A method of treating putrescible cakes to reduce the E. Coli and odor present in the cake and prevent further odor generation comprising the step of maintaining the cake under substantially anoxic condition in the presence of ammonium and/or nitrate moieties at pH 7.5 to pH 10.5 for a period of more than 1 day, the cake having a solids content of between 20% to 75% by weight.

Biodegradable organic wastes are produced in large quantities annually by industrial, agricultural and domestic activities. In the treatment of municipal sewage, for instance, at least three such waste streams are produced, namely grits, screenings, and sewage sludge. All biodegradable materials are capable of undergoing putrefaction, however, the process only occurs in the presence of at least 10% water. Normally, significant putrefaction can be observed when such a waste contains over 20% water. It is known that in the process of putrefaction many volatile components such as hydrogen sulphide, mercaptans, volatile fatty acids and ammonia are generated. Such compounds are responsible for the offensive odour that is characteristic of rotting matters. In industrialised countries such organic wastes are disposed off in incinerators, landfills or recycled to agriculture as fertiliser or soil conditioner. However, incineration and land filling are regarded as needless destruction of valuable resources and environmentally harmful. Thus, in Europe for instance, recycling is encouraged while both incineration and land filling are being restricted.
There are regulations governing the recycling of any waste products to agriculture. They vary from country to country, but an important underlying principle of recycling is that it should bring an agricultural benefit and have regards for environment health and odour nuisance. Agricultural benefit will be achieved when an application of a waste to land improves soil conditions for crop growth whilst ensuring the protection of the environment. If the wastes contain pathogens, as is the case with sewage sludge, health risks may exist for farm workers and animals. Suitable treatment processes must therefore be applied to the wastes before recycling. Such treatments must be capable of significantly reducing the E. coli content of the waste and preventing odour generation by imparting stability to the material.
Known treatments for organic wastes include biological, physical and chemical processes. Biological processes such as anaerobic digestion or composting impart stability to the waste by reducing its organic content. Thermal drying is a physical treatment that does not alter the chemical make up of the waste and stabilisation can only be achieved by reducing and maintaining the water content of the waste to a level below 10%. Lime is the most common chemical treatment for sewage sludge. In this case, the organic content of the sludge remains unchanged. The lime typically raises the pH of sludge to over pH 12 whereby pathogens such as E. coli are deactivated.
The mentioned treatment processes all have disadvantages and drawbacks. Digestion and composting, for instance, are very slow processes. Typically, they take several weeks to complete and require very costly processing plants. On the other hand, drying is very energy intensive and sludge drying, in particular, is often a hazardous process because of the risk of explosion with the ever presence of dust. Lime treatment is only favourable for applications on acid soils. On exposure to air, particularly during a long stockpiling period, reaction between the lime and carbon dioxide rapidly reduces the pH of sludge to a level where biological activities can resume and the resulting odour release may cause a nuisance.
There have also been attempts to convert organic wastes to fertilisers. Such methods combine chemical treatment at elevated temperature to kill pathogen and odour causing bacteria and simultaneously achieve nutrient enhancement. EP 0143392 A1 (ECODECO spa) describes a salting process for sludge slurry having dry solid content of 0.1% to 20% by weights. The process uses high salt concentration, for example, saturated ammonium sulphate with acidic pH. WO 93/14046 A1 (KAMBI AS) describes a very high temperature acid treatment to dissolve the solids followed by neutralization of the resulting hydrolysate with ammonia. In yet another application (US 2002/0088749 A1) Highsmith describe a treatment method involving ammonium and phosphate salts with acids. The Highsmith method applies to anaerobically digested sludge rather than raw sludge and it does not address the odour issue in any satisfactory manner. While the increased nutrient value of such organic fertilisers make them valuable, the high cost of their manufacture has not facilitated their commercialisation.


An autonomous automated intent mining system extracts intents from stored conversations in a text-based chat corpus for use in an AI-driven dialog system. The intent mining system includes an intelligent pre-processor for extracting the conversation data from a computer memory and operating on the conversation data to identify relevant utterances. The system additionally includes a representation processor for operating on the identified relevant utterances to create a numerical representation. The system also includes a clustering processor for generating clusters of utterances and classifying each of the identified relevant utterances into a cluster based on the numerical representation of each utterance. Each generated cluster represents a unique intent for use in the AI-driven dialog system.

The growth of AI has fueled progress in intelligent conversational AI driven dialog systems and chatbots. Recent advances in machine learning and natural language processing have led to the development of virtual conversational agents such as Apple Siri™, Google Assistant™, Amazon Alexa™, etc. In order to operate successfully, AI dialog systems require the ability to understand human utterances. Building automated intelligent dialog systems that can hold successful and human-like conversations requires the intelligent dialog system to understand the intent behind the human utterance. Understanding of the intent requires the development of sophisticated intent recognition techniques for identifying intent from human utterances.
Intent detection is typically formulated as a supervised intent classification problem where a human dialog designer manually specifies the intents and their corresponding sample utterances in order to train a supervised intent classifier. Given a piece of text, namely the human user utterance, and each of the intents defined by the dialog designer, the task of predicting the intent of a new utterance reduces to a standard text classification problem. Popular commercial and open source conversational platforms such as Microsoft's LUIS™, Google's DialogFlow™ and RASA™ typically have a natural language understanding (NLU) module, which provides such an intent classifier. These systems require a large volume of labelled data of <utterance, intent> pairs to train the intent classifier. As set forth above, the acquisition of these pairs requires repeated action by a human dialog agent.
Many problems arise in the context of currently available intent classifiers. Typically, for domain specific chatbots, there is insufficient labelled data for each intent. Customer intents repeat in the dataset and there are different ways of expressing the same intent. Typically to train a dialog agent, a labelled dataset is required that captures all possible customer intents expressed in multiple ways.
Manual labelling of a dialog dataset/conversation corpus is extremely time-consuming, error-prone and expensive. More importantly, the dialog designer ends up having to manually specify intents. Additionally, a wide and diverse set of sample utterances must be provided for each intent. The manual labelling process not only consumes considerable time and effort but is further prone to missed dialog system configurations due to human oversight.
Thus, existing processes are error-prone and costly, and require repetitive efforts for each domain as each will have its own set of intents and corresponding utterances. Conversations go awry when user intent is not recognized correctly. When an AI dialog system fails to make a correct response, this is often due to intent recognition errors resultant from missed intents, undefined intents, and misclassified intents. Each of these errors requires different handling to improve intent recognition.
Accordingly, a solution is needed for reducing both the manual effort required to build a high-quality labelled training dataset needed for training an intent recognition model, and the frequency of intent recognition errors. An automated intent mining system is needed that will automatically extract intents and sample utterances from a raw and unlabeled historical conversation corpus. Such an automatic intent mining system will considerably reduce the manual effort and will help the dialog designer in building a high-quality training dataset that includes all intents expressed in the conversation corpus in a diverse set of ways. Training an intent recognition model on such a high coverage and diverse dataset will further reduce the chances of intent misclassification thereby improving the performance of an automated dialog system.

Method and system for automated autonomous intent mining


A case hardened steel with excellent cold forgeability and excellent impact properties after case hardening processing contains C, Si, Mn, S, Cr, Al, Ti, Nb, B, and N, with the balance being iron and unavoidable impurities. Of precipitates containing Ti and/or Nb, precipitates having a size of not less than 20 μm2 are at a number density of not more than 1.0/mm2. Of precipitates containing Ti and/or Nb, precipitates having a size of more than 5 μm2 and less than 20 μm2 and containing Mn and S are at a number density of more than 0.7/mm2 and not more than 3.0/mm2. The ferrite fraction is more than 77% by area.

With respect to mechanical parts used for automobiles, construction machines, and other various industrial machines, parts that are required to have particularly high strength are conventionally subjected to a surface-hardening heat treatment (case hardening treatment) such as carburizing, carbonitriding, or nitriding. For these applications, usually, case hardened steels specified by JIS, such as SCr, SCM, and SNCM, are used. The steel is formed into a desired part shape by machining such as cutting or forging and then subjected to a surface-hardening heat treatment as mentioned above, followed by a finishing process such as polishing, whereby a part is produced.
In recent years, in such mechanical parts, it has been desired to reduce the production cost, shorten the lead time, and reduce the CO2 emission during production, for example. Accordingly, part-forming methods are being changed from conventional cutting or hot forging to cold forging, and excellent cold forgeability is thus required. In addition, in a case hardened steel specified by JIS, the coarsening of crystal grains occurs due to the surface-hardening heat treatment after cold forging. Thus, it is also important to suppress the coarsening of crystal grains. In order to solve the problem of the coarsening of crystal grains, there is a conventionally used technique in which elements such as Al, Nb, and Ti are added to finely disperse precipitates such as AlN, Nb (CN), and TiC, and such fine precipitates are used to stop the migration of the crystal grain boundary (e.g., Patent Documents 1 to 8).
Japanese Patent Application Laid-Open Publication Nos. 2007-217761, 2006-307271, 2006-307270, 2007-321211, 2004-183064, 11-335777, 2006-161142, and 2007-162128 each disclose that the coarsening of crystal grains can be prevented by controlling the number of Nb- and/or Ti-containing precipitates having a predetermined grain size or composition (carbides, carbon nitrides, etc.) within a predetermined range. Although the disclosures have some preventive effects on the coarsening of crystal grains, cold forgeability has not yet been sufficient.

