exists a limitation of play modes for the user-child. The ability of a Lego-like toy figurine to move, emit sound, change facial expression, and respond to external user defined, game defined, or other stimuli, would add vast new dimensions of play for the user. The disclosed invention allows the potential for the realization of a more realistic and adaptive toy figure.
In yet another aspect of the disclosed invention, the ability of the toy figurine to become incorporated into a video game is made possible by the interactive simplex "polling" of figures using radio frequency, magnetic, electric, optical or acoustic means. Complete duplex data "handshake" is disclosed that can identify the toy figurine power status, figure type, and proclaimed game capabilities.
Thus there is a need for a toy action figure with remote and local power, play, identification, and selective activation that overcomes the above listed and other disadvantages.

Toy action figure with remote and local power, play, identification, and selective activation


There is disclosed a process for producing a potassium sulfate electrochemically. The process involves the use of sodium sulfate which is electrolyzed in an electrolytic cell and which results in the production of sodium hydroxide and ammonium sulfate. The process carried out in a two or three-compartment electrolytic cell and the ammonium sulfate is converted by ammoniation and treatment of the ammoniated mixture with potassium chloride to produce potassium sulfate. Potassium sulfate may then also undergo electrochemical treatment to produce potassium hydroxide and ammonium sulfate.

This invention relates to manufacturing of sodium hydroxide. More particularly, the invention relates to manufacturing of potassium hydroxide and potassium sulfate by electrolyzing sodium sulfate.
Demonstrated worldwide demand for some sodium-based chemicals, particularly for sodium hydroxide (caustic soda), has been on the rise in recent years. This strong demand, which is forecast to continue, keeps this chemical in tight supply position, thereby holding the price at a high level. This trend is not the same with respect to all sodium-based chemicals. In particular, the demand for sodium sulfate and, as a consequence, the price of this chemical is declining at the same time as the demand for caustic soda is rising.
This declining trend in the demand for and prices of sodium sulfate combined with the strong demand for and relatively high prices of other sodium-based chemicals, in particular of caustic soda, created a need for a simple and economical process for producing sodium hydroxide from sodium sulfate as feedstock. This need is even more strongly perceived in countries endowed with vast natural resources of sodium sulfate. This is, for example, the case in Canada, which has large deposits of natural sodium sulfate located in Southern Saskatchewan.
The most direct process for producing sodium hydroxide from sodium sulfate is the electrolytic conversion of an aqueous solution of sodium sulfate into aqueous solutions of sulfuric acid and caustic soda. Numerous implementations of this process are known in the prior art. Most of them make use of electrolytic cells employing diaphragms or ion permeable membranes to separate the product solutions from the feed solution, thus avoiding contamination of the products by the feedstock material.
U.S. Pat. No. 2,829,095, issued Apr. 1, 1958, to Oda et al., discloses a process for the production of acidic and alkaline solutions by electrolysis of a salt solution in a multi-compartment electrolytic cell partitioned by a plurality of anion and cation exchange membranes. The patent also discloses the use of the process for direct production of sodium hydroxide and sulfuric acid from Glauber""s salt (sodium sulfate decahydrate).
U.S. Pat. Nos. 3,135,673, issued Jun. 2, 1964, to Tirrell et al., and 3,222,267, issued Dec. 7, 1965, to Tirrell et al. claim a method and apparatus for converting aqueous electrolytic salt solutions to their corresponding acid and base solutions. A three or four compartment electrolytic cell separated by a cation exchange membrane and one or two porous, non-selective diaphragms is used for this purpose. When a solution of sodium sulfate is used as the salt solution, solutions of sodium hydroxide and sulfuric acid or sodium bisulfate are produced.
U.S. Pat. No. 3,398,069, issued Aug. 20, 1968, to Juda, claims a process for the electrolysis of an aqueous saline electrolyte in a multicellular device having cells separated by gas permeable electrodes and further partitioned by microporous fluid-permeable diaphragms or ion-permselective membranes. When applied to a solution of sodium sulfate, the process produces solutions of sodium hydroxide and sulfuric acid.
U.S. Pat. No. 3,907,654, issued Sep. 23, 1975, to Radd et al., discloses an electrolytic cell particularly useful in electrolysis of sodium sulfate to form sulfuric acid and sodium hydroxide. The cell, which does not employ any ion permeable membranes, comprises a housing having a parent solution chamber and two electrode compartments located on the lower side of the housing and separated from each other but in communication with the parent solution chamber and positioned vertically beneath or above. Mounted within the electrode compartments are an anode and a cathode, each of which is porous to permit passage of a product solution therethrough. The product solutions of sodium hydroxide and sulfuric acid separated by gravity forces are withdrawn through the porous electrodes.
