pH values of precipitation in dilute solutions. (Dean et al 1972).
\r\n\tTo sum up, there are numerous engineering applications of diamond which are yet to be realized and this book will address some of the mentioned and hopefully open some new topics.
\r\n\t
Lead (Pb) is a toxic element that accumulates in the body by inhaled air or ingested in food or water. Lead has been used for centuries to make water pipes and cooking utensils. In fact, lead is a very rare element in the lithosphere. Lead is one of the heavy metal that has a great number of applications in industrial activities that are necessary to life and its contact effects have been studied by some of researchers. Lead is present in applications such as: manufacture of accumulators, centralized waste landfill, copper smelter, electric-electronic components, electrowinning, inorganic chemicals, cast iron and steel, metal finishing, fusion and metal forming, powder metallurgy ferrous and non-ferrous, non-ferrous metal casting, organic chemicals plastics and synthetic fibers, chemical pesticides, storage batteries, anti-knock gasoline, pigments porcelain enamel, plastics manufacturing, electricity generating by steam, transportation of cleaning equipment and combustion wastes. All these applications are due to its physicochemical properties than allows it to be compatible and shape easily to others materials with modified properties. It can be mixed with other metals to form useful materials. Most of these materials can be largely recovered, so that lead can be recycled. The environmental threat comes from the one used in chemical compounds.
\n\t\t\tIts asymptomatic presence is one of the most important aspects in different diseases and also of environment caused by its contact or consumption of waters with low contents of this element (Naicker et al, 2010, Albalak et al, 2003& Noona et al, 2001 ). There is great concern in cities of underdeveloped countries on five continents by the fact that lead influence in the human body can develop: anemia, kidney disease, brain damage, impaired nervous system function peripheral, high blood pressure, reproductive abnormalities, developmental defects, abnormal metabolism of vitamins, low intelligence quotient and sometimes death, (Hrudey et al., 1995 USEPA, 1992). The greatest concern that its presence there affects mainly children under 6 years and unborn babies (Zhang et al., 2005, Naicker et al., 2010, & Riddell et al., 2007). On the other hand, lead plays an important role in the food chain and is of vital environmental importance because it alters the ecosystems and natural soils(Tong et al, 2000).
\n\t\t\tThe lethal dose of lead absorbed is estimated at 0.5 mg. The accumulation and toxicity appear if was adsorbed more than 0.5 mg per day. The half life of lead in bone is 32 years and in the kidney of 7 years. The exposure limit for lead in air is 0.15 mg/m3. The exposure limit for lead in food is 2.56 mg/kg according to The U.S. Centers for Disease Control and Prevention (CDC) who has defined an elevated blood lead level (BLL) as 10 micrograms per deciliter (mg/dl).
\n\t\t\tRecently Potassium Polytitanates (K2TinO2n+1) have been recognized like functional advanced materials and adsorbents of metallic ions(Tan et al., 2007), they can be present with different behaviors e.g. with relationships among n=4 to 6 they present adsorption and ion exchange properties (Wang et al, 2009) and with relationships between 6 to 8 they could be present excellent mechanical properties (Bavykin et al., 2006). Microstructure is influenced by this relationship for K2Ti4O9 layer morphology regularly is presented, fibers, whiskers or cylindrical forms to K2O•6TiO2 or K2Ti6O13(potassium hexatitanate). Potassium polytitanates have been applied like raw materials to fabricate ceramics (filters, barriers, high temperature sensors (Gratzel, M., 2001; Fox M. A & Dulay M. T., 1993), and their excellent mechanical and frictional properties are useful for their application as:reinforcing additives, as well as, antifriction properties(Zhuang et al., 2007) in different materials. Low friction coefficient has shown that they could be excellent applications as solids lubricants and frictionant materials (Xie et al., 2010). Additionally its low thermal conductivity and its high reflectance at the ultraviolet range, near to infrared region favors its application in manufacture heat resistance materials, also as isolating of materials and coatings.
\n\t\t\tTo counteract lead pollution of air, soil and water adsorbents have been developed based on activated coal (Ayyapan et al., 2005), biological mixture(TSezos., 1984), ion exchange resins(Matsumiya et al., 2003), (Plaza et al., 2009), and natural or synthetic zeolites(Barrier, 1978) which ones intended to diminish the concentration of lead in solution. Limitations such as high cost of synthesis reactors, processing equipment and maintenance, long times adsorbent synthesis, bogged down process, complications for storage the exhaust adsorbents all of these reasons generate the necessity to develop adsorbents that combine excellent adsorption properties, low cost, high efficiency, short and immediate processes and a post-treatment or confinement environmentally safe.
\n\t\t\tFor this reason in this research has been synthesized PPN (Potassium Polytitanates Nanoadsorbents) as effective adsorbents of lead in contaminated water.
\n\t\t\tAmong several chemical routes available for the synthesis of nanoadsorbents materials, molten salts technique has been proved to be very promising due to its uniqueness in being facile, cost effective, environmentally benign and crystalline regulated in order to adsorption applications (Afanasiev, 2006).
\n\t\t\tBelow are described some investigations which have involved different techniques for obtaining nanomateriales with interesting adsorption properties.
\n\t\t\tOne method to obtain layered alkali titanates in nanometric scale is the called soft chemical route, which is a type of chemical reactions used at room temperature in open systems, based on polymerization reactions in which a molecular precursor solution becomes a chemical reaction and subsequently dried and densified into a solid material with properties different from that of the starting materials. Riss et al., 2007 adjusted the photoelectronics properties of layered titanates nanostructures by changing the nature and bonding state of ions in the interlayer region studies. Also they have shown that a facile ion exchange behavior in titanates nanostructures control these properties by interactions in the interlayer region.
\n\t\t\t\t\tIt is well known that cationic ions that exist in the structure of the titanates are weakly attached to each interlayer channel (Unal, et al, 2003); therefore the adsorption and ion exchange properties are due to that the distances more higher between alkali ions negatively charged and the oxygen ions than those distances of protons and octahedral oxygen ions. Zhang et al., 2005 proposed that the protonation of the TiO6 block influences the electron density in the moiety of the Ti-O to the OH bonds leading to an increase in the length of adjacent Ti-O bond.
\n\t\t\t\tThe hydrothermal synthesis appeared in the decade of the 80´s and was proposed as a method of synthesis of crystalline ceramic materials with high purity features. Through this method can be obtained high-quality crystals without the need of routines of grinding or a further heat treatment of materials, using low surface area powders and high pressures at temperatures below 200° C. Besides exploits the reactivity of powders with low specific surface areas. Some types of zeolites and titanates as adsorbents for various applications have been synthesized (Hayashi, H. & Hakuta, Y. 2010).
\n\t\t\t\t\t\n\t\t\t\t\t\tYang et al., 2010 prepared layered titanates nanofibers and sodium titanates and sodium titanates in acid form by hydrothermal synthesis, they studied these materials as adsorbents for removal of toxics radioactive (Sr2+, Ba2+ as substitute of 226 Ra2+) and heavy metals ions from water (Pb2+). This method consists in mixing hydroxides and titanium compounds under hydrothermal conditions. So two aqueous solutions containing salts are mixed y treated during 2 days in an autoclave at 245 °C (hydrothermal reaction) to yield titanates fibers. The solid after drying at 178° C during 6 h in the mixture can be recovered and washed with deionized water. They can convert to trititanate to a new phase Na1.5H0.5Ti3O7. The chemical equation for this transition is:
\n\t\t\t\t\tSol gel Route it is described as a structural synthesis from drawing upon particles in solution (Schmidt et al., 2010). It´s similar to the precipitation route but different due in this method is more stable the environment inside of the solution as result of chemical interactions. The conventional agglomerated sizes are presented around of 1-100 nm. The overall sol-gel process can be described in four stages:
\n\t\t\t\t\thomogeneous precipitation (kinetic control),
Initial nucleation where by decomposition of compounds it is release the necessary precursors to particle precipitation,
metallic hydrolysis or deprotonation of hydrous metal oxides and
control of parameters that influences in the hydrolysis as such as: control of the temperature, concentration, and pH of the solution.
Finally hydrolysis process is promoted by compounds chemical interactions as organic liquids which ones OH- ions in systematical form.
\n\t\t\t\tIn this technique analytical-grade reagents as KF and TiO2 (anatase or amorphous gel) are used as starting materials. Afterward powders are dried at 720° C for 20 min before being mixed. The weight ratio of KF to TiO2 in the mixtures can adjusted to various values, to investigate the influences of weight ratio on the formation of titanates whiskers. Powders are mixed homogeneously to form a precursor powder and then put into a furnace. The heat treatment is basically fixed at 720° C for 4 h(Li et al., 1999).
\n\t\t\t\tThe synthesis method of molten salts, is the fusion of salts to solubilize reagents that lead to better dissemination of materials and reduced the reaction temperature. The term "Molten Salt" is self-descriptive; it is melted salt(s). The molten salt fusion is usually performed in a temperature range from 200 to 600 ° C. When liquid is stable, has a heat capacity similar to water (by volume) and flows much like water does. In this method it loses the difference between "solvent" and "solute" in the sense that the flux must provide atoms or structural building units ending in a final crystal product or “quasi-crystalline”. Moreover, the chemical properties of flux, as the acidity and redox potential, have a controlling influence on the nature of the products. Salts are simple, usually ionic (that is the chemical bonds are a simple ionic type) and stable compounds. The most common example of which is "table salt", or sodium chloride (NaCl). Both sodium and chlorine are notoriously reactive; sodium is one of the most electropositive substances (wants to lose an electron) and chlorine one of the most electronegative (wants to take an electron). These two opposite substances readily join to form stable sodium chloride via a strong ionic bond.
\n\t\t\t\tUnique properties and behavior different among the oxides family, potassium polytitanates are a large class of semi-crystalline titanates materials, arrangements in their lamellar or stringy nanostructures, uniformly linked and with interlayer spaces between them. Also the exfoliation and intercalation could be properties present in this kind of materials (Unal et al., 2003).
\n\t\t\t\tThe procedure for obtaining powders by molten salt consists as follow: TiO2 powders were mixed with KNO3 and KOH and then heated to a temperature range from 450 to 550 ° C and afterward treated for a period of time 1 hour. The synthesized powders should be washed (purified) with distilled water and separated with a filter paper. Finally the powders are treated inside furnace at a temperature of 90° C during 2 hours. Complete description for the potassium polytitanates is given in the experimental part of this chapter.
\n\t\t\t\tHowever, the fibrous powders have a bulky nature, poor fluidity, and inconvenience in handling. Thus, in spite of their attractive properties, fibrous potassium titanates are difficult to use to produce ceramic green bodies by conventional ceramic technologies and require very high pressures. Moreover, the fibrous powders tend to cause dusting, which represents a health risk in the working environment; the fibrous morphology of some potassium titanates has been associated with carcinogenicity. For these reason in this work potassium polytitanates nanoadsorbents were bonding with potato starch according previous studies (Gregorová et al, 2007). Potato starch was used to bind the nanoadsorbent and generate porous structure due that is an organic material with an ash content low to negligible (at least from the standpoint of materials science.) This is above the sintering can say that the end products of starch will always be CO2 and H2O, provided that during the burning is conducted in an oxidizing atmosphere. Of course, under reducing conditions may occur residual carbon. The potato starch breakdown begins to be detected below 300° C (Laurentin et al., 2003).