Case hardened steel and method for producing same


A silver waste recovery system including a container having an inlet and an outlet at a lower elevation than the inlet, filler material in a silver cell is in communication with the inlet and a separate non-silver reactive filter is in communication with the outlet. A catch basin is positioned about the silver cell and the non-silver reactive filter contains particulates in the area of the filter and the filler material. Fluid entering the inlet passes through the silver cell and exits into the catch basin. It thereafter enters the non-silver reactive filter and exits from it through the outlet.

This invention relates to apparatus for silver waste recovery, and more specifically, to a gravity-flow apparatus for use in the recovery of silver from photo processor waste streams.
A number of devices employing containers for recovering silver from photo processor waste streams such as spent fixing solutions from photographic paper and film processes are known in the industry. These devices generally pass the solution containing silver salts through a metal filter. The metal utilized in the metal filter is selected due to its electromotive force series characteristic being higher than that of silver. As the silver salts pass through the metal filter, a chemical replacement action causes the silver to be deposited on the metal filter. When the supply of metal on the metal filter for exchange is exhausted, the contents of the container, especially the used metal filter, are processed at a refinery to recover the silver left therefrom.
In order to safeguard the environment, it is important to be able to control the release of silver-containing solutions into the environment. Known sources of silver containing solutions have traditionally been treated to remove the silver salts from these solutions prior to disposing of the remaining solution into the environment. Attempts have been made, in the prior art, to fashion silver recovery systems that remove a large quantity of silver from the solution prior to the disposal of the solution. Some of these prior art methods unfortunately leave a relatively large silver component in the solution after the solution passes through the silver recovery systems. Currently the EPA has a requirement that waste water have no greater than five parts per million silver content. Additionally, it is also possible that city and state clean water requirements may be more strict. Accordingly, many users of silver containing solutions are in need of an effective silver recovery system.
U.S. Pat. No. 5,837,188 issued to Peterson on Nov. 17, 1998, discloses a metal filter utilized in conjunction with a non-metallic mesh material positioned about and to closely adjacent to an exterior surface of the filler filter material. This patent discusses at least some of the known prior art silver recovery systems. Some of these prior art silver recovery systems utilize steel wool as a metal filter. Others utilize large openings in screen wire permitting solution to bypass the filter material and exit the vessel with silver remaining in the solution. Others utilize solution flow from the bottom of a tube upward through metal shavings and a bed of neutralizing material. While still others utilize a mesh bag to contain the silver material when the core is moved from the interior bag. Finally, others utilize fluid deflectors and baffles to increase the length of fluid flow through the filter.
These prior art silver recovery systems suffer from a number of perceived problems. First, the affluent of the silver recovery systems exits the units after passing last through the metal filter. Accordingly, if any silver particulate breaks off on the metal filter, the silver will likely end up passing out of the unit as effluent. Secondly, if the capacity of the metal filter or filler material is close to the end of its useful life, the user may have trouble visually inspecting to see the amount of useful life left by the unit.
Although some prior art systems have employed a mesh bag around a silver recovery filter, a need exists to provide a more suitable catch for particulate matter in the solution. In the prior art, external portions of the mesh bag may become fouled with particulate and perhaps pass to the outlet and into the environment.
If the filter material of these prior art systems is depleted, then the silver-containing effluent will pass directly to the outlet. As such, the silver-containing effluent may flow outwardly of the system without reacting with the filter material.


A method and apparatus is provided for performing a filter control of a delay lock loop circuit. A coarse delay and/or a fine delay are implemented upon a reference signal based upon a phase shift between the reference signal and a feedback signal. A synchronized output signal is generated based upon the coarse delay and the fine delay. The apparatus of the present invention includes a delay lock loop to provide an output signal based upon a phase difference between a reference signal and a feedback signal. The delay lock loop comprises a filter to provide a filter response to the phase difference. The filter response is capable of providing a coarse delay and/or a fine delay.

1. Field of the Invention
This invention generally relates to a semiconductor memory device, and, in particular, to a majority filter control of a delay lock loop.
2. Description of the Related Art
Modem integrated circuit devices are comprised of millions of semiconductor devices, e.g., transistors, formed above a semiconductor substrate, such as silicon. These devices are very densely packed, i.e., there is little space between them. Similarly densely packed electrically conducting lines may also be formed in the semiconductor substrate. By forming selected electrical connections between selected semiconductor devices and selected conducting lines, circuits capable of performing complex functions may be created. For example, bits of data may be stored by providing electrical current to a plurality of bit lines and an orthogonal plurality of word lines that may be electrically coupled to one or more capacitors in a semiconductor memory.
The semiconductor memory may be a dynamic random access memory, a flash memory, and the like. The semiconductor memory typically comprises an array of memory cells, address decoding circuitry for selection one, or a group, of the memory cells for reading or writing data, sensing circuitry for detecting the digital state of the selected memory cell or memory cells, and input/output lines to receive the sensed data and convey that information for eventual output from the semiconductor memory. In many cases, the array of memory cells will be sub-divided into several sub-arrays, or subsets, of the complete collection of memory cells. For example, a semiconductor memory having 16 megabits (224 bits) of storage capacity may be divided into 64 sub-arrays, each having 256 K (218) memory cells.
Flash memory (sometimes called xe2x80x9cflash RAMxe2x80x9d) is a type of non-volatile memory that can be erased and reprogrammed in units of memory called blocks. Other types of memory may be erased and rewritten in smaller units, such as units at the byte level, which is more flexible, but slower than the block operations of flash memory. Flash memory is commonly used to hold control code such as the basic input/output system (BIOS) in a personal computer. When BIOS needs to be changed (rewritten), the flash memory can be written in block (rather than byte) sizes, making it faster to update. Applications employing flash memory include digital cellular phones, digital cameras, LAN switches, computers, digital set-up boxes, embedded controllers, and other devices.
Although forming the selected electrical connections may enable the circuits to perform their intended functions, undesirable electrical connections may result in a variety of malfunctions, e.g., short circuit paths may be established. Thus, semiconductor devices, such as the capacitors in memory cells, and conducting lines, such as the input/output lines, may generally be electrically isolated. For example, to ensure that devices, lines, and/or groups thereof, that form the semiconductor memory, are properly isolated, modem semiconductor processing involves the formation of shallow trench isolations (STI) in various regions of the substrate. These shallow trench isolations are typically formed by etching a trench in the semiconductor substrate and, thereafter, filling the trench with an isolation material, e.g., an insulator, such as silicon dioxide, silicon oxynitride, silicon nitride, or other like materials. However, it may be difficult to completely isolate the devices and/or lines. For example, defects in the semiconductor substrate or in the manufacturing process may form an undesirable conducting path between the devices and/or lines in the semiconductor memory that may cause the semiconductor memory to malfunction.
Typically, digital systems, such as memory systems, may comprise a delay lock loop that may be used to align the edges of a plurality of digital signals. For example, a delay lock loop circuit may be used to align the rising edge and/or the falling edge of a clock signal based upon a reference clock signal, to produce a synchronized clock signal. Many times, digital signals from multiple sources access one or more memory spaces in a memory, unit. It is desirable that these digital signals be synchronized for proper access of memory. Typical delay lock loops comprise a phase detect unit that detects the phase differences between a plurality of signals. The output of the phase detect unit is then used to affect the operation of a filter that adjusts the delay of an output of the delay lock loop.
The problems associated with the current methodologies of implementing the delay lock loop include an overreaction when performing delay compensation due to external factors on a digital line. These external factors that cause inadvertent adjustments of the delay lock loop include a noise spike on a bus or a control signal. These noise spikes may cause a delay lock loop circuit to be over-dynamic, wherein the delay lock loop circuit tracks a noise spike, thereby adding unintentional delays to the line.
The present invention is directed to overcoming, or at least reducing, the effects of, one or more of the problems set forth above.
In one aspect of the instant invention, a device is provided to perform a filter control of a delay lock loop circuit. The device of the present invention includes a delay lock loop to provide an output signal based upon a phase difference between a reference signal and a feedback signal. The delay lock loop includes a filter to provide a filter response to the phase difference. The filter response is capable of providing a coarse delay and/or a fine delay.
In another aspect of the instant invention, a delay lock loop is provided to perform a delay function upon a signal. The delay lock loop of the present invention includes a forward path comprising an input path for receiving a reference signal and a delay path for providing at least one of a coarse delay and a fine delay upon the reference signal to provide an output signal. The delay lock loop of the present invention also includes: a feedback path to provide a feedback signal based upon the output signal; a phase detector to generate a shift signal based upon a phase comparison of the feedback signal and the reference signal; and a filter to receive the shift signal from the phase detector and provide at least one of a fine delay signal and a coarse delay signal for generating the output signal.
In another aspect of the instant invention, a circuit is provided to perform a filter control of a delay lock loop circuit. The circuit of the present invention comprises: a first delay unit to receive a reference signal and provide a delay upon the reference signal; a filter to apply a second delay upon the reference signal to generate an output signal; a feedback delay unit to provide a delay upon the output signal to generate a feedback signal; and a phase detector to determine a phase difference between the reference signal and the feedback signal and generate a shift signal.
In yet another aspect of the instant invention, a system board is provided for performing a filter control of a delay lock loop circuit. The system board of the present invention comprises a first device and a second device. The first device includes a memory location for storing data and a delay lock loop to provide an output signal based upon a phase difference between a reference signal and a feedback signal. The delay lock loop includes a filter to provide a filter response to the phase difference. The filter response includes providing at least one of a coarse delay and a fine delay. The second device is operatively coupled to the first device. The second device is adapted to access data from the first device based upon an operation performed by the delay lock loop.
In yet another of the instant invention, a memory device, which is capable of performing a filter control of a delay lock loop circuit, is provided. The memory device of the present invention includes delay lock loop to provide an output signal based upon a phase difference between a reference signal and a feedback signal. The delay lock loop includes a filter to provide a filter response to the phase difference. The filter response includes providing at least one of a coarse delay and a fine delay.
In another aspect of the instant invention, a method is provided for performing a filter control of a delay lock loop circuit. A coarse delay and/or a fine delay are implemented upon a reference signal based upon a phase shift between the reference signal and a feedback signal. A synchronized output signal is generated based upon the coarse delay and the fine delay.
In yet another aspect of the present invention, a computer readable program storage device encoded with instructions is provided for performing delay function upon a signal. A computer readable program storage device encoded with instructions that, when executed by a computer, performs a method, which comprises: providing at least one of a coarse delay and a fine delay upon a reference signal based upon a phase shift between the reference signal and a feedback signal; and generating a synchronized output signal based upon the coarse delay and the fine delay.