U.S. Pat. No. 4,561,945, issued Dec. 31, 1985, to Coker et al., claims a process for producing sulfuric acid and caustic soda by electrolysis of an alkali metal sulfate in a three-compartment membrane cell having a hydrogen depolarized anode. Hydrogen gas in the anode chamber is oxidized to produce hydrogen cations which migrate to the central (buffer) chamber through a membrane and combine with the sulfate anions from the alkali metal sulfate solution to produce sulfuric acid. Alkali metal ions are transported across another membrane to the cathode chamber to produce caustic and gaseous hydrogen. Both membranes used in the cell are cation selective membranes.
A similar process for increasing concentration of sulfuric acid in solutions containing an alkali metal sulfate, sulfuric acid and alkaline earth metal ions is disclosed in U.S. Pat. No. 4,613,416, issued Sep. 23, 1986, to Kau et al. Also in this case the anode compartment and the cathode compartment of a three-compartment cell are each bounded by cation exchange membranes.
In U.S. Pat. No. 5,445,717 issued to Karki et al., issued Aug. 29, 1995, there is disclosed a method for the simultaneous production of alkali metal or ammonium peroxodisulphate salts and alkali metal hydroxide. In the reference, the electrolytic phase of the method is performed in a three-compartment electrolytic cell with the middle space conducting alkali metal sulfate, the anode space ammonium or alkali metal sulfate or a mixture thereof and into the cathode space water diluted alkali metal hydroxide.
This patent proceeds according to a different process to that described herein and does not provide for the preparation of potassium sulfate from a sodium sulfate starting material.
A further variation on electrosynthesis is demonstrated in Toomey, U.S. Pat. No. 5,290,404, issued Mar. 1, 1994. In this reference, an electrochemical cell is employed for producing an alcohol or carboxylic acid from a corresponding metal salt. Metal cations and residues are also recovered during the process. This process does not employ a three-compartment desalination cell, but rather employs a standard two compartment cell divided by cation permeable membrane.
In U.S. Pat. No. 5,246,551, issued Sep. 21, 1993, to Pletcher et al., an electrochemical method for the production of alkali metal hydroxides without co-production of chlorine is disclosed. In this reference, the use of a specific group of salts such as alkali metal carbonates, alkali metal bicarbonates and the like are electrolyzed in a single membrane-two solution cell with hydrogen consuming anodes. One of the advantages of this reference is the lack of the co-production of chlorine, however, the use of these specific salts is not necessary and has been overcome by the instant application.
Martin, in U.S. Pat. No. 5.230,779, issued Jul. 27, 1993, provides an electrochemical process for the production of sodium hydroxide and sulfuric acid from acidified sodium sulfate solutions. The process particularly takes place in a two compartment electrolytic cell and does not provide any teachings with respect to potassium sulfate generation, potassium chloride or ammonium sulfate generation.
Other references generally related to electrolysis and electrosynthesis include U.S. Pat. Nos. 4,033,842 and 5,286,354.
It would be desirable if there were a process where electrosynthesis or other electrochemical methods could be employed to produce useful potassium compounds such as potassium sulfate, potassium chloride as well as fertilizer compositions, namely ammonium sulfate. The present invention employs additional unit operations onto existing processes to result in the preparation of these desirable compounds.
One object of the present invention is to provide an improved electrochemical process for preparation of potassium sulfate and potassium hydroxide.
A further object of one embodiment of the present invention is to provide a process for producing potassium sulfate in an electrolytic cell, comprising the steps of:
passing a solution of sodium sulfate through a central compartment of a three-compartment electrolytic cell having a cathode compartment and an anode compartment separated from the central compartment by a cation selective ion exchange membrane and an anion selective ion exchange membrane, respectively;
passing a catholyte through the cathode compartment and an anolyte through the anode compartment;
passing a direct electric current between an anode and a cathode located in the anode compartment and the cathode compartment, respectively, thus producing sodium hydroxide in the cathode compartment and sulfuric acid in the anode compartment;
generating ammonium sulfate;
elevating the pH of the ammonium sulfate product;
introducing a potassium chloride; and
precipitating potassium sulfate.