\n\t\t\t\tMolten salt through the following reaction is proposed:
\n\t\t\t\tIn this work, we describe the preparation and characterization of nanoadsorbents of potassium polytitanates produced by the molten salt synthesis which ones contain both combined structures potassium titanate. Figure 1.
\n\t\t\t\tIdealized structural arrangements from K2Ti4O9 (potassium tetratitanate) and K2Ti6013 (potassium hexatitanate).
Nanoadsorbents of potassium polytitanates were produced with KNO3 (Merck brand with 98.9% of purity), KOH( brand Aldrich with flakes form and Powdered TiO2 (anatase of purity of 99%, with average particle size of 3 mm brand Aldrich, Milwaukee, WI) in a relationship of 8.2:1.0:0.8 all of them were treated, using Steel Stainless crucibles(750 ml of capacity). First stage consists of treat in molten mixtures KNO3 y KOH. The synthesis was carried out in an electric muffle furnace (Thermolyne 27000), 500° C for 1 h in air atmosphere compounds. Afterward having reached a temperature of 500 was added to the TiO2 anhydrous. Preliminary tests showed that this time was sufficient to obtain products consisting mainly of potassium titanates with some of un-reacted TiO2. The ideal time of heat treatment of this technique to produce pure potassium titanates is three hours, but this option was rejected for economic and energy saving reasons. After that molten material was separated, in this stage soluble compound were separated of the solid material. Nanoadsorbents fine powders were washed in distilled water to dilute any remaining of soluble nitrates and chlorides in the molten salt mixture, these powders were washer using 1000 ml of bidistilled water for each 250 g of powders and then were filtrated with paper Whatman No. 42 four times each set. The ultimate suspension was ultrasonically treated (Fisher Scientific, Model 550, USA) for 30 min (80.75 kW at 20 kHz) and filtrated. The powders thus obtained were finally dried for 2 h at 90° C.The dried powders Were used directly and also in granular form as adsorbent material in adsorption columns. Thermal events of nanoadsorbents powders and their dehydration processes were investigated by thermal analysis, (TGA/DTA, in Perkin Elmer, Pyris Diamond instrument).
\n\t\t\tPhase composition of nanoadsorbents were analyzed by X-ray diffractometry (XRD, Philips X’Pert using CuKa radiation with a nickel filter, with the continuous scan mode at 51–601 2y at a rate of 0.0212 y/s; the operation conditions were: 40 kV and 100 mA. The reflection positions and relative intensities were referred to the International Center for Diffraction Data (ICDD-2004). Quantitative XRD analysis was carried out to determine the TiO2 contents in the PTP, using TiO2-anatase phase as an internal standard.
\n\t\t\tThe kinetics of adsorption of Pb (II) present in aqueous solutions was determined by an atomic emission spectrometer (ICP, Thermoelemental Thermojarrel Ash model Iris Intrepid II). The spectrometer was calibrated with NIST certified standards.
\n\t\t\tThe specific surface area was determined on a sorptometer (Quantachrome Autosorb1C, Asic-xtcd6) using the principle of adsorption/desorption of a monolayer of nitrogen on the surface of the solid, based on the methods of Brunauer-Emmett-Teller (BET) and micro-pores analysis. The pore size distribution was investigated by mercury intrusion porosimetry (MIP Pore Master 60 GT). IUPAC (International Union of Pure and Applied Chemistry) classification was used to identify the porosity of the samples characterized. On the other hand, isotherms were adjusted according.(Gregg and Sing, 1952: Rouquerol et al., 1994)
\n\t\t\tThe observations and energy dispersive X-ray spectroscopy (EDS) patterns of nanosorbents were obtained of the scanning electron microscopy (SEM) were carried out in a XL30-ESEM FEI Philips instrument, operating at 20 kV. Transmission electron microphotographs (TEM), high-resolution transmission electron microphotographs (HRTEM), selected-area electron diffraction (SAED) in a TEM Titan 80-300 FEG is a high-resolution analytical transmission electron microscope operating at 200 kV. The sample for TEM/HRTEM observations was prepared by deposition of a drop of the colloidal dispersion of K2Ti6O13 onto 200 mesh Cu grids coated with a carbon layer.
\n\t\t\tFact Sage software has been used to predict and of to calculate phases than could precipitate and phase transformation during adsorption processes in the aqueous system.
\n\t\t\t\n\t\t\t\tFigure 2 shows processing stages of manufacturing process of potassium polytitanates nanoadsorbents.
\n\t\t\tFlow chart of manufacturing process of potassium polytitanates nanoadsorbents.
For the fixed-bed experiments, potassium polytitanates nanoadsorbents were prepared in the form of granules.
\n\t\t\t\tThe initial metal stock solution was prepared from the nitrate salt, Pb(NO3)2 6H2O. All chemicals were reagent grade and they were used without further purification. All solutions were prepared with deionized water and the glassware was cleaned by soaking in 10% HCl and rinsed with water. The background electrolyte was potassium nitrate.
\n\t\t\t\t\tpH, adsorbent dose and concentration of the solutions were selected considering that the pH of operation of polytitanate potassium in nanoasorbentes is 10.24 (stable after 24 hours) this was based on previous studies and preliminary evidences of PPN electrochemical studies than were performed.
\n\t\t\t\t\tAccording to these electrochemical studies that were carried out in the nanoadsorbents and research made by Dean et al, 1972, pH values for precipitation of lead in dilute solutions is located close to 6 (Table 1). These values were considered for the systematization and synchronization of the experiments, as well as taking the value of 3.5 which is a real industrial value in the treatment of lead wastewaters. In the table 1 are presented pH values of precipitation of different bivalent metallic ions.
\n\t\t\t\t\tPrecipitation values in diluted solutions | \n\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t\t\tpH\n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t
\n\t\t\t\t\t\t\t\t\tFe3+\n\t\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\t2.0 | \n\t\t\t\t\t\t\t
\n\t\t\t\t\t\t\t\t\tAl3+\n\t\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\t4.1 | \n\t\t\t\t\t\t\t
\n\t\t\t\t\t\t\t\t\tCr3+\n\t\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\t5.3 | \n\t\t\t\t\t\t\t
\n\t\t\t\t\t\t\t\t\tCu2+\n\t\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\t5.3 | \n\t\t\t\t\t\t\t
\n\t\t\t\t\t\t\t\t\tFe2+\n\t\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\t5.5 | \n\t\t\t\t\t\t\t
\n\t\t\t\t\t\t\t\t\tPb2+\n\t\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\t6.0 | \n\t\t\t\t\t\t\t
\n\t\t\t\t\t\t\t\t\tNi2+\n\t\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\t6.7 | \n\t\t\t\t\t\t\t
\n\t\t\t\t\t\t\t\t\tCd2+\n\t\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\t6.7 | \n\t\t\t\t\t\t\t
\n\t\t\t\t\t\t\t\t\tZn2+\n\t\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\t7.0 | \n\t\t\t\t\t\t\t
\n\t\t\t\t\t\t\t\t\tHg2+\n\t\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\t7.3 | \n\t\t\t\t\t\t\t
\n\t\t\t\t\t\t\t\t\tMn2+\n\t\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\t8.5 | \n\t\t\t\t\t\t\t
\n\t\t\t\t\t\t\t\t\tCo2+\n\t\t\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t\t | \n\t\t\t\t\t\t\t\t6.9 | \n\t\t\t\t\t\t\t
pH values of precipitation in dilute solutions. (Dean et al 1972).
Lead nitrate used in adsorption tests (Aldrich, 99% purity) was an aqueous solution with a concentration of 155 mg/dm3, using distilled water and pHo= 5.5 without initial pH adjustment. Then the solutions were stirred for a period of 30 minutes at 120 rpm, with the aid of a magnetic stirrer Corning brand. This solution, No. 1, was used in direct adsorption tests. Additionally, solution 2 was prepared by mixing 1 with nitric acid (1M) for a pH0= 3.5. Both solutions were used to investigate the influence of pH on the effectiveness and mechanism of removal of Pb2+ of acidic solutions, usually produced as industrial waste
\n\t\t\t\t\t\n\t\t\t\t\t\tDean et al, 1972. pH measurements were made with a pH-Meter, Make plusmeter Orion Model 420, with a glass electrode Thermo brand.
\n\t\t\t\tAll experiments were conducted at 25 ± 2° C. Pyrex ® glass column with the dimensions of 25 mm in diameter and volume Vc = 75 cm3, which was filled with 165g of adsorbent granules (with sizes from 2 to 3.5mm), occupying a volume of Vo = 70 cm3. Granules in turn were supported by a stainless steel mesh (standard mesh # 325) of 24mm of diameter, not to drag all this fine material produced during the elution process. The top of the column was covered with a lid that contains a connecting tube to remove air bubbles. Flow of metal solutions was controlled by a valve located at the bottom of the column. Others research have applied fiberglass to support the materials adsorbents. In this work, previous studies were conducted (with distilled water only) to determine the flow rate of solutions through the porous ceramic adsorbents. The optimum rate was determined at 70 ml/min, this was made trying to consider bibliographic information found for columns packed with activated carbon and porosity content in the adsorbents.
\n\t\t\t\tThe corresponding aqueous solution was added with a burette to the adsorbent, to control the rate of delivery. The initial rate of elution corresponded to a value of 2Vo/h (140 cm3/ h), this rate is within the typical values for industrial adsorption columns (Klein 1985) and samples were monitored and passed through the adsorbent at different times (0, 2, 5, 11, 20, 37 and 40 hours.). The aqueous solution was poured into to the column using a system of two attached vessels located over the column with a stable hydrostatic pressure of liquid (Figure. 2). To determine the elution rate, the solution was passed through the column and collected in samples of 100 cm3, which determined the pH (Orion potentiometer 420) and the contents of K and Pb by ICP spectrometry (Thermoelemental Thermojarrel Ash, Iris Intrepid II).
\n\t\t\t\tThe results of Pb and K in each period were evaluated by chemical analysis technique of atomic absorption spectrophotometry in order to study the mechanisms of reaction column and also pH of solutions were determined in each of the different samples.The amount added in this device was enough to supply each experiment by 40 hours continuously.
\n\t\t\t\tSchematic representation of the attached vessels for dynamic adsorption experiments on lead removal by potassium polytitanates nanoadsorbents.