Aquatic apparatus formed by a support with a fixed tube positioned thereon and having an open end; a movable tube encircles the fixed tube is sealed thereto, and has a pivoted end cap beyond the position of the seal and at least one vent below the position of the seal; the end cap is controlled and pressurized fluid is applied to the fixed tube.

This invention relates to fluid controlled aquatic platforms and, more particularly, to fluid controlled platforms that can be used for general recreation.
Conventional dive platforms generally are fixed structures that have fixed locations in relation to the bodies of water where they are used.
Accordingly, it is an object of the invention to provide greater flexibility for platforms that are used for aquatic recreation, such as diving and jumping.
Another object of the invention is to make use of fluidic induced movements in conjunction with aquatic or dive platforms.
A further object of the invention is to provide aquatic platforms that give enhanced recreational effects.
In accomplishing the foregoing and related objects, the invention provides aquatic apparatus in which a fixed tube or cylinder, with an open end, is positioned on a support in the form of a base frame that may connect to a poolside or ladder. A movable tube or cylinder having a pivoted end cap encircles the fixed tube or cylinder and is sealed to it. At least one vent is located in the movable tube or cylinder below the position of the seal to the fixed tube or cylinder. Provision is made for controlling the end cap, illustratively by an aquatic or dive platform, and pressurized fluid is applied to the fixed tube.
In accordance with one aspect of the invention, the float support is formed by a plurality of at least three pontoons connected to the fixed tube. Adjoining ones of the pontoons can be connected by legs, and a platform is pivotally connected to the moveable tube.
In accordance with another aspect of the invention, the platform controls the end cap of the movable tube, for example, by at least one cable, rod, or the like, that extends from the platform to the end cap; whereby the downward pivoting of the platform can produce closure by the action of the end cap on the movable tube.
When pressurized fluid is applied to the fixed tube, for example, through a hose, and the platform is free to move, the pressurized fluid forces the end cap to an open position and the fluid exits from the aquatic structure in the form of a spray. When pressure is applied to the platform, for example, by having a person stand on it, the end cap is moved downwardly to a closed position and pressurized fluid (between the top of the fixed tube and the moveable tube) causes the movable tube to rise, simultaneously elevating the platform on which a person, such as a swimmer, is standing. When the swimmer dives from the elevated platform, the system returns to its prior condition with the end cap open and fluid exiting in the form of a spray.
In accordance with a further aspect of the invention, the seal between the fixed and movable tubes is provided by a grommet that surrounds a cylindrical ring at an intermediate or top end location on the fixed tube. The grommet engages the inner wall of the movable tube. A keyway and key can be provided between the fixed and movable tubes to stabilize the movement of the movable tube relative to the fixed tube.
In a method of the invention for using aquatic apparatus, the steps include (a) applying fluid pressure to a fixed tube connected to a float support and surrounded by a movable tube with a seal therebetween; (b) allowing the fluid applied to the fixed tube to exit at the ends of both the fixed and movable tubes; and (c) capping the exit end of the movable tube so that the applied fluid causes the movable tube to rise in relation to the fixed tube.
The method further includes the step of pivotally connecting a platform to a moveable tube and linking the platform with the capping member of the movable tube by at least one cable, whereby downward pivoting of the platform caps the movable tube and causes it to rise in relation to said fixed tube.
The method can also include the step of providing fluid exhaust holes in the movable tube below the location of the seal between the fixed and movable tubes in order to control the extent to which the movable tube can rise in relation to the fixed tube when the movable tube is capped.
In a method of the invention for manufacturing aquatic apparatus, the steps include (a) fabricating a float support; (b) attaching a hollow outlet tube to the float support; (c) surrounding the hollow outlet tube by a movable tube having an openable end cap, and (d) providing a seal between the hollow outlet tube and the surrounding movable tube. The openable end cap can be pivotable, slidable or otherwise openable. A platform can be connected to the moveable tube for controlling the end cap.


The invention relates to novel surface modified semi-gels, to a method for producing same, and to the use thereof.