The unit operation patented in U.S. Pat. No. 5,098,532, is a particularly useful unit operation and it has been found that by augmenting this unit operation with further process steps, useful products such as potassium sulfate, potassium chloride, ammonium sulfate and potassium hydroxide all can be easily formed without concomitant production of chlorine.
As was proposed in the prior art, metal hydroxides have been previously synthesized electrochemically, but the prior art references failed to provide a process where sodium sulfate could be used as an initial feedstock to prepare the compounds indicated above.
It is known that sodium sulfate can be split into caustic and ammonium sulfate in a three-compartment electrochemical cell by the teachings of U.S. Pat. No. 5,098,532. This technology, as well as other technologies often encounter technical challenges created by the concentrations of acids and basis formed in the electrochemical cell and the back migration of protons across the anion exchange membrane. These problems manifest in negative effect on the current efficiency. The acid concentration in the anolyte also contributes to accelerated anode degradation.
In the instant invention, these problems are alleviated by the introduction of ammonia into the anolyte compartment. This produces caustic with ammonium sulfate the ladder commonly used as fertilizer. The fertilizer (ammonium sulfate) can then be upgraded by chemical transformation in the electrochemical cell to potassium sulfate.
In accordance with a further object of one embodiment of the present invention there is provided a process for producing potassium hydroxide and potassium sulfate, the process comprising the steps of:
(a) providing a first and a second three-compartment electrolytic cell, each cell having a cathode compartment and an anode compartment separated from a central compartment by a cation selective ion exchange membrane and anion selective ion exchange membrane;
(b) passing a solution of sodium sulfate through the central compartment;
(c) passing a catholyte through the cathode compartment and an anolyte through the anode compartment of the first three-compartment electrolytic cell;
(d) passing a direct current between an anode and a cathode located in the anode compartment and the cathode compartment, respectively, to produce sodium hydroxide in the cathode compartment and sulfuric acid in the anode compartment;
(e) generating ammonium sulfate;
(f) elevating the pH of the ammonium sulfate;
(g) introducing potassium chloride into the ammonium sulfate;
(h) forming potassium sulfate;
(i) feeding a solution of the potassium sulfate into the central compartment of a second three-compartment electrolytic cell;
(j) elevating the pH of said potassium sulfate; and
(k) forming potassium hydroxide.
To carry out the process according to the invention, any electrolytic flow cell using a two or three-compartment configuration can be used in either continuous or batch mode of operation.
In the process, the anolyte, the catholyte and the feed solution are circulated through the respective compartments of the cell at a flow rate depending on the cell used, typically of from about 0.1 L/min to about 30 L/min. The current density is limited by the efficiency considerations (current efficiency of the process decreases with growing current density) and by the stability of the membranes used. Typical current densities are in a range of from about 1 mA/cm2 to about 500 mA/cm2.
The feed solution of sodium sulfate may have a concentration of from about 0.1M to the solubility limit. The concentration of from about 1M to about 1.1M is preferred. For concentrated feed solutions, it may be necessary to heat the solution generally to about 60xc2x0 C. prior to circulating it through the cell, to prevent the crystallization of the salt.
The feed solution should be as free as possible of heavy metal contaminants that are usually present in the naturally occurring Glauber""s salt. If this salt is used as a starting material, the bulk of heavy metal ions can be precipitated, for example, by addition of sodium carbonate and/or sodium hydroxide to a solution of the salt. The remaining amounts of polyvalent cations, in particular of calcium and magnesium ions, can be removed by treating the resulting solution with an ion exchange resin, e.g. by passing the solution through an ion exchange column packed with a suitable ion exchange material, for example Duolite(trademark) C-467 from Rohm and Haas, or an equivalent material. After such a treatment the heavy metal ion concentration normally will not exceed about 20 ppb.
The catholyte and the anolyte can both be water, but it is preferred that they are solutions of sodium hydroxide and ammonium sulfate, respectively, as this gives improved conductivity. In the case of sodium hydroxide solution, the starting concentration should be in the range of from about 0.01M to about 2.74M. In the case of ammonium sulfate solution the starting concentrations should be in the range of from about 0.01M to about 3.5M. A concentration of about 3M is preferred. The choice of the starting concentrations of the anolyte and the catholyte may be also affected by the mode of operation of the electrolytic cell. For example, for the continuous mode of operation, starting concentrations closer to the upper limits of the above ranges are preferred.