All experiments were performed independently for each condition of pH and concentration. The maximum time of pass of the lead nitrate solutions was 40 hours (adsorbents saturated), then the adsorbents were removed from the column, dried at a temperature of 60 ° C for one hour. These adsorbents were characterized by the techniques of SEM, XRD, thermal analysis, IR and specific surface area.
\n\t\t\t\tOperating conditions in the dynamic adsorption experiments in columns for aqueous solutions of lead are summarized in Table 2. This work has applied a method based on the originally described by Michaels et al., 1952 for ion exchange resins and subsequently by Weber, 1972& Lukchis, 1973, for activated carbon beds.
\n\t\t\t\tProperty/Feature | \n\t\t\t\t\t\t\tInorganic Media | \n\t\t\t\t\t\t
Agglomerate Size | \n\t\t\t\t\t\t\t0.25-3 mm. | \n\t\t\t\t\t\t
Column Volume | \n\t\t\t\t\t\t\t175 ml. | \n\t\t\t\t\t\t
Volume ocupaded by adsorbent | \n\t\t\t\t\t\t\t53 ml | \n\t\t\t\t\t\t
Density | \n\t\t\t\t\t\t\t3.1 | \n\t\t\t\t\t\t
Weight of adsorbent | \n\t\t\t\t\t\t\t169.6 g | \n\t\t\t\t\t\t
Volume of solution in the area occupied by the adsorbent. | \n\t\t\t\t\t\t\t35 ml. | \n\t\t\t\t\t\t
Ion-Exchange class | \n\t\t\t\t\t\t\tcationic | \n\t\t\t\t\t\t
pH | \n\t\t\t\t\t\t\t3.5, 5.5, 5.8 | \n\t\t\t\t\t\t
Elution Rate | \n\t\t\t\t\t\t\t2.33 ml/min.=140mL/H | \n\t\t\t\t\t\t
Water content after draining | \n\t\t\t\t\t\t\t40-50% | \n\t\t\t\t\t\t
Initial concentration of Pb2+ in solution | \n\t\t\t\t\t\t\t≈150, 330 mg/L | \n\t\t\t\t\t\t
Column and nanoadsorbents experimental conditions used in adsorption processes: Properties/features and Inorganic media.
The results showed that the introduction of KOH in molten potassium nitrate allows for different titanates as a function of the variation in the chemical composition of the melt. The probable mechanisms of the process that takes place in the investigated systems are represented in the figure 4.
\n\t\t\t\tIn this work were considered two ways in the formation of simple titanates ions:
\n\t\t\t\tThe dissolution of TiO2 as a result of interaction with OH- ions.
The acid-base interaction of the Lux-Flood of O2-ions directly with TiO2 particles
The interaction between TiO2+O2+K ions promotes the formation of ions, which ones may not participate in the formation of K2TiO3 as product by high solubility in the melt and hydrolysis by water during washing of the sediments.
\n\t\t\t\tStructural fragments of the TiO2 network formed by interactions with OH-(solution) can also be transformed into simple structural units titanate anion by the interaction of Lux-Flood (TiO2+02-). This anion can participate in the formation of ions polytitanate (K2TinO2n+1 +OH-).
\n\t\t\t\tThe formation of titanates (polytitanates) of potassium can occur in hot melt but the rate of hydrolysis and decomposition of them is high so that the formation of potassium titanate crystal in the melt is of low probability.
\n\t\t\t\tKinetic data obtained showed that the amount of potassium titanate formed by the molten salts treatment after the end of induction period (1 hour) does not depend of temperature or KOH content in the melt.
\n\t\t\t\tThis can consider this period of induction and the time needed to obtain the product system in thermodynamic equilibrium. The process of obtaining of this equilibrium system includes the processes indicated in Figure 4. Taking into account that the rate of these elementary processes is different, it is can say that the amount of product obtained is due to the ion content variation O2-(KNO3) in the melt.
\n\t\t\t\tIn the washing process, free positions of potassium cations in the crystal lattice may be occupied by cations of hydrogen during the washing process. Previous results indicate that the anionic structure of sintered polytitanate does not depend on potassium content. High rate of hydrolysis of simple potassium titanate by the washing allows obtain solids products in the form of potassium polytitanate formed as nanometric particles with molar relationships of K2TiO/TiO2=5.1, at 500° C of temperature.
\n\t\t\t\tIn the cooling stage, it is possible that the formation of crystalline titanates includes both titanium compounds: oxides and titanates and then the generation of different forms of TiO2 as: anatase, brookite, and rutile and one part of titanium oxide crystals was formed by interactions between anions of titanate.
\n\t\t\t\tChemical processes scheme in systems treated by the KNO3-KOH-TiO2 molten salts processes.
Before performing adsorption column, it is necessary to determine the coefficients of adsorption in static systems, for lead present in the different waters, with the aim of designing appropriate operating conditions.
\n\t\t\t\t\tIn addition adsorption results have determined that it is possible to perform adsorption studies by column experiments under real conditions of flow (non-equilibrium situation).
\n\t\t\t\t\tChemical analysis data (Figure 5.) showed than the adsorbent effectively removal Pb2+ ions in the solution with pH0= 5.5. After passing the solution 1 through the adsorption column, the lead concentration decreased to 0.5-0.6 mg/dm3, meeting the requirements of national rules for river water (1.0 mg/dm3). The best lead removal of Pb2+ was observed after three hours of contact, and then the saturation time did not influence the effectiveness of the removal of lead is shown in Figure 4. However, for solution 2 (pH0= 3.5), the remaining concentration of Pb2+ was relatively higher but decreased to 14-23 mg/dm3.
\n\t\t\t\t\tEffect of contact time on the content of Pb in the passed aqueous solution prepared at pH of 3.5 and 5.5.
During adsorption process, both eluted (purified) solutions showed a high content of K, whose concentration changed during the time of saturation of the adsorbent (Figure 6.). During first ten hours, the content of K increased from 0.07 to 118 mg/dm3 (solution 1) and 205 mg/dm3 (solution 2) and then decreased between 86 and 93 mg / dm 3 (pH0= 5.6) and between 133 and 143 mg/dm3 (pH0= 3.5).
\n\t\t\t\t\tPotassium concentration in the eluted solution was higher for the solution 1 than those in solution 2, which can be explained by the presence of two parallel processes of ion exchange:
\n\t\t\t\t\tPb2+ ↔ 2K + (PbOH+ ↔ K+) and
H+↔K+, by reducing the pH, second process rate increases strongly, dominating the first.
With increasing K content increased the pH value of the eluted solution to 10.6 (solution 1) to 11.3 (solution 2), (Figure 6). It is noteworthy that the maximum value of pH was observed in the first sample collected and gradually decreased (solution 1) or stabilized (solution 2). The elution rate retained its original value during 15 hours of contact under conditions of constant hydrostatic pressure, and then gradually decreased from 140 to 100 cm3/h (38 contact hours) is shown in Figure 7.
\n\t\t\t\t\tEffect of contact time on the content of K in the passed aqueous solution prepared at pH of 3.5 and 5.5.
Effect of contact time vs Ph in adsorption process with potassium polytitanates.
The behavior of pH in solutions with Pb, has shown that in solution with pH0=3.5 were obtained higher values after the first hour of sampling compared with those in which ones carried out with pH0 5.5. This may be due to adsorption capacity lower in solutions with lower pH0 to 5.5 inducing the formation of more precipitation of hydroxide-like compounds in the initial stage of the experiment and therefore a lower activity between the adsorbent surface interactions and lead ions in solution.
\n\t\t\t\t\t\n\t\t\t\t\t\tFigure 9 shows a comparison in measuring the pH of the dynamic experiments carried out at this stage lead.
\n\t\t\t\t\tInfluence of solution volume passed through column versus elution rate of Pb solution and versus pH. The experiments were done on a pH0=5.5. The initial concentration was: Pb = 150.55, K =.065 in mg/L.
\n\t\t\t\t\t\tFigure 8 shows a graph of the volume passed through the column vs. elution rate and versus pH. In the figure 9 it can be seen that the elution rate on dynamic adsorption experiments of Pb 150mg / L remains constant during the first stage almost as much as 50% of the passage of total solution volume, the rate decreases in the last quarter of the experiment, this may be due to saturation of available adsorption sites on the adsorbent.
\n\t\t\t\t\tEffect of contact time on the flow rate of aqueous solution.
The goal of the XRD studies in this research was indentify crystalline phases, also chemical composition of materials applied in the different stages of processing. Studies were first realized in the start materials. The quantify of crystalline phases was made in previous studies by Li et al, 1999.
\n\t\t\t\t\n\t\t\t\t\tFigure 7 shows X-ray diffraction pattern corresponding to the obtained samples in the method of making of potassium polytitanates nanoadsorbents by means of precursors route in molten salts. Details of synthesis for each material is given and described in the experimental methodology of this research. Chart 74-0275 was identified as K2Ti6013 of ICDD database.
\n\t\t\t\tCrystalline phases contents in selected composition as optimum have shown quasi-crystalline behavior for a N value (K20/TiO2) of 5.1. Whit this relationship the main XRD diffraction intensities obtained in 2θ degrees were: 11.2, 23.9, 29.8, 33.1, 34.7, 37.8, 43.1, 47.5, 47.7, 51.9, 55.1, 57.3, 58.7, 59.2, 61.9 y 66.4°(main reflexions in volume) these results are in agreement with Li et al 2009.
\n\t\t\t\tBesides it is very important to note than potassium titanates pure compounds as: K2Ti2O5 (potassium dititanate), K2Ti4O9 (potassium tetratitanate) and K2Ti6O13 (potassium hexatitanate) all of them includes closed reflections in 2 teta degrees scale. Figure 11 shows a graph corresponding to potassium titanates in form of pure compounds.
\n\t\t\t\tX-ray diffraction (XRD) patterns of potassium polytitanates nanoadsorbents from samples prepared by molten salts synthesis,, with relationship of TiO2/K2O = 5.1.
X-ray diffraction (XRD) patterns from pure potassium titanate: K2Ti4O9, K2Ti6O13 y K2Ti8O17.
According to EDX-S analysis results the crystalline phases of the material produced from mixtures of PTP containing oxides of titanium as K2Ti6013.
\n\t\t\t\t\n\t\t\t\t\tFigure 12 shows atomic arrangements obtained from the data of X-ray diffraction for nanoadsorbents designed in powder cell program software.
\n\t\t\t\tAtomic arrangements obtained with nanosorbents data, nanostructure was modeled by Powder Cell Software and ICDD 2004 data base.
There exist three parameters used in the measurement of porosity: specific surface area, the specific pore volume (open porosity) and size and distribution pore. Results show values of surface area were similar than those obtained by Wallenberg et al.,1990 from potassium tetratitanate of 13.9m2/g, in potassium polytitanates nanoadsorbents was obtained 13.96m2/g as result from without treatment samples
\n\t\t\t\t\tIn order to know the surface characteristics of both external and internal, in the adsorbents, there was an isotherm nitrogen adsorption on a sample of granular adsorbent with BET technique, the method for sample preparation described previously in experimental part.