The present invention relates to new surface-modified semi-gels, to a process for preparing them, and to their use.
Inorganic oxides based on SiO2 are divided, on the basis of their preparation process and their properties, into fumed silicas (Aerosils), precipitated silicas, silica sols, silica gels, and semi-gels.
Among silica gels, a distinction is made between hydrogels, aerogels and xerogels. Hydrogels—or else aquagels—are prepared in water, and so their pores are filled with water. A xerogel is a hydrogel from which the water has been removed. An aerogel is a xerogel from which the liquid has been removed in such a way that there is only minimal change to the structure of the gel and the pore volume is largely retained.
Silica gels have been known for a long time (Iler, "Chemistry of Silica", p. 462 ff, 1979). They are prepared under conditions which promote coalescence of primary particles (average particle size: 1 to 10 nm), so that in contrast to precipitated or fumed silicas a relatively rigid, three-dimensional network is formed. Consequently silica gel particles differ distinctly from precipitated silica particles.
The preparation of silica gels is well known to the skilled person; see, for example, U.S. Pat. No. 4,097,303, DE 41 32 230, and EP 0 384 226. It involves mixing sodium silicate and sulphuric acid with one another rapidly and continuously at low temperatures, low pH, and high concentrations, to form a hydrosol, which in turn, after a short time, is condensed to the hydrogel. Alternatively the gelling can also take place under alkaline conditions (see, for example, GB 1,219,877, GB 1,279,250, WO9825 851 or EP 0 588 497). A further alternative is proposed in EP 0 765 764.
The resultant hydrogel is broken into relatively small pieces and washed to remove soluble salts and impurities. During the washing cycle the pore structure of the hydrogel is adjusted by varying pH (e.g., adding bases such as ammonia, for example), temperature, and time. The procedure is well known to the skilled person. Examples can be found in EP 0 384 226 or WO00002814, for instance.
Following the washing cycle the washed hydrogel is dried by thermal means in order to form a silica gel or xerogel. The nature and mode of drying have a substantial influence on the pore volume of the silica gel. With rapid drying the pore volume can be very largely maintained; in the case of slow drying, the pore volume reduces. Finally the silica gel can be ground or comminuted to a specific particle size and particle distribution.
Fumed silicas differ from silica gels in that fumed silicas are constructed from aggregates of primary particles, whereas silica gels feature a three-dimensional network of primary particles. These structural differences are caused by the preparation process. Detailed information on the structure of fumed silicas is found in Kirk-Othmer's Encyclopedia of Chemistry, page 776.
Precipitated silicas have a different structure again, characterized not only by aggregates but also, in particular, by agglomerates. They are obtained by the so-called wet process, in which waterglass and acids are reacted so as to form aggregates and agglomerates, and not, as in the case of gels or gel-like products, three-dimensional networks of primary particles. The structural differences between precipitated silicas and fumed silicas are described in Kirk-Othmer's Encyclopedia of Chemistry.
A fourth variant of the amorphous silicon dioxides is represented by the semi-gels. In comparison to silica gels, semi-gels have a broader pore size distribution, a lower mechanical stability, and a different fractal dimension (3-D networks). In comparison to precipitated silicas, on the other hand, they have a narrower pore size distribution, and so in terms of the pore size distribution, semi-gels can be placed between silica gels and precipitated silicas.
In terms of the preparation process as well there are differences. Thus silica gels are prepared, as described above, with a constant concentration of dissolved colloidal silica. Waterglass and acid are mixed so that there are no longer any changes in concentration. After optional ageing, this produces silica gels in more or less large blocks.
Semi-gels, in contrast, are prepared with constant stirring or introduction of shearing energy, the SiO2 concentration being increased during the reaction, with the result that, at the end, particulate structures, rather than a "block", are obtained. Semi-gels are sold, for example, by the Beijing Aerospace Sai De Power Material Technical Company Ltd., Yuquan Road No. 16, Haidian District, Beijing (China).
Both precipitated silicas and silica gels are used as matting agents in coatings. U.S. Pat. No. 4,285,846 also discloses the use of semi-gels as matting agents.
Besides the advantage of reducing the gloss of coatings, however, the use of matting agents in coatings also leads to problems. For instance, in certain coating systems, the addition of the matting agent undesirably increases their viscosity. As described in EP 0 442 325, particularly thixotropic, conventional solventborne alkyd coatings are difficult to matt in light of their rheological properties. This relates in particular to aqueous coating systems on acrylate or acrylate-polyurethane, or corresponding hybrid systems.
A further problem frequently observed with matting agents is that they have a propensity towards sedimentation. In order to prevent matting agents sedimenting in coatings, the surface of the majority of commercially customary matting agents is coated with a surface modifier. Here, organic components are attached to the SiO2 surface. This attachment may be chemical, so that true chemical bonds form between SiO2 surface and organic component, and may also be physical, i.e., the organic component is adsorbed onto the SiO2 surface by means of Van der Waals interactions or hydrogen bonds. Surface modification, however, carries problems in its wake. Thus commercially customary, surface-modified matting agents often have the disadvantage that during storage of the coating material the coating may become detached and hence the desired effect is at least partly annulled again. This can lead to impairments of the coating properties.
The document WO200342293 discloses a matting agent where a silica gel has been coated with wax. WO9951692 proposes coating the silica gel with a urea-urethane derivative.
Coating a silica gel with a polyol in accordance with patent EP 0 442 325 produces a matting agent which has very little effect, if any, on the thixotropic behaviour of inks and coating materials based on polyamide-modified alkyd resins.
DE 102004029069, in turn, discloses the surface modification of silica gels with organopolysiloxanes, and DE 102004012090 discloses the surface modification of precipitated silicas with organopolysiloxanes.
As far as semi-gels are concerned, only waxing as a surface modification has been disclosed to date. Corresponding products are sold by Beijing Aerospace Sai De Power Material Technical Company Ltd., Yuquan Road No. 16, Haidian District, Beijing (China).
For different applications there are a large number of different coating materials and different coating-material compositions. In order to allow even greater flexibility and improvement in the performance properties of the coatings, there is a continuous need for new, alternative matting agents.
It was an object of the present invention, therefore, to provide new, surface-modified semi-gels which can be used as matting agents in coatings. A specific object was to provide surface-modified semi-gels which have better performance properties than the wax-modified semi-gels known in the prior art.
A further object was to provide a process with which the surface-modified semi-gels of the invention can be prepared.
Further objects, not explicitly mentioned, arise from the overall context of the subsequent description and examples.
Surprisingly it has been found that these objects are achieved by means of the surface-modified semi-gels of the invention, defined in more detail in the following description and also in the claims and the examples, and by means of the process described in more detail in the description, the examples, and the claims.
The present invention provides surface-modified semi-gels characterized in that at least parts of the surface of the semi-gel have been modified with at least one organopoly-siloxane and/or at least one modified organopolysiloxane.
The invention further provides semi-gels characterized in that at least parts of the surface of the semi-gel have been modified with at least one organopolysiloxane and/or at least one modified organopolysiloxane, and in that they have                a BET surface area of 200 to 400 m2/g, preferably of 210 to 350 m2/g,        a mesopore volume for pores having a diameter of 2-30 nm of 0.95 to 1.5 ml/g, preferably of 1.0 to 1.4 ml/g,        a mesopore volume for pores having a diameter of 2-50 nm of 1.2 to 1.8 ml/g, preferably of 1.3 to 1.7 ml/g,        a pore maximum in the range from 10 to 50 nm from 15 to 45 nm.
Likewise provided by the present invention are processes with which the surface-modified semi-gels of the invention can be prepared, characterized in that the surface of a semi-gel is contacted with at least one organopolysiloxane and/or at least one modified organopolysiloxane.
The invention provides, lastly, for the use of the surface-modified semi-gels of the invention, especially as matting agents in paints and coatings.
The advantages of the surface-modified semi-gels of the invention over commercial, SiO2-based matting agents include the following:
matting agents based on semi-gels have advantages over precipitated-silica-based matting agents in the sector of coil coating, since they are more transparent.
Semi-gels coated with polysiloxanes have the advantage over wax-coated silicon dioxides that the surface modifier is attached by true chemical binding and not by physical effects. Hence there is a lower risk of detachment of the surface modifier. Furthermore, very thin siloxane layers on the semi-gel can be realised, leading to economic advantages.
Semi-gels of the invention with carbon-carbon multiple bonds in the polysiloxane have particular advantages in the context of use in UV coating materials such as UV varnishes, for example. These systems can be matted significantly more effectively with the products of the invention than with commercial matting agents based on silicon dioxide. Without being tied to any particular theory, the inventors are of the view that the multiple bond is also crosslinked in the course of curing, and hence ensures a particularly good attachment.
The present invention is described in detail below. To start with, however, a number of important terms are defined.
Silica gels for the purposes of the present invention are inorganic oxides based on SiO2 which are prepared via a gel process. Silica gels subdivide into the groups of the hydrogels, the aerogels, and the xerogels. Hydrogels—or else aquagels—are prepared in water and so their pores are filled with water. A xerogel is a hydrogel from which the water has been removed. An aerogel is a xerogel from which the liquid has been removed in such a way that there is only minimal change to the structure of the gel and the pore volume is largely retained.
Semi-gels are amorphous silicon dioxides which in comparison to silica gels have a broader pore size distribution and in comparison to precipitated silicas have a narrower pore size distribution, and so in terms of the pore size distribution, semi-gels can be placed between silica gels and precipitated silicas.
By surface modification is meant the chemical and/or physical attachment of organopolysiloxanes and/or modified organopoly-siloxanes. In other words, in surface-modified semi-gels, at least part of the surface of at least some of the semi-gel particles is coated with the surface modifier.
The terms organopolysiloxane and polyorganosiloxane, and modified organopolysiloxane and modified polyorganosiloxane, are each used synonymously.
The surface-modified semi-gels of the invention are characterized in that at least parts of the surface of the semi-gel have been modified with at least one organopolysiloxane and/or at least one modified organopolysiloxane.
The surface-modified semi-gels of the invention preferably, moreover, have the following physicochemical parameters:
The BET surface area influences the surface activity of the semi-gel and hence the stabilization of the network within the coating system, and this in turn affects the rheological properties of said system, especially the viscosity. The BET surface area is therefore preferably in the range from 200 to 400 m2/g, preferably from 200 to 350 m2/g, more preferably from 200 to 300 m2/g.
The pore structure of the semi-gels of the invention substantially influences their interactions with the coating system. If the pores are too small or the pore volume is too low, then the coating material is unable to penetrate the polymer components sufficiently, and there are therefore hardly any interactions. If, on the other hand, the pores are too large, the interactions are again too weak, since the polymers can easily be dissolved out of the pores again. The semi-gels of the invention therefore preferably have the following pore characteristics:                a mesopore volume for pores having a diameter of 2-30 nm of 0.7 to 1.5 ml/g, preferably 0.95 to 1.4 ml/g, preferably of 1.0 to 1.3 ml/g,        a mesopore volume for pores having a diameter of 2-50 nm of 0.9 to 1.8 ml/g, preferably of 1.0 to 1.7 ml/g, more preferably 1.1 to 1.6 ml/g, and        a pore maximum in the range from 10 to 50 nm, preferably from 15 to 45 nm, preferably from 15 to 40 nm, and very preferably from 20 to 35 nm.
In specific embodiments, the semi-gels of the invention preferably have at least one of the following properties:
It has been found that the DBP oil absorption of the semi-gels of the invention can be correlated to a certain extent with the matting efficiency. Moreover, the DBP is important for ensuring optimum uptake of organopolysiloxane. The DBP oil absorption of the semi-gels of the invention is therefore preferably in the range of 150-500 g/100 g, more preferably 200-450 g/100 g and especially preferably 250-400 g/100 g.
In order to be able to obtain a particularly good matting effect, but at the same time allowing a smooth coating surface, the average particle size d50 of the surface-modified silicon dioxides of the invention is situated preferably in the range of 1-50 μm, more preferably 1-40 μm, very preferably 1-30 μm, especially preferably 2-20 μm, and very especially preferably 3-15 μm. The average particle size may be varied according to the film thickness of the coating.
The sedimentation behaviour of the surface-modified semi-gels of the invention is generally 1 to 2.
All stated ranges of preference may be set independently of one another.
The particular properties of the semi-gels of the invention can be attributed, as well as to their specific physicochemical properties in particular to the polymers used for the surface modification. Semi-gels which exhibit the properties according to the invention preferably have a surface which has been treated with one or more polyorganosiloxanes or modified polyorganosiloxanes. With particular preference the semi-gels involved are semi-gels which have been treated with polyether-, acrylate- and/or polyacrylate-modified polyorganosiloxanes or polyalkoxysiloxanes.
In one particularly preferred embodiment of the present invention the semi-gels have a surface coated with polyorgano-siloxanes of the following general structure:

where
Y═—OH, —OR or
Y═H5C2—O—(C2H4O)m—, H7C3—O—(C3H6O)m— or

R=-alkyl especially methyl or ethyl,
R2=alkyl or H,
R3=alkyl,
R4═H or alkyl,
a=0-100, b=0-100, c=0-100, d=0-100,
sum a+b+c+d is or preferably is not equal to 0,
m=0-100 and k=0-100.
In a further preferred embodiment of the present invention the surface of the semi-gels is coated with a polyorganosiloxane of the following general structure:

where
R1=a methyl radical or

and the sum of the units a=0 to 100, the sum of the units b=0 to 15, the ratio of methyl to alkoxy radicals R1 being less than 50:1, and b>1 if a=0 and a>5 if b=0. Further details, relating in particular to the preparation of these polyorganosiloxanes, can be found in DE 36 27 782 A1. The content of that patent application is likewise subject matter of the present specification.
The term "alkyl radical" embraces straight-chain and branched-chain alkyl radicals having 1 to 100 C atoms, preferably 1 to 25, more preferably 1 to 10 C atoms, and also cycloalkyl radicals having 1 to 15 C atoms. The alkyl radicals may contain one or more double or triple bonds, and individual atoms may be replaced by heteroatoms such as O, N or S.
In another preferred embodiment of the present invention, silicone polyether acrylate polymers or silicone polyether methacrylate polymers are used. Particular preference is given to using acrylic esters and/or methacrylic esters of hydroxy-functional siloxanes and/or polyalkylene-modified siloxanes. Particular preference is given to using organopolysiloxanes which are obtained by esterification or transesterification of acrylic acid and/or methacrylic acid or acrylic esters and/or methacrylic esters, in the presence of an enzyme which catalyses the esterification or transesterification, with hydroxy-functional and/or polyoxyalkylene-modified siloxane derivatives of the general formula (I)