To avoid an excessive accumulation of hydrogen ions in the anolyte, ammonia in either the liquid or the gaseous form is introduced into the anolyte at such a rate as to keep the pH of the solution at a predetermined level. The choice of suitable pH of the anolyte may be affected by several other factors, in particular by the ion exchange membranes and anode materials used. Generally, the pH of the anolyte may be maintained at any level in the range of from about 0.5 to about 12. A pH of from about 0.5 to about 7 is preferred and pH of from about 0.5 to about 3.5 is particularly preferred. It appears that under these acidic conditions there is little or no anode corrosion as well as no or very little formation of nitrogen and ammonium nitrate due to electrooxidation of ammonia.
The materials for electrodes, beside providing good current conduction, must be corrosion resistant under the operating conditions of the cell. Suitable cathodes are low hydrogen over potential cathodes, for example gold, platinum, nickel or stainless steel. Because of the lower cost, nickel and stainless steel are preferred.
The choice of the anode material is mostly restricted by the presence of ammonia in the anolyte solution. Under conditions (pH 9 to 12) cathode made of some materials, such as nickel, graphite and stainless steel may corrode quickly. In this range of pH anodes made of platinum, platinized titanium, magnetite or anodes of low oxygen over potential such as DSA(trademark) type electrodes (iridium or platinum oxides on a titanium substrate) are preferred. Under acidic conditions (pH 0.5 to 2) DSA-O2 anodes are preferred. However, less expensive materials, such as lead dioxide on titanium or Ebonex(trademark) (material comprising Ti4 O7) may be used. Lead dioxide on lead would be even less expensive anode material, but there exists a possibility that this material might liberate lead into the anolyte, thus making ammonium sulfate unacceptable for use as a fertilizer.
The ion-selective membranes used to separate the anode and cathode compartments from the central compartment are essentially insoluble, synthetic, polymeric organic ion-exchange resins in sheet form. Those selective to cations usually have sulfonate and/or carboxylate groups bound to the polymers; those selective to anions usually have amino functionality bound to the polymer. These ion exchange membranes are commercially available under various trade names, for example Nafion(trademark) or Flemion(trademark) (cation exchange membranes) or Neosepta(trademark) (anion exchange membranes). Cation selective membranes made of stable perfluorinated cation exchange resins are preferred.
Even though, in principle, any cation or anion exchange membrane may be used in the process according to the invention, their choice may be in practice limited to those showing sufficiently good stability under operating conditions of the electrolytic cell. For example, the choice of the anion selective membrane maybe limited by both the concentration of sulfate ion and/or ammonia in the anolyte and the presence of hydroxyl ions in the feed solution, due to the back migration of hydroxyl ions from the catholyte. Of the membranes showing good stability, membranes having high ionic selectivity and low electrical resistance are preferred. A person skilled in the art will be able to choose suitable membranes without difficulty.
An example of the anion exchange membrane preferred for carrying out the process of the invention is Neosepta(trademark) AMH membrane, which shows good stability at the anolyte pH in a range of 1-12. Examples of preferred cation exchange membranes are perfluorinated membranes such as Nafion(trademark) and Flemion(trademark) membranes, which show good stability for NaOH concentration up to 50%.
Having thus generally described the invention, reference will now be made to the accompanying drawings.

Process for producing potassium hydroxide and potassium sulfate from sodium sulfate


An eating utensil including a chopsticks 1, 1A-1H that includes a self-elevating eating section 10, 10A-H feature regardless of placement of a handling section 12, 12A-12H on a horizontal surface 32 (when a chopstick is rested by a User). Other embodiments may be described and claimed.

A pair of chopsticks are commonly used as eating utensils. Each chopstick commonly has two sections, one section for picking up food that can be referred to as an eating section and the other end for holding by a user that can be referred to as a handling section. In use the section for picking up food, also the chopstick eating section, may become covered with bits of food or sauce. When not in use, chopsticks may be placed flat on a horizontal surface, such as a tabletop commonly causing an area of the chopstick eating section to contact the horizontal surface. To avoid contaminating a chopstick eating section or a selected horizontal resting surface area (i.e. table), a user may rest or lean the chopsticks on a chopstick rest or other item to prevent undesired eating section contamination. It may be inconvenient and wasteful to employ a separate object to rest a chopstick. The present invention eliminates the need for a separate rest object.