\n\t\t\t\t\tThe nitrogen adsorption isotherm obtained of the based in potassium polytitanates, is presented in figure 13. BET measurements were realized for three sections of column: top, middle and bottom, also one sample without adsorption. Such plots are typical for microporous solids with a significant contribution to the meso and macroporous scale (Ruthven, 1984). The higher value was presented in the sample corresponding to top of column of 2.54m2/g. Figure 13\n\t\t\t\t\t
\n\t\t\t\t\tIn the nanoadsorbent particles analyzed (sample without treatment), were found in the dimensions range from 100 to 150 microns. Results (shape of the isotherm) have indicated that the porosity detected, corresponding to type mesoporous adsorbents with regions of porosity of relative pressures (P/Po) 0 to 0.2, then from 0.2 to 0.32 on the scale corresponds to the inter-lamellar distances that exist in the structure of the potassium titanates. The results showed that there is a pore size distribution variation, containing a scale small fraction less than 50 A ˚ assessed by TEM.
\n\t\t\t\t\tResults of specific surface area measurement of dynamic experiments for samples with Pb: 1) granular adsorbents agglomerated with potato starch, without adsorption proceses, 2), 3) and 4) same adsorbents extracted from the adsorption column with solutions of Pb, on the top, middle and bottom, respectively
The morphologies of the start material samples were investigated by scanning electron microscopy. Figure 14 shows the SEM images of quasicristalline potassium polytititanate nanoadsorbent. From figure 2a, was found that the this material consisted of agglomerates of well-defined layers with sizes of 100 to 500 nm. The surfaces of these layers were relatively smooth. After crystallization, the sizes of these layers kept unchanged. However, their surfaces became rough (Figure 17). Obviously, the layers of quasicrystalline K2Ti4O9 were composed of small agglomerates primary particles of several nanometers in size.
\n\t\t\t\t\n\t\t\t\t\tFigure 15 shows a 10000X photomicrograph of a sample of adsorbent after the adsorption process of lead. Samples have remained for a contact time of one hour with the solution corresponding to the concentration of 155mg/L of Pb(NO3)2. They can be observed with the morphology of agglomerates of lead adsorbed on the surface of potassium polytitanates.
\n\t\t\t\tSEM Photomicrography. Agglomerates of potassium polytitanates nanoadsorbents a) y b) spectrum obtained by SEM-EDXS Technique.
Photomicrography of nanoadsorbents in lead adsorption. The concentration of solution was 155 mg/L of solution. The contact time corresponded to one hour.
Thermal analysis data of Figure 16, corresponding to PTP have indicated that the obtained material contained adsorbed water (removed from 350 to 550 ° C) and structural water (removed from 500 to 700 ° C). The thermogram ATG showed a partial loss of sample weight during their analysis of 8.8% (wt%) at 555° C, subsequently detected a loss of 4.7 (wt%) to 714° C generated by the decomposition of groups Ti -OH (Shimizu et al., 1981) (removal of structural water).
\n\t\t\t\tThe DTA thermogram indicated the presence of an exothermic reaction to 703° C, which corresponds to the onset of crystallization of the PTP (Bergon et al., 1984). At a temperature of 1030 ° C, there is only the transformation of anatase and rutile TiO2.
\n\t\t\t\tThermal analysis of Potassium polytitanates nanoadsorbents.
Morphology of the nanaoadsorbents was further investigated by transmission electron microscopy. Figure 17 shows the TEM image of quasi-crystalline K2Ti409(layers) and K2Ti6O13(fibers). It was found that some well-defined lamellar agglomerates of about 100 nm in sizes were connected to each other to form pores in the range of 30 to 50 nm. During the sonication for TEM measurement, some small primary particles were dropped from the fibers of K2Ti6O13. These monodispersed primary particles are of about lower than 50 nm in size, in agreement with SEM observation. Most of the morphology of the particles in PPN was still preserved well after sonication. These secondary agglomerates are slightly larger than those of anatase phase. Mesopores formed among the small interlayer spaces in nanoadsorbents, while macropores or large mesopores produced among of PPN were also observed. This confirms the existence of a hierarchical porous structure in the nanoadsorbents. The TEM image of this is consistent with the XRD and SEM results obtained.
\n\t\t\tThe IR analysis confirms that there is no generation of new functional groups at the end of the adsorption process. When comparing the spectrums of figure 18, are very similar, there is only a small variation in the intensity of some small peaks located around 1440 and 1750 WLcm-1, these peaks can be attributed to ion exchange occurred between ions of K+ and Pb2+ during the adsorption process. Nakamoto et al, 1978.
\n\t\t\t\tThe adsorption promotes a decrease in the intensity of the absorption bands of 1448 and 1613 cm.-1 (angular vibration groups Ti-OH and HOH). This indicates that the incorporation of Pb2+ in the surface structure of titanate decreases the concentration of Ti-OH groups and adsorption of H2O in the air. While, there is a variety of characteristics of Ti-O bonds in the octahedral TiO6, instead of an adsorption peak at 500 nm where two peaks at 500 and 650 nm.
\n\t\t\t\tTEM images of scratched nanoadsorbents: a) TEM image of a nanoadsorbents composed of several lamellae, b) scratched surface morphology (c) SAED pattern of this whisker showing the same crystallographic orientation of lamellae and d) interlayer spacing on potassium polytitanates structure.
After the adsorption experiments samples were milled, mixed, heat treated (780 and 900° C) and afterward poured into glass flasks, in a 10% v/v of adsorbent with the rest of water. These solutions were heat treated of 96° C during a period of 5 hours (Japanese rule JISR-3520 and Russian rule GOST 10134-82). The finality of these processing was the assess of the final lead content and consider as free in solution and its total solubility. Results (Table 3) have shown, that final content in the samples were treated to 900°C has met with a lower level for water for human consume(Abalak et al, 2003).
\n\t\t\t\tHeat treatment Samples | \n\t\t\t\t\t\t\tLead Concentration (mg/L) | \n\t\t\t\t\t\t
780° C | \n\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t\t0.140\n\t\t\t\t\t\t\t | \n\t\t\t\t\t\t
900° C | \n\t\t\t\t\t\t\t\n\t\t\t\t\t\t\t\t0.064\n\t\t\t\t\t\t\t | \n\t\t\t\t\t\t
Results of chemical analysis by ICP technique for nanoadsorbents heat treated samples to 780 and 900° C.
IR spectrums for two samples a) without adsorption process and b) adsorbed with lead ions.
In this study was developed a new adsorbent for the removal of divalent cations on metal oxides, which allows continuity between surface reactions and precipitation. The model applied in Figura 19 fits the model of surface complexity, whereas the precipitation in the solid is described by the formation of a solid solution whose composition varies continuously between that of the original material and a pure precipitate cationic adsorption. It demonstrated the ability of the surface precipitation model to describe the adsorption equilibrium of metal cations in potassium hydroxide amorphous. The model can also be extended to describe competitive cationic and anionic adsorption.
\n\t\t\t\tScheme of surface complexation/precipitation reactions. Modified from Lützenkirchen J. & Behra, Ph (1996) of the original model of Farley et al. (1996).
Farley et al, 1984 proposed surface precipitation model in order to cations adsorption in metallic oxides.
\n\t\t\t\tOur working group will shortly present a study on the transformation of potassium titanate about this nanoadsorbents kind being that it is possible carry out after the adsorption process a treatment to convert an orthorhombic structure(potassium titanate) in a new metallic titanate(metallic titanate) with new functional properties.
\n\t\t\t\tStructural transformation of the nanoadsorbents with help of heat treatment.
The results confirmed that the nanoadsorbents based on potassium polytitanates promoted the removal of lead ions from aqueous solutions. The greatest efficiency of removal was obtained in the No.1 solution, slightly acidic (pH0 5.6). To explain the action of the investigated nanoadsorbents, it is to consider the mechanism of interaction between potassium titanates and Pb-containing solutions with different pH. It is well known that the chemical speciation of Pb in aqueous solutions depends on the pH (Dean et al. 1972). In acidic solutions (pH <5) Pb2+ ions predominate, for pH values in the range from 5 and up to 6, the solutions have a high ion content PbOH+, and also Pb2 +. In solutions with pH> 6 is favored precipitation of Pb (OH)2. The investigated adsorbent has a hydrolysis high rate and becomes to its hydrated form (Zheng et al., 2005, Nunes et al., 2006), thus increasing the pH and the concentration of K+ ions in aqueous solution. In the first stage of interaction of the adsorbent with the solution of lead salts, can be seen two parallel processes: the adsorption of Pb2+ and PbOH+ ions on the inner surface of the potassium titanates crystals as well as the hydrolysis of titanate potassium. After adsorption of Pb2+ ions, they are involved in a process of ion exchange with K+ cations, which are located between channels from the crystals of the adsorbent (Figure 1 ). Our results can be applied perfectly to Farley model et, al 1996.
\n\t\t\t\tThe most important aspect in this work is that it is possible to obtain new materials from contaminated materials using a single heat treatment and without human health risks.
\n\t\t\tIn this work were developed potassium polytitanates nanoadsorbents by molten salt synthesis with general formula (K2TinO2n+1), where the relationship (K2O/TiO2)= 5.1, with a homogeneous structure and high functional properties. Nanoadsorbents obtained with a lamellar and fibrous structure, have shown a high intercalation of cations, ion exchange activity and structure layer, and fibrous, characterized by high adsorption properties.
\n\t\t\tNanoadsorbents were obtained as ceramic materials whit porosity and quasi-crystalline phases regulated. They serve for the immobilization of Pb2 + and with an additional heat treatment can be obtained ceramics general interest.
\n\t\t\tThe lead removal mechanisms in the adsorbent produced in granular form and applied to adsorption columns, was carried out by a combination of ion exchange-adsorption-coprecipitation of Pb2+. During the continuous contact time, nanoadsorbents structure was deteriorated, slowing the elution rate, but this did not influence in the effectiveness of metallic removal.
\n\t\t\tThe intra-particular Pb2+ diffusion into adsorbent, has occurred in 2 stages:
\n\t\t\twhile the metal ions, rapidly diffuse between particles of the nanoadsorbents, at the beginning of adsorption and
when the intra-particular diffusion is reduced and then stabilized.
The kinetics of adsorption depends of: metal ions concentration in solution, adsorbent dose, pH and contact time, and does not depend on the particle size of adsorbent.
\n\t\t\tIn the sintering is transformed species generating titanate Pb metal. (PbTiO3). One possible application can be as electronic sensors and piezoelectric devices.
\n\t\t\tPolytitanates potassium consisted of particles agglomerate like-flake shape with a nominal diameter of 50-300 nm and a thickness of 20-60 nm, which in turn have a lamellar structure, the space between the plates, which forms nanopores. When heating the particles to a temperature of potassium polytitanates 500 ° C, they crystallize to nanowiskers.