where
R1 and/or R7═R2 or [R4]w—[R5]x—[R6]y—R8,
R2═R3 or ≠R3 stands for identical or different alkyl radicals or alkylene radicals having 1 to 24 carbon atoms or optionally substituted phenyl radicals having up to 24 carbon atoms,
R4=a divalent radical of the formula O, NH, NR2, S or a radical of the formula (OSi(CH3)2)u, where
u=1 to 200,
R5=identical or different alkyl radicals or alkylene radicals having 1 to 24 carbon atoms, or
CnH2n-fR2f—R4—CmH2m-gR2g, where
f=0 to 12,
g=0 to 12,
n=1 to 18,
m=1 to 18,
R6═O—(C2H4-aR2aO)b (CcH2cO)d, where
a=0 to 3,
b=0 to 100,
c=2 to 12,
d=0 to 100,
the sum of (b+d)=1 to 200,
and the sequence of the individual polyoxyalkylene segments (C2H4-aR2aO)b and (CcH2cO)d may be arbitrary and encompasses especially block copolymers, such as random polymers and also combinations thereof, or
R6═Oe—ChH2h—CiH2i-jR9j, where
e=0 or 1,
h=0 to 24,
i=0 to 24,
j=1 to 3,
the sum of (w+e)=0 to 1
and R9 in each case is a divalent radical of the formula O, a hydroxyl group, a radical of the formula ChH2h or a radical of the formula CkH2k-1(OH)l, where
k=0 to 24 and
l=1 to 3,
R8=a hydrogen radical or a monovalent organic radical, when y is 1, it being necessary for there to be at least one hydrogen radical present per molecule, or an OH group or a monovalent organic radical, when y=0, there being at least one OH group present per molecule,
v=0 to 200,
w=0 or 1,
x=0 or 1,
y=0 or 1,
z=0 to 200
and the sum of (w+x+y)=1 to 3
and, when z=0, R1 and/or R7 are
[R4]w—[R5]x—[R6]y—R8
and, when x=0, then w=0 as well.
It is a familiar concept to the skilled person that the compounds are present in the form of a mixture with a distribution governed essentially by laws of statistics. In particular, the values for the indices b, d, u, v and z therefore represent average values.
Examples of siloxane derivatives which can be reacted in accordance with the invention by enzymatically catalysed esterification or transesterification of acrylic and/or methacrylic acid or acrylic and/or methacrylic esters are as follows:

The enzymatic esterification or transesterification of acrylic and/or methacrylic acid or acrylic and/or methacrylic esters with the compounds stated above at low temperatures, more particularly 20 to 100° C., preferably 40 to 70° C., under mild conditions is advantageous on account of the paler colour of the product, the avoidance of the formation of by-products, which may otherwise originate, for example, from chemical catalysts, the uncomplicated removal of the enzyme catalyst from the product, and the avoidance of unwanted and uncontrolled free-radical polymerization of the acryloyl and/or methacryloyl compounds.
The acryloyl- and/or methacryloyl-functional siloxane derivatives obtainable in this way are notable for the fact that 5% to 100% of all of the hydroxyl groups originally present have undergone conversion to acrylic and/or methacrylic ester.
The acrylicization and/or methacrylicization take place ideally in high yields with esters of acrylic and/or methacrylic acid as donor molecules, more particularly methyl, ethyl or butyl methacrylate and/or acrylate.
Enzymes which can be employed preferably as catalysts are hydrolases, especially esterases, lipases and proteases. A specific example thereof is Novozym® 435. The enzymes can be used in pure form or in a form in which they are immobilised on a support, on which they are bound chemically or physically. The amount of the enzyme catalyst, based on the modified siloxane employed, is in particular 0.1% to 20% by weight, preferably 1% to 10% by weight. The reaction time is dependent on the amount used and on the activity of the enzyme catalyst, and is for example up to 48 hours, preferably up to 24 hours.
In order to arrive at high degrees of conversion rapidly and under simple reaction conditions, it is advantageous to use an excess of at least 10% by weight of acrylic acid and/or methacrylic acid and/or their corresponding esters (as donors) in the reaction mixture.
The production system can be characterized either by a stirred tank reactor or a fixed bed reactor. The stirred tank reactor may be equipped with apparatus for distilling off the alcohol liberated from the acrylic and/or methacrylic acid donor, or the water liberated from the acrylic and/or methacrylic acid.
The reaction is preferably continued until the desired conversion is achieved. A reaction regime with simultaneous distillation is preferred, since the removal of the water of reaction or alkanol of reaction leads to higher yields in shorter reaction times, owing to the shifting of the reaction equilibrium.
In order to maximize degrees of conversion it is advisable to remove the water or alkanol of reaction.
After the end of the reaction, the enzyme catalyst can be removed by suitable measures, such as filtration or decanting, and if desired can be used a number of times.
The fixed bed reactor is packed with immobilized enzymes, the reaction mixture being pumped through the catalyst-packed column. With an enzyme immobilized on a support it is also possible to carry out the reaction in a fluidized bed.
The reaction mixture can be pumped continuously through the column, the residence time and hence the desired conversion being controllable via the flow rate. It is also possible to pump the reaction mixture through the column in circulation, in which case the water or alkanol of reaction may be distilled off at the same time under reduced pressure.
Other methods of removing the water or alkanol of reaction can also be used, such as absorption or pervaporation.
These silicone polyether acrylate- or silicone polyether methacrylate-polysiloxane-modified semi-gels are particularly suitable for use in UV-curing coating systems, since the double bond in the polymers is also able to crosslink in the course of curing.
The surface-modified semi-gels of the invention can be prepared by various processes, in each of which the surface of the semi-gel is contacted with at least one organopolysiloxane and/or at least one modified organopolysiloxane.
In one embodiment I of the present invention, the organopolysiloxane and an optionally pre-ground semi-gel are intensely mixed. The addition is made such as to ensure a homogeneous distribution over the semi-gel. Thereafter the mixture is preferably dried, ground and, if desired, sieved or classified.
In one embodiment II of the present invention, dried semi-gel having a residual moisture content of ≦10% is mixed intensely with the organopolysiloxane. The addition of the organopoly-siloxane is made such as to ensure a homogeneous distribution of the semi-gel. Thereafter the mixture is optionally ground and, if desired, sieved or classified.
In one embodiment III of the present invention, semi-gel is ground and at the same time the surface is modified. For this purpose the polymer is conveyed into the milling chamber of the mill in such a way as to bring about the desired coating ratio. Thereafter the product is optionally sieved or classified and, if desired, dried.
In the case of process variants I and II it is preferred to introduce a semi-gel into a mixer, to add the surface modifier and to carry out intense mixing with the semi-gel. With regard to the mixer there are no particular restrictions. Lödige mixers or tumble mixers, for example, can be used.
The addition is made preferably such as to ensure a homogeneous distribution over the semi-gel. This is possible, for example, through spray introduction or nozzle introduction or dropwise addition, or other methods known to the skilled person.
It possible to use dry semi-gel and also moist semi-gel, i.e., a filter cake. The moisture content of the semi-gel may be from 1% to 15% by weight.
In process variants I and II, the semi-gel is preferably subjected to pre-grinding prior to coating. Where a dry semi-gel is used, it is preferably dried by accelerated drying. Drying assemblies which have been found particularly suitable include spray dryers, grinding dryers, pneumatic dryers or spin-flash dryers. The moisture content of the dry semi-gels is preferably 1% to 15%, more preferably 2% to 10%, very preferably 3% to 5%, by weight.
In process variant 3, the surface modification takes place in a milling apparatus, and the semi-gel is preferably simultaneously ground, surface-modified, and, very preferably, also dried at the same time. In this variant as well it is possible to use a pre-ground semi-gel, but preferably no preliminary grinding takes place.
For the preliminary grinding in the process variants described above, all kinds of mills are suitable, but mechanical beater mills are preferred.
For fine grinding to give the end product, which is necessary for the product to be finely divided as needed for application as a matting agent, air and steam jet mills have proved to be particularly suitable. With particular preference the fine grinding is carried out on an opposed-jet fluidized-bed mill.
In order to avoid oversize or bits it is advantageous to remove particles having a diameter of more than 50 μm, preferably more than 30 μm, in particular more than 20 μm. Depending on the fineness of the matting agent, this can be done by means, for example, of an appropriate sieve or a classifier device, which may also be integrated into the mill.
The surface modification may take place, as described above, before, during or after grinding or drying. The surface modifier may be added in pure, undiluted form or in dilute form as an aqueous emulsion. It is preferred to add 0.2% to 12%, more preferably 1% to 10%, very preferably 2% to 8%, and especially preferably 3% to 8%, by weight, of the organopoly-siloxane, relative to the semi-gel.
The unmodified semi-gel precursors used in the process of the invention may be prepared by known processes or acquired commercially. Particular preference is given to using the semi-gels SD 500, SD 520, SD 530, SD 538, SD 540, SD 600, SD 640 and SD 690 from Beijing Aerospace Sai De Power Material Technical Company Ltd., Yuquan Road No. 16, Haidian District, Beijing (China) (China).
As starting material it is preferred to use a semi-gel, more preferably a semi-gel which is not surface-modified with an organopolysiloxane, that has the following physicochemical properties:                BET surface area of 200 to 400 m2/g, preferably of 210 to 350 m2/g,        mesopore volume for pores having a diameter of 2-30 nm of 0.95 to 1.5 ml/g, preferably of 1.0 to 1.4 ml/g,        mesopore volume for pores having a diameter of 2-50 nm of 1.2 to 1.8 ml/g, preferably of 1.3 to 1.7 ml/g,        pore maximum in the range from 10 to 50 nm from 15 to 45 nm.
It emerges from this that the surface modification step can be integrated as an additional step into known processes for preparing semi-gels, or else semi-gel precursors can be acquired and can be used as starting material for one of process variants I-III.
As surface-modifying organopolysiloxanes it is preferred in the process of the invention to use the polyorganosiloxanes or modified polyorganosiloxanes that have already been described above.
The surface-modified semi-gels of the invention are used preferably as matting agents in inks and paints.
In addition the surface-modified semi-gels of the invention can be used in all fields of application in which semi-gels are normally used, such as, for example, as a constituent of paper coatings, as a constituent of defoamer formulations, as a reinforcing agent in silicone rubber, or in polymer formulations, as antiblocking agents, for example.
The physicochemical data of the surface-modified semi-gels of the invention are determined by the following methods:
Determination of BET Surface Area
The BET surface area of semi-gels is determined in a method based on DIN ISO 9277 by means of the nitrogen adsorption method of Brunauer, Emmett and Teller (BET). The method is based on the work of S. Brunauer, P. H. Emmett and E. Teller, J. Am. Chem. Soc., 60, 309 (1938).
The measurements are made on the Tristar 3000 instrument (Micromeritics). The samples under analysis are degassed under vacuum (p<10−3 mbar) at 160° C. prior to measurement until the pressure over the sample under a closed vacuum remains constant for 30 minutes.
Determination of Mesopore Volume
The mesopore distribution is determined by the method of Barret, Joyner and Halenda (BJH) and is based on work by E. P. Barret, L. G. Joyner and P. H. Halenda, J. Am. Chem. Soc., 73, 373, (1951).
The measurements are made on the ASAP 2400 instrument (Micromeritics). The samples under analysis are degassed under vacuum (p<10−3 mbar) at 200° C. prior to measurement until the pressure over the sample under a closed vacuum remains constant for 30 minutes.
Determination of Loss on Drying
The moisture content or loss on drying (LD) of semi-gels is determined in a method based on ISO 787-2 after 2-hour drying at 105° C. This loss on drying is accounted for predominantly by aqueous moisture.
10 g of the pulverulent semi-gel are weighed to an accuracy of 0.1 mg (initial mass E) into a dry glass beaker on a precision balance (Sartorius LC621S). The glass beaker is covered with aluminium foil into which a number of holes (Ø1 mm) have been drilled. The glass beaker covered in this way is dried in a drying oven at 105° C. for 2 h. Thereafter the hot glass beaker is cooled to room temperature in a desiccator over drying agent for at least one hour.
In order to determine the final mass A, the glass beaker is weighed to an accuracy of 0.1 mg on the precision balance. The moisture content (LD) in % is determined in accordance withLD=(1−A/E)*100,
where A=final mass in g and E=initial mass in g.
Determination of Loss on Ignition
According to this method the weight loss of semi-gels is determined in a method based on DIN EN ISO 3262-1 at 1000° C. At this temperature, physically and chemically bound water and other volatile constituents escape. The moisture content (LD) of the sample investigated is determined by the above-described method "Determination of loss on drying" based on DIN EN ISO 787-2.
0.5 g of semi-gel is weighed to an accuracy of 0.1 mg (initial mass E) into a tared porcelain crucible which has been calcined beforehand. The sample is heated in a muffle furnace at 1000±50° C. for 2 h. The porcelain crucible is subsequently cooled to room temperature in a desiccator cabinet with silica gel as drying agent. The final mass A is determined gravimetrically.
The loss on ignition, LOI, in % is obtained in accordance withLOI=(1−A/F)*100,
where F is the corrected initial mass, based on dry matter, in g, and is calculated according toF=E*(1−LD/100).
In the calculations, F=final mass in g, E=initial mass in g, and LD=loss on drying, in %.
Determination of DBP Number
The DBP absorption (DBP number), which is a measure of the absorbency of the semi-gel, is determined in a method based on the DIN 53601 standard, as follows:
12.50 g of pulverulent semi-gel (moisture content 4±2%) are introduced into the kneader chamber (article number 279061) of the Brabender absorptometer "E" (without damping of the outlet filter of the torque sensor). With continuous mixing (kneader paddles rotating at a speed of 125 rpm), dibutyl phthalate is added dropwise to the mixture at a rate of 4 ml/min at room temperature by means of the Brabender T 90/50 Dosimat. Its incorporation by mixing takes place with only a small amount of force, and is monitored by means of the digital display. Toward the end of the determination the mixture becomes pasty, which is indicated by a sharp increase in the required force. At a display reading of 600 digits (torque of 0.6 Nm), an electrical contact shuts off both the kneader and the DBP feed. The synchronous motor for the DBP feed is coupled to a digital counter, so that the consumption of DBP in ml can be read off.
The DBP absorption is expressed in g/100 g and is calculated using the following formula:
  DBP  =                              V          *          D          *          100                E            *              g                  100                                                              g                      +    K
where DBP=DBP absorption in g/100 g                V=consumption of DBP in ml        D=density of DBP in g/ml (1.047 g/ml at 20° C.)        E=initial mass of semi-gel in g        K=correction value as per Table 1        (moisture correction table) in g/100 g
The DBP absorption is defined for anhydrous, dried semi-gel. When moist semi-gels are used it is necessary to take into account the correction value K for calculating the DBP absorption. This value can be determined using Table 1; for example, a semi-gel having a water content of 5.8% would mean an addition of 33 g/100 g for the DBP absorption. The moisture content of the semi-gel is determined in accordance with the "Determination of loss on drying" method described.
TABLE 1Moisture correction table for dibutyl phthalateabsorption - anhydrous -.% Water% Water.0.2.4.6.800245719101213152161819202232324262728428292930315313232333363434353536736373838398394040414194243434444104545464647
Determination of Particle Size
The application of laser diffraction for determining particle size distributions of solids in powder form is based on the phenomenon whereby particles, as a function of their size, scatter—or diffract—the light of a monochromatic laser beam with different intensity patterns in all directions. The smaller the diameter of the irradiated particle, the larger the scattering or diffraction angles of the monochromatic laser beam.
Sample preparation and measurement take place, in the case of hydrophilic silicon dioxides, with deionized water as the liquid for dispersing, or, in the case of silicon dioxides that cannot be adequately wetted with water, with pure ethanol. Prior to measurement being commenced, the laser diffraction instrument LS 230 (Beckman Coulter; measuring range: 0.04-2000 μm) and the liquid module (Small Volume Module Plus, 120 ml, Beckman Coulter) are run for 2 hours to warm up, and the module is rinsed three times with deionized water. For the measurement of hydrophobic precipitated silicas, the rinsing operation is carried out with pure ethanol.
In the instrumental software of the LS 230 laser diffraction instrument, the following optical parameters, relevant for evaluation in accordance with the Mie theory, are defined in an .rfd file:
refractive index of the dispersing liquid B. I. Realwater=1.332 (1.359 for ethanol); refractive index of the solid (sample material) RealSiO2=1.46
imaginary=0.1
form factor=1
In addition, the following parameters relevant to particle measurement must be set:
measuring time=60 s
number of measurements=1
pump speed=75%
Depending on the nature of the sample, it may be introduced directly in the form of the powder solid, using a spatula, or in suspended form, using a 2 ml single-use pipette, into the liquid module (Small Volume Module Plus) of the instrument. When the sample concentration needed for measurement has been reached (optimum optical shading), the instrumental software of the LS 230 laser diffraction instrument reports "OK". Ground silicon dioxides are dispersed in the liquid module by 60 s of ultrasonication using a Vibra Cell VCX 130 ultrasound processer from Sonics, with CV 181 ultrasound converter and 6 mm ultrasound tip, at 70% amplitude, with simultaneous pumped circulation. In the case of unground silicon dioxides, dispersing takes place without ultrasonication, by pumped circulation for 60 s in the liquid module. Measurement is carried out at room temperature. From the raw data, the instrumental software uses the previously defined optical parameters (.rfd file) to make a calculation, on the basis of the Mie theory, of the volume distribution of the particle sizes and the d50 value (median value).
ISO 13320 "Particle Size Analysis—Guide to Laser Diffraction Methods" describes in detail the method of laser diffraction for determining particle size distributions.
Determination of Carbon Content
The carbon content of semi-gels is determined using the C-mat 500 (Ströhlein Instruments). The samples are heat treated at about 1350° C. and the carbon is oxidized to CO2 by a stream of oxygen. The CO2 is measured in an infrared cell.
In the course of the measurements a distinction is made as to whether the carbon content is greater than or less than 1 per cent. If the carbon content of the homogeneous samples is above 1 per cent, measurement is carried out in the "High" range of the instrument; if it is below 1 per cent, measurement is carried out in the "Low" range.
First of all the control sample is measured. For that purpose, 0.14-0.18 g of the control sample is weighed out on an analytical balance into a porcelain boat purified by calcining and cooled to room temperature. When the start button is operated the weight is carried over, since the balance is coupled with the C-mat. The boat must be pushed into the middle of the combustion tube within 30 seconds. When combustion is at an end the measurement is converted into pulses and evaluated by the computer. At least 3 determinations (depending on agreement) are carried out. It may be necessary to readjust the factor of the instrument (for details see operating instructions for C-mat 500, Ströhlein Instruments). This factor is calculated according to the following formula:
  factor  =                    setpoint                          (          standard          )                    *      initial                                      mass                                              (        standard        )                                            in                                      g      *              10        8              pulses
Subsequently the semi-gel samples are measured. The initial mass is 0.04-0.05 g. The porcelain boat is covered with a porcelain lid. In the event of deviations >0.005% a greater number of measurements are carried out and the average is calculated.
The operation of the C-mat 500 is taken from the operating instructions from the company Ströhlein Instruments.
The carbon content is calculated as follows and expressed in the unit %:carbon content=(P*F*10−8)/E
p=pulse
F=factor
E=initial mass in g
Determination of Coat Thickness
The reflectometer value of matted coating materials is influenced by, among other factors, the coat thickness of the coating. It is therefore necessary to monitor the thickness of the dried coating film precisely.
The following procedure applies only to the measurement of single-coat films on glass substrates. Prior to the implementation of the measurement, the probe of the ultrasonic coat-thickness measuring instrument (QuintSonic, Elektro Physik) must be calibrated in accordance with the instrument operating instructions. After sufficient coupling agent has been applied to the probe measurement area, the probe is placed perpendicularly onto the surface of the coating and the measurement is started by pressing the probe button. After a short time the measured value is displayed. The probe is lifted from the measurement area.
At least 5 measurements are carried out at measurement sites distributed uniformly on the object to be measured. It should be ensured that the measurement sites do not exhibit any defects, such as craters, inclusions, scratches, air bubbles, etc., or any soiling.
From the measurement data obtained an average shall be formed and rounded to an accuracy of 1 μm.
Determination of 60° and 85° Reflectometer Value
The effect exerted on reflectance as a result of deliberate roughening of coating film surfaces is the outstanding property of matting agents based on SiO2. The reflectometer value is therefore an important criterion for characterizing matted coating films.
A prerequisite for the measurement is that the coating film surfaces to be measured should be planar, clean and cured.
The measurement is to be carried out on at least 3 representative sites on the sample by means of a reflectometer with measuring geometry according to DIN 67530 (e.g. Haze-gloss, BYK Instruments). If the individual measurements deviate from one another too greatly, then generally a further measurement should be carried out at representative sites, or the number of individual measurements should be increased to >3. On the BYK haze-gloss the display shows the standard deviation of the measurements. If the standard deviation s is >0.5 it is advisable to carry out the abovementioned measures. The average value shall be reported to 1 decimal place.
In the characterization of matted coating film surfaces it has been found appropriate to carry out measurement with the 60° and the 85° measuring geometries. In deviation from DIN 67530, therefore, the reflectometer values of matted coating film surfaces are determined using both measuring geometries.