\n\t\t\tThe chosen methodology has included in the study of the effect of synthesis parameters on the physico-chemical and adsorption properties of potassium polytitanates and optimization of the properties of nanomaterials for use as a highly effective adsorbent for bivalents cations.
\n\t\t\tStudies identified the optimal synthesis regimes of potassium polytitanates (weight ratio of raw materials TiO2: KOH: KNO3 = 1:1:32; at 500 °C of temperature, time 1 h) and its further processing (sequentially washed with water and 0.1 N aqueous solution of hydrochloric acid, drying, milling. In potassium polytitanates, always get ultrafine materials (the average size of agglomerates of nanoparticles of hydrated potassium polytitanates of 1.4 microns.
\n\t\t\tThe structure and composition of Potassium Polytitanates studied by Xray diffraction analysis (Fig. 10), infrared spectroscopy and scanning electron microscopy (Fig. 18). IRS show slight differences in the adsorbed samples, data no revels differences among the obtained samples. According XRD data base ICDD 2004 shows that the composition of phase is variable and its depends of the reagents relationship, the selected technology and the synthesis temperature conditions. Its means that in the stage of synthesis is very important to have a PPN with low content of impurities as K2Ti4O9 K2Ti6O13, the product structure will depends largely of the synthesis temperature and their process of purification(washes).
\n\t\tAuthor thanks the financial support of Consejo Nacional de Ciencia y Tecnología (CONACYT, México), through the project SEP-CONACYT-2006 No 54883 and the scholarship given to M.A. Aguilar-González (No. 201784).
\n\t\tIn order to enhance road safety as well as to satisfy increasingly stringent government regulations in western countries, automobile makers are confronted with incorporating a range of diverse technologies for driver assistance to their new model. These technologies help drivers to avoid accidents, both at high speeds and for backward movement for parking. This system can be placed into the category of advanced driver-assistance systems (ADAS). Besides increasing safety, ADAS [1] applications are concerned with to enhancing comfort, convenience, and energy efficiency. It is emerging as new driving technology supported with Adaptive Cruise Control, Automatic Emergency Brake, blind spot monitoring, lane change assistance, and forward collision warnings etc. It is an important platform to integrate these multiple applications by using data from radar, lidar, and ultra sound sensors etc. The vehicle engine related to hardware such as actuators, engine, brake, steering get the commands from the above sensors to enable the ADAS to take desired actions with respect to alerting the driver for detection of hazardous object or location or stopping the vehicle if necessary. For example, the recognition of black spot warning, lane change assistance and forward collision warning are extremely becoming useful in the ADAS.
During the gradual emergence of Connected and Automated vehicle (CAV), driver behavior modeling (DBM) coupled with simulation system modeling appears to be an instrumental in predicting driving maneuvers, driver intent, vehicle and driver state, and environmental factors, to improve transportation safety and the driving experience as a whole. These models can play an effective role by incorporating its desired safety-proof output into Advanced Driver Assistance System (ADAS. To cite an example, it could be said with confidence that the information generated from all types of sensors in an ADAS driven vehicle with accurate lane changing prediction models could prevent road accidents by alerting the driver ahead of time of potential danger. It is increasingly felt that DBM developed by incorporating personal driving incentives and preferences, with contextual factors such as weather and lighting, is still required to be refined, calibrated and validated to make it robust so that it turns into more better personalized and generic models. In regard to the modeling of personalized navigation and travel systems, earlier studies in this area have mainly considered ideal knowledge and information of the road network and environment, which does not seem to be very realistic. More researches are required to be conducted to address this real life challenges to make ADAS more acceptable to society.
There are an increasing evidences from the various literatures that a single vehicle making inferences based on sensed measurement of the driver, the vehicle, and its environment is mostly focused for DBM where there is any hardly attempt made to develop DBM in the traffic environment in the presence of vehicle to vehicle (V2V), and vehicle to infrastructure (V2I) scenario- communications system. It would be interesting to develop DBM with respect to connected and automated vehicle (CAV) to leverage information from multiple vehicles so that more global behavioral models can be developed.. This would be useful to apply the output of the CAV modeling in the design of ADAS driven vehicle to create a safety proof driving-scenario for diverse applications.
There are a number of sensors which are increasingly being used. These are namely cameras, medium and long-range radar, ultrasonic, and LIDAR.. Data generated from these sensors go through fusion process to authenticate the data so as to enable the computer software perform the necessary tasks to activate the driver assistance system to take correct decisions. These decisions are related to parking assistance, automatic emergency breaking, pedestrian detection, surrounding view, and even drowsiness of the driver. The functional components such as various types of sensors collecting data from immediate surrounding environment are related to ADAS architecture that helps to perform necessary tasks as shown in the Figure 1. The forward collision-avoidance ECU module is located in the windshield, supported with the blind spot ultrasonic sensors and related ADAS processor may be located in the side mirrors or other location areas.
Functional components and various types of sensors. Source: http://www.hitachi-automotive.us/Products/oem/DCS/ADAS/index.htm
The architecture [2, 3, 4] of the electronic control units (ECUs) is responsible for executing advanced driver assistance systems (ADAS) in vehicles which is changing for its response during the process of driving. Automotive system architect integrates multiple applications into ADAS ECUs that serve multiple functions of ITS architecture as shown in the Figure 2. Figures 3 and 4 show Architecture for other functions related to Forward Collision and Parking Assistance respectively.
Architecture of ADAS, source: Ref [3].
Architecture of forward collision avoidance & blind spot avoidance. Source: Ian Riches, strategy analytics.
Architecture of ADAS -Parking Avoidance & Blind. Source: http://www.techdesignforums.com/practice/technique/managing-the-evolving-architecture-of-integrated-adas-controllers/.
Hardware architecture of ADAS and autonomous driving, includes automotive Ethernet, TSN, Ethernet switch and gateway, and domain controller while Software architecture of ADAS and autonomous driving, including AUTOSAR Classic and Adaptive, ROS 2.0 and QNX.
Advanced driver assistance systems (ADAS) need a number of integrated sensors to accurately determine situational assessment and action implementation. In ADAS technologies [5, 6, 7] sensors such as video, radar, LIDAR, ultrasonic and infrared (IR) sensors are being increasingly utilized. Sensor fusion with advanced algorithms and computing power, connectivity and data transmission, contextual awareness and processing, and virtual sensors is extremely important for success of ADAS.
There are six levels of vehicle automation as shown in Figure 5 defined by the Society of Automotive Engineers (SAE) [8] with a span from Level 0, which has no automation, to Level 5, which involve fully autonomous vehicles. As automation expands, driver assistance and ADAS plays an increasingly important role.
Various levels of ADAS, source: https://www.sae.org/news/press-room/2018/12/sae-international-releases-updated-visual-chart-for-its-%E2%80%9Clevels-of-driving- automation%E2%80%9D-standard-for-self-driving-vehicles.
Level 0: Driver only: the driving is controlled by the human driver using with driving aids independently including steering, throttle, brakes, etc.
Level 1: Assisted driving: driver needs assistance during vehicle operation with respect to Cruise Control, ACC.
Level 2: Partial automation: the system is monitored during driving. At least one system, such as cruise control and lane centering, is fully automated.
Level 3: Conditional automation: the system is monitored by the operator and can intervene when it is necessary. Safety-critical functions, under certain circumstances, are shifted to the vehicle.
Level 4: High automation: there is no monitoring required by the driver. Vehicles are designed to operate safety-critical functions and monitor road conditions for an entire trip. However, the functions do not cover all every driving scenario and are limited to the operational design of the vehicle.
Level 5: Full automation: it ensures operator-free driving without any intervention.
As of today, no car manufacturer has achieved level 3 or higher in production, although several have produced demonstration vehicles. The legislature of some countries is working on a possible admission of “Level 3” vehicles, which is expected to be available in 2020/21. Driver assistance systems enabling autonomous driving from level 3 onwards will require at least three types of sensor systems: camera, radar, and LIDAR systems. As can be seen in Figure 5, several of each type of sensor operates at various locations on the vehicle. The development of the LIDAR system is still posing the bigger and most dynamic challenge in technical and commercial terms.
There are a number of sub systems associated in performing various tasks of ADAS. A vehicle’s movement detected by the ADAS can be seen in the main system inside the vehicle when the driver is present. This system interacts with the environment. There are different functions of the system as can be clearly distinguished in Figure 6. The following distinctive features of fusion are mentioned as under:
Information has to be gathered;
Information needs to be evaluated;
A safety measure need to be taken;
Fusion of data at ECU received from various types of sensors housed in ADAS, Source: Ref No: [3].
These functions are synonymous to as Sense (1), Think(2), and Act(3). Only the Sense sensors are reviewed and only the systems in which the driver is inside the loop. Figure 6 shows the process of ‘multi sensor processing’, starting with the sensor data acquisition. Next, the sensors processing, divided into several tasks, as ‘Calibration, ‘Feature Extraction’, ‘Object Detection’, etc., begins to analyze the sensors data and, in the end, serves the application with a more or less detailed model of the environment [4].
Fusion of data received from complementary and independent sources place the data into a single description. Data association and data assimilation are two important components to be addressed for data fusion as a part of the process that matches sensor data with the description of the environment that requires synchronization of the sensor data and the associated object state (e.g., position and velocity).
It is extremely important to know which sensors are required for autonomous driving from Levels 1 to 5. As already mentioned, there are three main groups of sensor systems camera-, radar-, and LIDAR-based systems. Although, for parking, ultrasonic sensors are available today and are widespread, they are of minor importance for autonomous driving. Camera and radar systems are in the Level 1 and 2 vehicles today and are prerequisite for all further levels of automation.
This advanced Camera (digital HDR CMOS cameras) with large dynamic range is well suited to poor light conditions and primary differences are due to its brightness.
A large number of digital interfaces are available with camera for automobiles along with digital signal processor and internal memory capacity. The camera generates processed video images for evaluation using software algorithm. It also help images transformed in to signals to merge with other sensor signals such as other as radar and lidar etc. Due to the inherent intelligence of the camera, all the signals are processed in the fusion mode to enable the ADAS to take correct decision. The camera used as sensor [9] is required to go through the quality management (ISO/TS/16949 in the automobile industry and are suited for adaptability which is quick and flexible. Current digital camera system is continuously receiving raw data that is then processed and forwarded to the display unit for image display. This procedure is shown in Figure 7.
Video data transfer to head unit of camera through Ethernet, source: https://www.fierceelectronics.com/components/three-sensor-types-drive-autonomous-vehicles
Besides this, the infrared (IR) camera consists of several components. It is important to distinguish 2 different versions of the IR camera:
The infrared (IR) camera consists of several components. It is important to distinguish 2 different versions of the IR camera:
Near Infra Red(NIR);
Far Infra-Red(FIR);
In both systems a camera plays an important role in identifying radiation of objects. It may be mentioned that NIR technology offer an extra illumination by IR-headlights while the FIR systems is not characterized with special headlights. The primary difference between the two is picking up the extra-radiated objects by the NIR systems while FIR only accepts only the regular radiation of objects.
Table 1 presents transmission of data rate from sensors [10].Figure 8 shows the functioning of Lidar.
Sensor | Data rate required to transmit raw data |
---|---|
Camera | 1Gb/sec to 24Gb/sec |
Radar | 5Gb/sec to 120Gb/sec |
Lidar | 2 Mb/sec to 10Gb/sec |
Data rate required for transmission of data.
Principle of the functioning of LIDAR. Source: https://www.fierceelectronics.com/components/three-sensor-types-drive-autonomous-vehicles.
For purpose of measuring distance and creation of three-dimensional images of the environment, LIDAR system [11] is fitted and integrated ever more frequently into vehicles and mobile machines. A pulsed laser beam assesses the signal‘s transit time from the object back to the detector as shown in Figure 8. A highly sensitive technique using Avalanche Photodiodes along with internal amplification measure the light pulses in the nanosecond range across wider bandwidths. Lidar optical system requires the high spatial resolutions. Therefore sensor has the capability to develop APD arrays comprising with multiple sensor elements. The APD arrays from sensor addresses the effect of temperature due to its high voltage. Their highly accurate amplification offers excellent APD signal quality. The modules can be adapted to as per the specific application. Development boards with digital output signal and Low Voltage Differentiating Signal (LVDS) is interfaced. With the help of Lidar and Radar System, the object of the road can easily be identified. But in addition to these, there is a necessity for a camera for classification and detection of an object in a correct way. With the development of point density cloud from the reflections from radar and lidar, the distance and closing speed of the object can easily be measured. It may be mentioned that due to lower resolutions from these sensors as compared to camera, the detection of the objects are not easily made. To optimize the detection at varying ranges with lower resolution, a number of units are installed from a medium-range unit for emergency brake assist to long-range radar for adaptive cruise control although LIDAR & radar, functions in a similar way at longer ranges with lower point-density.
RADAR is meant to define its full form “Radio Detection And Ranging.”. By this sensor, the object is detected with the identification of localization of objects using radio waves with a frequency range from 24 to 77 GHz. It is noteworthy to mention that the higher measurement of accuracy with respect to distance and speed along with precise angular resolution depends on high intensity of radio wave frequency. Generally the frequency over 24 GHz is used for the smaller antenna size with the lower interference problem. The examples of various types of frequency band [12] used for different sensors are as under:
Short-range radio applications include:
Blind Spot Detection (Blind Spot Monitoring)
The lane and the lane-change assistant
Rear end radar for collision warning or collision avoidance
Park Assist
Brake Assist
Emergency braking,
Automatic distance control
Radar configurations can be broadly categorized into three categories namely short-range radar with a maximum distance of about 30 meters, medium range radar with about 60 meters and long- range radar with about 250 meters. It may be mentioned that the use of Short Range Radar is increasingly seen with the detection of blind spot, rear and forward mitigation, parking assist etc. On the other, there are a number of detection system namely forward collision warnings, cross traffic alert, stop & go etc. operated by Medium Range Radar. So far there is no specific distinction made between SRR and MRR by the industry. It is seen now a days that ultrasonic sensors and highly automated driving are gradually replaced by the SRR. We do not have as such specific definitions and distinctions between the SSR and MDR as formulated by the industries. As far as the placement of sensors in the vehicles, the forward looking sensor for long range detection is generally placed in the front of the vehicle.
For a ‘cocoon’ radar system, extra sensors are placed on each side mid-body. Ideally, these radar sensors work on the 79-GHz frequency band with a 4-GHZ bandwidth. It may be mentioned that, global frequency specifications so far allow only 1 GHZ bandwidth at 77 GHz. Now a days a radar MMIC (monolithic microwave integrated circuit) comprises of three transmission channels (TX) and four-receiver channel (RX) to be monolithically integrated. Whether it creates a sense to integrate base band processing in the monolithic microwave integrated circuit (MMIC) or whether it is better to concentrate on a raw data radar sensor, it is a matter of debate.
The difference is that the output of the baseband processor provides so called pre-targets. In this case, data is pre-processed such as unverified information on speed, distance, signal strength, horizontal angle, and vertical angle for each detected object. The raw data radar sensor presents unfiltered raw data, to the ECU for processing. Figure 9 demonstrates the architecture of such a raw data radar sensor. The radar sensor used as partitioned simplifies the data fusion of the video and radar data, and LIDAR data since the same communication interface can be used A prerequisite for the development of MWICs (Millimeter Wave Integrated Circuit) is dedicated high-frequency (HF) technologies to realize the frequencies (24 GHz or 77 GHz) and the corresponding output power. Table 2 presents summary table of the properties of a radar sensor in certain ADAS.
Radar architecture for processing of raw data. Source: (https://www.sensorsmag.com/components/three-sensor-types-drive-autonomous-vehicles
Property | Present in systems | Comment |
---|---|---|
Frequency: 76–77 GHz Range: 1 to 200 m Search Area: 12° Speed measurement precision: < 0.2 km/h |
| Long range, Pulse Doppler, Active sensor, |
Angular Precision: < 0.3° | ||
Frequency: 24.125 Ghz Distance range: 10 m Velocity range: 60 m/s Field of view:
Dimensions: 90 x 40 x 15 mm |
| Short range |
Frequency: 24 GHz |
| Forward looking, long Range |
Frequency: 24 GHz Frequency: 5.8 GHz |
| Side looking, short range Side looking, short Range |
F = 76.5 GHz Resolution = 100 cm Bandwidth = 100–500 MHz Range = 7–150 m | Long range, Pulse Doppler, Active sensor, | |
Radar |
| Active sensor, |
Frequency: 24 GHz UWD (Ultra Wide Band) Resolution = 3 cm Bandwidth = 5 GHz Range: 0.3–30 m |
| Short range, Active sensor, |
Transmission Power = −41.3 dBm/ MHz | ||
Infrared Radar |
| Near InfraRed (NIR), Far Infra Red (FIR), |
Summary table of the properties of a radar sensor in certain ADAS, source: Ref. [12].
Multiple transmitters and receivers are generally are in-built to determine range, angle, and velocity of objects in their field of view. As various sensors are concerned, it consists of ultra-short-range- radar (USRR), short-range-radar (SRR), medium-range-radar (MRR), and long-range-radar (LRR) sensors or systems.
The primary philosophy of working with the ultrasonic technology is to transmit short bursts of sound waves that return back after hitting objects for which the measurement are to be taken in terms of time required to bounce back with speed of approximately 346 m/s which is the speed of the sound. For detection of short distance range obstacle, Ultrasonic sensors are increasing being used in the automobile industries which is generally characterized by with a sound pressure kHz and detection covering range of one to three meters supported by horizontal beam width of maximum100°and60°vertical. The ultrasonic and radar technology complements each other to determine the higher degree of accuracy,
Ultrasonic sensing is generally meant for short-distance applications at low speeds, such as park assist, self-parking, and blind-spot detection. For maximum coverage, an automotive ultrasonic system typically performs with multiple sensors placed in the wing mirror and front and rear bumpers. Ultrasonic sensing is a more cost-effective approach than cameras, which have poor close- distance detection. Though infrared sensing is cheaper than ultrasonic, it’s less accurate and cannot function properly in direct sunlight. Objects closer to the transmitter generate a stronger echo than an object with more distantly located. In order to avoid false positives, the system neglects all inputs that are less than that of the noise. The important parameters related to the specifications of ultrasonic sensor are the frequency, sensitivity, and directivity. The system is further characterized by the tunable transformer that is required to excite the transducer.
A tuning capacitor built into the system is concerned with matching the resonant frequency between the transducer and transformer. The speed of sound in air is affected by air temperature, humidity, and wind. If multiple sensors are applied, they must be placed in sufficient space so that the sensor signals do not interfere. Figure 10 shows the features of ultrasonic system (Table 3).
This ultrasonic system features a PGA450 analog front end (source: Author/PGA450-Q1 PDF).
Property | Present in systems | Comment |
---|---|---|
F = 40 kHz Distance range: 0 to 3 |
| In adverse weather conditions |
meter Distance accuracy: | ||
10 cm Angular range: | ||
120° Angular accuracy: | ||
+/− 5° | ||
Response time: 60 ms |
Summary table of the properties of an ultrasonic sensor in certain ADAS, source:
It is realized that in order to make the ADAS commercially viable, three aspects on designing, testing and validating are of great importance and challenge to researchers/ scientists and manufacturer. The processing and sharing of information requiring a huge computation effort, within its fusion system in real time situation is a complex and difficult task in view of the computational load and the time-constraints placed on the system.
The inertial navigation systems identify, measures position, orientation, and velocity measurements. The sensor of RT-Ranges [13] is responsible for creating a real-time network, which is capable of tracking multiple targets, calculating distance, time to collision, and other relative measurements. Targets include primarily road vehicles, vulnerable road users (VRUs) such as cyclists or pedestrians. Euro NCAP (The European New Car Assessment Programme,) targets traffic assets and more. Euro NCAP is a European car safety performance assessment programme. Data is available in real-time on a software dashboard captured to verify test outcomes. Vehicle-to-vehicle measurements can be made over a 1 km range. Many similar systems in different parts of the world are increasingly seen, all with a slightly different name.
Various system of ADAS associated with various sensors is presented in the Table 4. A number of sensors developed during the process of development of ADAS are briefly discussed below.
During night vision, one is more concerned with the proper visibility where the camera plays an important role. Therefore the camera for this purpose is designed with the use of near or far infrared to improve the perception of the driver in dark conditions. The improved sight vision created by the above near or far- infrared camera is displayed in the monitors of the vehicle. Human Machine interface though poses an issue for correctly showing the road-side picture for timely intervention plays an important role to the driver to enhance the safety to the driver so that the driver is not distracted. Table 5presents available sensors with their properties for night vision.
Various sensors related to their applications. Source: Automotive ADAS Systems, ST Developers Conference, Sep, 12, 2019, Santa Clara Convention Centre, Mission City Ballroom, Santa Clara, CA.
Sensor | Property | Comment | |
---|---|---|---|
Infrared camera | l = 800 nm | Near InfraRed (NIR) | |
(CMOS) | = 7–14 μm | Far InfraRed (FIR) | |
Both systems are mono-camera, | mono-camera, |
Available sensor and properties in night vision systems, source: [12].