This patent is subject to a terminal disclaimer.


Methods, apparatuses, and computer program products are herein provided for enabling use of external devices with pre-defined gestures. A method may include receiving operation information from a remote device, wherein the operation information indicates at least one operation that may be invoked by the remote device. The method may further include associating, by a processor, at least one pre-defined gesture with the at least one operation. The method may further include receiving user input. The method may further include determining that the user input corresponds to the at least one pre-defined gesture. The method may further include causing transmission of indication information to the remote device, wherein the indication information provides an indication to the remote device to perform the at least one operation associated with the pre-defined gesture. Corresponding apparatuses and computer program products are also provided.

Interactive systems (e.g., ticket dispensers for public transportation, information kiosks for directions, etc.) have become increasingly available and useful to the public. Such systems are capable of performing a vast array of functionality, often being specialized for each particular system. Such variation, however, may cause the interactive public system to include functionality that is new and/or foreign to certain users. Therefore, it can be difficult for a new user to interact with such systems. Moreover, some interactive systems may purposefully limit their own functionality to provide for an easier interaction between new users and the interactive system.
Advancement in technology has also brought about a tremendous expansion of wireline and wireless networks, and with it personal mobile computing devices. The combination of the robust functionality and small form factor of these mobile computing devices enable users to carry their personal mobile computing devices nearly everywhere. These mobile computing devices have even begun to interact with the interactive public systems, but to date, this interaction has been limited and less than intuitive.

Methods, apparatuses, and computer program products for enabling use of remote devices with pre-defined gestures


A memory arrangement, particularly a ROM, having memory cells, local virtual supply voltage lines, word lines and result lines may also include global virtual supply voltage lines that run along the width of the memory arrangement parallel to the word lines. The local virtual supply voltage lines run parallel to the result lines, and perpendicularly to the word lines where the each local virtual supply voltage line runs only within a block of the memory arrangement. Each global virtual supply voltage line, in each block through which it runs, is connected to one local virtual supply voltage line. The coupling capacitance between the supply voltage lines and the result lines, and the inherent capacitance of the supply voltage lines are reduced, reducing the power consumption and increasing the clock frequency of the memory arrangement.

1. Field of the Invention
This invention relates to memory arrangements such as a read only memory ("ROM"), and in particularly to a memory arrangement having reduced power consumption.
2. Description of the Related Art
FIG. 1 illustrates a prior art read-only memory (ROM) 8 having many 1-bit memory cells, corresponding to the memory capacity of the ROM. These 1-bit memory cells are divided into various sections (also called block columns below) of equal size (equal number of 1-bit memory cells), depending on a word length of an output data item of the ROM. In each section, the 1-bit memory cells are arranged in columns and rows. A word line 3 of the ROM runs along the same row in all sections of the ROM. On the other hand, a virtual supply voltage line 1 and a bit line 2 run along a column in only one section of the ROM. This means that the virtual supply voltage lines 1 run parallel to the bit lines 2 along all memory cells which are arranged in a column.
In the case of traditional ROMs, a 1-bit memory cell which represents a logical "0" is usually constructed out of an NMOS transistor having a gate terminal connected to a word line 3, one of the source or drain terminals connected to a virtual supply voltage line 1, and the other terminal being connected to a bit line 2. There are several possibilities for constructing a 1-bit memory cell 4 that represents a logical "1". For instance, both the source and the drain terminals can be connected to the same bit line 2, or to the same virtual supply voltage line 1, or at least one of the two source and drain terminals hangs in the air, i.e. is connected neither to a bit line 1 nor to a virtual supply voltage line 1.
In the case of a ROM read operation, in which a data item for an address is read, starting from the address, one word line 3 and n (n corresponds to the word width, or number of bits, of the data item to be read) virtual supply voltage lines 1 are specified, and are then activated in the course of the read operation. The address is divided into a row address part and a column address part, the word line 3 being determined by means of the row address part and the virtual supply voltage lines 1 being determined by means of the column address part.
When a 1-bit memory cell 4 which represents a logical "0" is read, the following occurs: Whereas all bit lines 2 are on a first supply voltage potential before the read operation, the virtual supply voltage line 1 corresponding to the address and a bit position in the data item to be read are put or activated onto a second supply voltage potential only in the course of the read operation, and the word line 3 corresponding to the address is activated. In this way the NMOS transistor which represents the logical "0" becomes conducting, so that the bit line which is connected to the NMOS transistor is charged onto the second supply voltage potential. On the other hand, when a 1-bit memory cell 4 which represents a logical "1" is read, the NMOS transistor (if a transistor is present at all) becomes non-conducting, so that the bit line is not charged onto the second supply voltage potential.
For instance, the first supply voltage potential could be VSS and the second supply voltage potential could be VDD, or conversely the first supply voltage potential could be VDD and the second supply voltage potential could be VSS.
In FIG. 1, two sections or block columns 12 are shown. Result bit lines 5 of these two block columns 12 represent the least significant and most significant bits of the data item to be read from the ROM 8. The block columns between these two block columns 12 are only indicated in FIG. 1. Each result bit line 5 is the output of a multiplexer 11, in which case, in the context of a read operation, the bit line 2 corresponding to the address or column address part is switched to the output of the multiplexer 11.
Since, in the case of the ROM 8 according to the prior art, in a column 16 a virtual supply voltage line 1 runs parallel to a bit line 2 over the whole column length, the gap between the virtual supply voltage line 1 and the bit line 2 being extremely small because of the dimensions, which are becoming ever smaller, of the design techniques which are used today, the coupling capacitance or cross-coupling between the virtual supply voltage line 1 and the bit line 2 is great. Because of the coupling capacitance, the bit line 2 is also charged onto the second supply voltage potential if the virtual supply voltage line 1 is charged onto the second supply voltage potential in the course of a read operation. In the case of reading a logical "0", this is a positive effect, since the bit line 2 is charged onto the second supply voltage potential in the course of an operation to read a logical "0". On the other hand, in the case of reading a logical "1" it is a counter-productive effect, since the bit line 2 should remain on the first supply voltage potential in the course of an operation to read a logical "1". Therefore, when reading a logical "1", it is necessary to wait for a restoration period, until the bit line 2 is again at least near the first supply voltage potential, before the result bit line 5 which corresponds to the bit line 2 is evaluated. Since it is in the nature of the matter that before a read operation it is not known whether a logical "0" or a logical "1" is read, it is always necessary to wait for the restoration period, irrespective of whether a logical "0" or a logical "1" is read. Thus the restoration period decides a clock rate at which the ROM 8 can be read.
In addition to the negative effect on the clock rate of the ROM 8, the coupling capacitance has a negative effect on the power consumption of the ROM 8. Additionally, there is a negative effect on the power consumption by the inherent capacitance of each virtual supply voltage line 1, which must be charged onto the second supply voltage at a read operation. That is, the greater the coupling capacitance and/or the inherent capacitance is, the greater the power consumption that is necessary to charge the corresponding virtual supply voltage lines 1 onto the second supply voltage potential.
In the case of a ROM, in which words with a word width of n bits are stored, in the course of a read operation, n virtual supply voltage lines 1 must be charged onto the second supply voltage potential, and brought back to the first supply voltage potential after the evaluation of the result bit lines 5. Therefore, specifically in the case of ROMs with a large word width, the inherent capacitance and also the coupling capacitance are decisive for the power consumption and maximum clock frequency of the ROM.
Therefore it is desirable to provide a memory arrangement in which the coupling capacitance and inherent capacitance are as small as possible in the case of a read operation.

Memory arrangement with low power consumption


An elastic film is provided with non-elastic regions and elastic regions formed from a multi-layer film of an elastomeric layer and a relatively inelastic layer (s).

Elastomeric films have for some time been used and discussed in the literature with regard to their applications in disposable products, such as baby diapers and adult incontinent devices. These elastomeric webs or films are used primarily in the body hugging portions of garments. Many of these elastics are temperature-treated to provide for controlled elastic recovery. In diapers, for example, elastomeric bands are typically used in the waistband portions such as discussed in U.S. Pat. No. 4,681,580, issued to Reising et al., and Lash, U.S. Pat. No. 4,710,189. Both of these patents describe the use of elastomeric materials which have a heat stable and a heat unstable form. The heat unstable form is created by stretching the material when heated around its crystalline or second phase transition temperature followed by a rapid quenching to freeze in the heat unstable extended form. The heat unstable elastomeric film can then be applied to the, e.g., diaper and then heated to its heat stable elastomeric form.
Berger, U.S. Pat. No. 3,694,815, proposed a method for attaching a stretched relaxed elastic ribbon to a garment by stretching conventional elastic ribbons and immediately freezing the elastomeric material at relatively extreme low temperatures (e.g., well below ambient).
UK Pat. Application 2190406 A proposed maintaining a conventional elastomer in a stretched condition, while attaching it to the member to be shirred (e.g., a diaper), by a rigidifying member, which would then be removed or destroyed following the attachment procedure. As described, the elastomers are first stretched then applied to the rigidifying member in its stretched form.
Matray et al., UK Pat. 2,160,473, proposes an elastomer which will shrink at an elevated temperature (e.g., at or above 175.degree. F. or 79.4.degree. C.). The allegedly novel feature of this material, compared to the heat shrink materials discussed above, is that it does not require preheating or cold treatment during the stretching operation but rather could be stretched at ambient temperatures by a differential speed roll process or by "cold rolling". The polymer proposed was a copolymer having alternating segments of polyamidepolyether block polymers, commercially available under the trade name Pebax, particularly Pebax Extrusion grades 2533 and 3533.
Problems with these elastomeric films include the difficulties inherent in applying a stretched elastic film to a flexible substrate such as a disposable diaper. For example, these film elastics, after being attached to a flexible substrate, such as by adhesives, will place shear stresses on the attachment areas. This can result in the elastic detaching from the flexible substrate, particularly after repeated elongations.
In copending application Ser. No. 07/438,593, filed Nov. 17, 1989, having a common assignee, there is disclosed an elastomeric laminate having at least one elastomeric layer and at least one skin layer which addresses some of the above-noted problems in the art.
Despite the numerous advantages in the materials of the copending application, there is room for improvement for some applications. In order to activate the nonelastomeric laminate into a state that will allow it to recover and become elastomeric, the laminate must be stretched a substantial amount, for many materials contemplated as useful for the skin and core layers. Further, when the elastic is applied to a garment, equally high stretch ratios are generally required to provide sufficient elastic force to functionally elasticize the garment. This is problematic for applications where low elastic stretch ratios would be desirable, for example, when high levels of gathering of a garment is undesirable or where required by manufacturing needs. There is also a need for elastics that will provide elasticity only in specified areas without requiring the application of separate discrete elastic elements at each area.
The desirability of obtaining elasticity in specified areas of a ribbon or tape-like substrate is illustrated by U.S. Pat. Nos. 3,800,796, 4,834,820, 4,778,701 and 4,227,952, which disclose the use of composite materials designed to have specified areas of elasticity for use in diaper systems. However, these composites require complicated construction mechanisms to bring the diverse elements of the composite together and/or special procedures for their manufacture and use, that limit their general applicability.

Minnesota Mining and Manufacturing Company


An embodiment wireless communication linkage control apparatus is configured to determine a position determination technique of a mobile terminal based on state information of a vehicle, to determine the current position of the mobile terminal, thereby controlling maintenance or release of wireless communication linkage with the mobile terminal depending on the position of the mobile terminal.

In general, a vehicular audio video navigation telematics (AVNT) system provides various conveniences to vehicle passengers by integrating various electronic devices such as an audio device, a video device, a navigation device and a telematics device mounted in a vehicle.
As such, the AVNT system has a plurality of electronic devices integrated therein and includes various functions and menus.
The AVNT system is wirelessly communication-linked with a mobile terminal such as a smartphone held by a vehicle passenger and provides convenience to the vehicle passenger.
The vehicular AVNT system is automatically and wirelessly communication-linked with a mobile terminal of a vehicle passenger through a wireless communication function such as Bluetooth when the mobile terminal held by the vehicle passenger is positioned within a vehicle.
However, when the mobile terminal of the vehicle passenger, which is wirelessly communication-linked with the vehicular AVNT system, is moved out of the vehicle from the inside of the vehicle, there is a problem in that the vehicular AVNT system maintains wireless communication linkage with the mobile terminal positioned outside the vehicle without releasing the wireless communication linkage, thereby providing inconvenience to a user.
In addition, when a mobile terminal of a driver and a mobile terminal of a passenger are each wirelessly communication-linked with the AVNT system and then wireless communication linkage is re-released within a vehicle, if the mobile terminal of the driver is moved out of the vehicle, the mobile terminal of the driver positioned outside the vehicle maintains wireless communication linkage without releasing wireless communication linkage with the AVNT system, but there is a problem in that the mobile terminal of the passenger positioned inside the vehicle is not capable of being wirelessly communication-linked with the AVNT system.
As such, conventionally, there is a problem in terms of a wireless communication linkage error whereby wireless communication linkage between a mobile terminal positioned outside a vehicle and a vehicular AVNT system is maintained rather than being released.
Accordingly, in the future, there is a need to develop a wireless communication linkage control device for reliably controlling maintenance or release of wireless communication linkage with a mobile terminal depending on a position of the mobile terminal.

Apparatus and method for controlling wireless communication linkage in vehicle


A calibration standard includes a silicon substrate having a plurality of defined regions and a plurality of calibration marks placed on respective defined regions of the silicon substrate. Each calibration mark comprises a different calibration dimension indicator and a corresponding dimension identifier. A method for calibrating a transmission electron microscope using the standard comprises positioning the calibration standard in a viewing area of the transmission electron microscope and sequentially viewing the marks and adjusting the calibration of the microscope for each mark viewed.

Semiconductor manufacturing consists of a number of crucial processing steps performed on wafer lots where measurements of minimum feature sizes known as critical dimensions (CD) are made to ensure proper device fabrication. The high-degree of precision during this processing requires the utilization of Scanning Transmission Electron Microscopes and Transmission Electron Microscopes (S/TEM) to calibrate in line CD-SEM instruments. These critical tools provide measurement capabilities in the low nanometer range. Accuracy of their measurements is essential since effective process controls depend on CDs they supply. S/TEMs require frequent calibration to ensure their accuracy since processing errors cause appreciable variation in CDs. Calibration procedures are very time consuming and have a negative impact on semiconductor fabrication workflow. Typical S/TEM magnification calibration approaches are also limited in accuracy.
A conventional calibration approach utilizes a standard that possesses a crystal lattice specimen to calibrate a S/TEM for a particular relatively high magnification. Measurements obtained from the specimen's crystal lattice spacing are compared to known data to determine if the S/TEM requires adjustment, or if the magnification results being calibrated are within tolerance. Calibration adjustments are then made accordingly. This approach requires that calibration for other magnifications in the range of magnifications, such as relatively lower magnifications, required to support semiconductor fabrication use different standards. Thus, multiple specimen exchanges along with new orientations to achieve calibration over a range of magnifications are required. In addition, the beam conditions must be reset for each standard. This iterative process is conducted until calibration is achieved for the full range of magnification required in support of semiconductor fabrication.
Another technique uses a calibration standard that includes one or two repeating features that are calibrated to a single dimensional value, such as a series of parallel lines spaced apart at a predetermined, calibrated distance. Such a standard is only useful over a certain portion of the usable magnification range of an S/TEM, thereby again requiring several different standards having appropriately varying sized features to allow the S/TEM to be calibrated over its useable range. Because S/TEM's are typically operating in a high vacuum environment, the vacuum must be broken and re-established each time a standard is changed for a different range of calibrations, resulting in an undesirable time delay. Furthermore, the use of repeating features such as uniformly spaced apart lines requires an operator calibrating the instrument to manually count the number of repeating features and cross reference the known feature dimensional values to arrive at a distance for the features to be used in calibrating the instrument. Accordingly, an operator may need to count as many as 50 repeating features, look up the dimensional value, and then multiply the number of features by the dimensional value to calculate a size measurement for calibration. This process may need to be repeated for multiple magnification values, typically 15 or more magnification values, using several different standards to cover the magnification range of the S/TEM. Such a process is time consuming and error prone.

Calibration standard for transmission electron microscopy