Lane departure warning mechanism works on the principles of certain thresholds with respect to distance, time to lane crossing. It is based on the decision made out from the data fusion analysis supported with computer software algorithm to warn the driver that he or she is about commit mistake in departing traffic lane. For example, sensors such as acoustic, optic means continuously generate and analyze the data along with the video image processing data created by the vehicle cameras results in the detection of warning to the vehicle. In order to make the warning system effective, the carriage way would have to be laid with Good visible lane markings system. These influence the complexity of the system on the roadside. This system aims to prevent involuntary lane departure, which constitutes a relevant cause of road accidents. With real-time measurement and positional accuracy which is generally at less than 2 cm, the system captures the data that the sensor performs the task of lane departure action as shown in Figure 11. This warns the Lane Departure Warning system if the vehicle suddenly decides to change the lane without proper indication. The camera used for the lane detection system is low cost generally mounted on the windscreen near the rear view. The position of this location of the camera helps continuously capture the image of solid lane line marking of the road towards the front side of driving. it also works along with the front (adaptive cruise control and, ii) forward collision warning), side (lane departure warning), and iii) rear side (blind spot detection).
How it works: Windshield camera tracks lane markings. Source:https://www.extremetech.com/extreme/165320-what-is-lane-departure-warning-and-how- does-it-work.
There are multiple collision warning systems (12) mentioned on the Table 6.
Sensor | Property | Comment | |
---|---|---|---|
Infrared camera | l = 800 nm | Near InfraRed (NIR) | |
(CMOS) | = 7–14 μm | Far InfraRed (FIR) | |
Both systems are mono-camera, | mono-camera, |
Available sensor and properties in night vision systems.
The finest example of the application of near field collision warning is the detection of blind spot, which takes very close proximity of the presence of vehicle. Lidar, radar or vision based sensors are generally used. It may also be acoustical, haptical or optical also. In many cases, the frequency of this kind sensor is found to be 24 GHz. To test and develop blind-spot detection systems, it is necessary to accurately measure the position and trajectory of targets relative to the vehicle under test (VUT). The system may require the following protocol accuracy:
Relative accuracy 2 cm
Heading accuracy 0.1°
Free post-processing software
Ability to track multiple objects in real-time
Perfectly suited to open-road testing
To evaluate blind-spot detection systems, an RT inertial navigation system and RT- Range S [7] are installed in the vehicle under test. This powerful system is designed to work in conjunction with GNSS-aided inertial navigation products. Automobiles can be equipped with GNSS receivers, which display moving maps and information about location, speed, direction, and nearby streets and points of interest. The manner in which sensor works is based the measurement of real-time distance between the sensor and the identified object. It may include any type of vehicle, blind corner of a junction, pedestrian and bicycle etc.
For real-time testing, range measurements from the RT-Range S Hunter can be used as output via Ethernet or CAN (Controller Area Network) which is a communication hardware that allows communication between parts of a system without the intermediary of a central computer. Or data can be logged internally and analyzed back at base where it can be post-processed and exported in CSV file format ((“Comma Separated Values”) which is often used to exchange data between differently similar applications).
Warning system developed by EATON-VORAD in the USA for trucks and busses [13] as the first step towards the Advanced Driver Assistance Systems (ADAS) can be considered as Forward Collision Warning System. Forward Collision warning with a frequency of 24 Ghz is first seen in the USA market in 1995. It used to detect the object with signal emitted through either optical or acoustical method to the driver when the object happens to be close to the path of collision.
This system addresses a side looking short-range radar that operates at 24 GHz. This sensor identifies and detects side obstacles that are signaled with a proper display. As a further option, the system can also be linked to engine control with a view to controlling speed. This function is called “Smart Cruise”. More recently, the side obstacle detection System has been introduced also on Volvo cars based on camera sensor and image processing.
This system communicates with the driver about speed limits and informed the recommended speed at curves. There are a number of relevant information generated from digital maps, image processing or communication system between the interactions of vehicles and road infrastructure. That is the reason that updated real time data is important to the driver generated from the above which helps in recognizing the speed limit of the road where the vehicle is traveling. It may be mentioned that the details of the road features such exact location of traffic marking, position of street light etc. are available in the form of digital map in ADAS that helps in identifying and recognizing the speed limit.
This system was introduced firstly inside Japan, and then in Europe for the car market. ACC systems are based on a front looking sensor designed with laser radar, (LIDAR) or microwave radar with a maximum detection range of around 100 m. The microwave radar sensor operates in the 76–77 GHz bands that have been reserved for application of automotive obstacle detection. Based on front vehicle information, mainly distance and speed, the ACC system regulates own vehicle speed by acting on engine control and braking system. The ACC is an extension of the standard Cruise.
Control system, with the extra capability to adapt the speed of the vehicle to the speed of the preceding one. This function was firstly introduced in Japan on 1995 based on LIDAR technology.
Europe experienced the emergence of lidar and microwave technology in the following years which led the introduction of these technologies in the Mercedes car during the year 1999. It is noteworthy to mention that the automatic cruise control system (ACC) was seen fitted with truck manufactured by Mercedes automobile industry. Presently around twenty automobile manufacturers are producing this type car and truck.
It is based on a high performance GNSS/INS for dynamic applications developed on the convenience of a conventional cruise control system by automatically changing speed to match the vehicular flow in front. It’s important to determine precisely when and how the system intervenes, how well it acquires and then it tracks the targets and how it performs in a number of different real-world scenarios [6]. Measurements such as target bearing, distance, relative velocity and time-to-collision are key to the evaluation of these systems. Sensors with RT and RT range for ACC offers the following characteristics:
Relative accuracy 2 cm
Heading accuracy 0.1°
Real-time birds eye view showing measurements
Ability to track multiple objects in real-time
Perfectly suited to open-road testing
In order to get accurate vehicle-to-vehicle measurements, an RT inertial navigation system and RT-Range S [7] are installed in the vehicle under test (VUT) and any target vehicles. An RT inertial navigation takes into account a number of parameters for operation. These include position with respect to latitude, longitude, altitude distance and its coordinate position. Besides the position of these, velocity, acceleration, orientation, angular rates and acceleration and slip angle are also taken into account. RT-XLAN Wi-Fi radios then send real-time information from target vehicles back to the VUT where the RT-Range S calculates, logs and outputs real- time measurements about the relative position of the target vehicles. The measurements being the output include the position of both the Hunter and target vehicles, orientation and velocity. The current status of the ACC hardware can also be logged with the data via a CAN bus interface, which is a robust vehicle bus standard designed to allow microcontrollers and devices to communicate with each other in applications without a host computer. It can also be or later synchronized with the measurements via a GPS time stamp. Moreover, from some manufacturers, ACC is given in combination with lane warning system.
It will have frequency allocation for 24 GHz sensors. The properties of various sensors associated with the functioning this ACC are presented in Table 7 as under:
Sensor | Property |
---|---|
LIDAR | Wavelength l: 850 nm |
Radar | Frequency: 76–77 GHz Range: 1 to 200 m Resolution: 100 cm Search Area: 12° Speed measurement precision: < 0.2 km/h Angular Precision: < 0.3° Frequency: 24.125 Ghz Distance range: 10 m Velocity range: 60 m/s Field of view:
|
Available sensors with their properties in ACC (source: Ref No. [12]).
Adaptive cruise control (ACC) permits a driver to travel with the flow in traffic. In this situation, a radar sensor monitors the situation in front of the vehicle. As the road is observed to be clear, ACC operates with the desired speed. If the radar sensor finds a slower vehicle ahead of it, ACC automatically maintains and adjusts the speed a preset distance. In the Stop & Go version, the system results in slowing the car down in a traffic jam, or even comes to a halt it completely. If the car has an automatic transmission, Stop & Go also restarts the engine once traffic gets moving again after a brief pause.
In this system the driver continues to receive support from this sensor with respect longitudinal control for the formation of queue. During the stop & go of the vehicle facing the front side, longitudinal control is carried out by the system for detecting the near side objects.
The function of a lane keeping assistant system includes the lane detection and the feedback to the driver if he is leaving a defined trajectory within the lane. Lane departure warning systems merely alert the driver when the car is leaving its lane, while lane-keeping assist actually works to keep the car from moving out of the lane. An active steering wheel can help the driver with a force feedback to keep on this trajectory. The lane is detected by a video image processing system. Additionally to the lane departure warning aspects especially regarding the infrastructure, the HMI becomes more important.
The driver gets all assistance through his touch with steering and other devices for taking decisions for the vehicular movement linking with the controller that also helps to lane keeping assistance to adhere to lane driving.
The Protocol accuracy requirements [12] for this are as under:
Axes to be in ISO 8855:1991 orientation
Longitudinal speed to 0.1 km/h
Update rate at least100 Hz
Time is required as a synchronization DGPS (Differential GPS)
Position to 0.03 m
Yaw velocity to 0.1°/s
Acceleration to 0.1 m/s2
Vehicle edge to lane edge measurements
For the LSS (Lane support System) LKA tests, the key measurements are the distance between the outer-edge bulge of the front tires and the inside edge of the lane markings when any intervention is triggered..
If a hazard occurs far away in front of the vehicle, so that the driver cannot see it, this system will warn him. By the means of communication, it is possible, to transfer this information over long distances. A usable frequency has to be allocated. Local Hazard Warning [14, 15] is a system that uses short-range communication between cars, and between a car and its surroundings, to give drivers early warning of safety hazards. For example, a car equipped with Local Hazard Warning might issue a warning to other vehicles if it had broken down in the middle of a carriageway or had been involved in a collision. Similarly, emergency vehicles equipped with such a system might send a signal to nearby vehicles to warn them of their presence, or temporary roadwork barriers could issue for such warnings. As well as transmitting such warnings, cars equipped with Local Hazard Warning can also receive these signals and use them to alert the driver to the danger [16].
The automatic parking is a function that helps the driver entering into a parking slot in a parallel maneuver by automatically acting on the steering wheel and engine control. The sensors measure [12] the object with following accuracy:
Relative accuracy 2 cm
Heading accuracy 0.1°
Real-time birds eye view showing measurements
Ability to track multiple objects in real-time
The vehicle is fitted with a GNSS-aided inertial navigation system (GNSS/INS). In most cases (because of the low speeds involved), a dual-antenna model is fitted to maintain the best headway accuracy at all times. The properties of various sensors [12] are presented in Table 8.
Sensor | Property | Comment |
---|---|---|
Laser | Beam deflection: horizontal Range: 0–80 m Range: 0–35 m @ Rr = 5% Resolution: 20 mm Accuracy: ± 50 mm Frequency: 10–40 Hz Cycle time: 25–100 ms Vertical opening angle: ~ 3,5° Horizontalangularfield:+ − 120° Lateral resolution: 0,25° - 1° | |
Radar | Frequency: 24.125 Ghz | Short range |
Distance range: 10 m Velocity range: 60 m/s Field of view:
| ||
Dimensions: 90 x 40 x 15 mm |
Various sensors available for automatic parking and their properties.
Pre Crash Safety Systems identify an imminent crash and deploy safety devices such as seat belt pretensions.
Pre Crash Safety Systems identify an imminent crash and deploy safety devices such as seat belt pretensions. In order to reduce the damages of an accident, this system has been designed that is capable of applying brake automatically after identification of imminent occurrence of collision. As discussed earlier, various sensors such as Lidar, Camera etc. play an important role in identifying the hindrance for an imminent collision. This feature is primarily designed to address the problem of safety, which integrates the sensitivity of seatbelt. If one happens to wear the seat belt during the occurrence of road accident, the chances of being injured is quite less. Most of the seat belts now available in the car are very sensitive, as the vehicle will not move if car users or someone does not wear seat belt.
The driver will be warned if a potential collision is detected with e.g. another car or obstacle. This warning can be, for example acoustic, visual. The functional limits of these systems have to be clearly pointed out.
In city environments, collision between vehicles and pedestrians or cyclists often result in serious injuries as there is a little time for either party to react. Protocol accuracy requirements [12] for this kind of collision are the following.
Update rate at least 100 Hz
Lateral path error
Time is required as a synchronization DGPS
Position to 0.03 m
VUT (Vehicle under test) Speed to 0.1 km/h
Yaw velocity to 0.1°/s
Acceleration to 0.1 m/s2
Polygon perimeter shapes
In an intersection situation especially in cities, a driver has to fulfill several tasks in parallel. In order to assist the driver in such situations, it is necessary to support certain tasks like approaching a stop sign/traffic light or right of way of crossing traffic. The complexity of the possible intersection scenarios leads to the high risk probabilities of causing accidents. As any intersections are designed to address a number of turning movements of automobile traffic coupled with the non-motorized and pedestrian traffic, the detection and recognition are not as simple as on a straight section of a road. Due to these complexities, the safety of the road intersection would have to be taken into all possible scenarios to make hazard free zone.
The driving of vehicle is controlled by a computeralgorithm in each situation. It is presently viewed that this fully AV cannot be reached at the present situation in the actual road network immediately. There is an expectation that true Level − 5 of AV to attain full autonomy is about ten-plus years away. It is also expected that geo-fenced applications of autonomous vehicles (AVs) would reach in the next three to five years. The progress on the hardware as well as software has actually been very significant. The cost of LIDARs [light detection and ranging sensors], for example, has dropped by a factor of ten over the last five years. Similarly, the amount of computational capacity that the GPUs [graphic processing unit] has also increased significantly. ISO 39003 is now working on Guidance on Safety Ethical Considerations for Autonomous Vehicles in order to ensure that this vehicle is absolute safe and smooth from operational point.
Although there are many demonstration seen on advanced vehicles up to Level 3 or more, so far automobile manufacturers have not been able to commercialize to the high level automated vehicle which requires detailed and comprehensive legislation in the countries.. International Standard Organization is presently working on the standards for this automated vehicle. A number of fundamentals aspects of ADAS that are a part of the complex process of the system have been discussed. ADAS with level-2 are becoming increasingly available in the market in western countries with implication of increase in its cost. It may be mentioned that the manufacturers of ADAS driven vehicles have not been able to make any significant impact on the sale of this type of vehicle. It may be mentioned that there is not significant negative values experienced so far. The R&D into ADAS is increasingly being accelerated to enhance safety.
Though the ADAS driven vehicle is yet to find its place in the market in spite of apprehension raised by many sections of people on the safety related issues, it would be important to appreciate when it turns into Cooperative Road Vehicle Highways System reducing the probability of accident to almost zero level.
The European Community (16) is leading by investing significantly in R&D into ADAS in Europe. Many countries such as France, the Netherlands and the UK are increasingly taking an active role by participating in research activities and promoting successful implementation. The most important issues of ADAS have two key factors: i) a high level of usability and ii) a low financial risk to the manufacturer. It seems for the time being, ADAS user benefits are not clear yet and financial risks still exists.
As far as legal aspects are concerned, the relation between ADAS and product liability is very important. The product liability for ADA systems will address specific additional requirements, in particular taking into account the interaction of the drivers/users with the product in view of the current legal framework. The Code of Practice is being developed by the European car manufacturers by addressing these requirements. Presently the ADASE II technology roadmap for ADAS confirmed the expectation that ADAS will have potential benefits on safety, throughput and comfort, ranging from positive to very positive. Related technology development, R&D is still required to improve the performance of ADAS to cover wider ranges of traffic scenarios and to bring down costs. Political motivations and intervention may be needed to advise to the different decision makers to accelerate and facilitate (or regulate) the market the introduction of ADAS.
Therefore the government should come forward along with the concerned stake holders like road operators, car manufactures, users etc. by jointly setting up proper conducive environment in order to promote the advances of ADAS. The ADAS driven vehicles should be commercially viable in the market by addressing concerned legal issues in the society.
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\\n\\n5.1 IntechOpen has a right to terminate this Publication Agreement for quality, program, technical or other reasons with immediate effect, including without limitation (i) if the Corresponding Author or any Co-Author commits a material breach of this Publication Agreement; (ii) if the Corresponding Author or any Co-Author (being an individual) is the subject of a bankruptcy petition, application or order; or (iii) if the Corresponding Author or any Co-Author (being a company) commences negotiations with all or any class of its creditors with a view to rescheduling any of its debts, or makes a proposal for or enters into any compromise or arrangement with any of its creditors.
\\n\\nIn case of termination, IntechOpen will notify the Corresponding Author, in writing, of the decision.
\\n\\n6. INTECHOPEN’S DUTIES AND RIGHTS
\\n\\n6.1 Unless prevented from doing so by events outside its reasonable control, IntechOpen, in its discretion, agrees to publish the Chapter attributing it to the Corresponding Author and any Co-Author.
\\n\\n6.2 IntechOpen has the right to use the Corresponding Author’s and any Co-Author’s names and likeness in connection with scientific dissemination, retrieval, archiving, web hosting and promotion and marketing of the Chapter and has the right to contact the Corresponding Author and any Co-Author until the Chapter is publicly available on any platform owned and/or operated by IntechOpen.
\\n\\n6.3 IntechOpen is granted the authority to enforce the rights from this Publication Agreement, on behalf of the Corresponding Author and any Co-Author, against third parties (for example in cases of plagiarism or copyright infringements). In respect of any such infringement or suspected infringement of the copyright in the Chapter, IntechOpen shall have absolute discretion in addressing any such infringement which is likely to affect IntechOpen's rights under this Publication Agreement, including issuing and conducting proceedings against the suspected infringer.
\\n\\n7. MISCELLANEOUS
\\n\\n7.1 Further Assurance: The Corresponding Author shall and will ensure that any relevant third party (including any Co-Author) shall, execute and deliver whatever further documents or deeds and perform such acts as IntechOpen reasonably requires from time to time for the purpose of giving IntechOpen the full benefit of the provisions of this Publication Agreement.
\\n\\n7.2 Third Party Rights: A person who is not a party to this Publication Agreement may not enforce any of its provisions under the Contracts (Rights of Third Parties) Act 1999.
\\n\\n7.3 Entire Agreement: This Publication Agreement constitutes the entire agreement between the parties in relation to its subject matter. It replaces and extinguishes all prior agreements, draft agreements, arrangements, collateral warranties, collateral contracts, statements, assurances, representations and undertakings of any nature made by or on behalf of the parties, whether oral or written, in relation to that subject matter. Each party acknowledges that in entering into this Publication Agreement it has not relied upon any oral or written statements, collateral or other warranties, assurances, representations or undertakings which were made by or on behalf of the other party in relation to the subject matter of this Publication Agreement at any time before its signature (together "Pre-Contractual Statements"), other than those which are set out in this Publication Agreement. Each party hereby waives all rights and remedies which might otherwise be available to it in relation to such Pre-Contractual Statements. Nothing in this clause shall exclude or restrict the liability of either party arising out of its pre-contract fraudulent misrepresentation or fraudulent concealment.
\\n\\n7.4 Waiver: No failure or delay by a party to exercise any right or remedy provided under this Publication Agreement or by law shall constitute a waiver of that or any other right or remedy, nor shall it preclude or restrict the further exercise of that or any other right or remedy. No single or partial exercise of such right or remedy shall preclude or restrict the further exercise of that or any other right or remedy.
\\n\\n7.5 Variation: No variation of this Publication Agreement shall be effective unless it is in writing and signed by the parties (or their duly authorized representatives).
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\\n\\nAny modification to or deletion of a provision or part-provision under this clause shall not affect the validity and enforceability of the rest of this Publication Agreement.
\\n\\n7.7 No partnership: Nothing in this Publication Agreement is intended to, or shall be deemed to, establish or create any partnership or joint venture or the relationship of principal and agent or employer and employee between IntechOpen and the Corresponding Author or any Co-Author, nor authorize any party to make or enter into any commitments for or on behalf of any other party.
\\n\\n7.8 Governing law: This Publication Agreement and any dispute or claim (including non-contractual disputes or claims) arising out of or in connection with it or its subject matter or formation shall be governed by and construed in accordance with the law of England and Wales. The parties submit to the exclusive jurisdiction of the English courts to settle any dispute or claim arising out of or in connection with this Publication Agreement (including any non-contractual disputes or claims).
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The Corresponding Author (acting on behalf of all Authors) and INTECHOPEN LIMITED, incorporated and registered in England and Wales with company number 11086078 and a registered office at 5 Princes Gate Court, London, United Kingdom, SW7 2QJ conclude the following Agreement regarding the publication of a Book Chapter:
\n\n1. DEFINITIONS
\n\nCorresponding Author: The Author of the Chapter who serves as a Signatory to this Agreement. The Corresponding Author acts on behalf of any other Co-Author.
\n\nCo-Author: All other Authors of the Chapter besides the Corresponding Author.
\n\nIntechOpen: IntechOpen Ltd., the Publisher of the Book.
\n\nBook: The publication as a collection of chapters compiled by IntechOpen including the Chapter. Chapter: The original literary work created by Corresponding Author and any Co-Author that is the subject of this Agreement.
\n\n2. CORRESPONDING AUTHOR'S GRANT OF RIGHTS
\n\n2.1 Subject to the following Article, the Corresponding Author grants and shall ensure that each Co-Author grants, to IntechOpen, during the full term of copyright and any extensions or renewals of that term the following:
\n\nThe aforementioned licenses shall survive the expiry or termination of this Agreement for any reason.
\n\n2.2 The Corresponding Author (on their own behalf and on behalf of any Co-Author) reserves the following rights to the Chapter but agrees not to exercise them in such a way as to adversely affect IntechOpen's ability to utilize the full benefit of this Publication Agreement: (i) reprographic rights worldwide, other than those which subsist in the typographical arrangement of the Chapter as published by IntechOpen; and (ii) public lending rights arising under the Public Lending Right Act 1979, as amended from time to time, and any similar rights arising in any part of the world.
\n\nThe Corresponding Author confirms that they (and any Co-Author) are and will remain a member of any applicable licensing and collecting society and any successor to that body responsible for administering royalties for the reprographic reproduction of copyright works.
\n\nSubject to the license granted above, copyright in the Chapter and all versions of it created during IntechOpen's editing process (including the published version) is retained by the Corresponding Author and any Co-Author.
\n\nSubject to the license granted above, the Corresponding Author and any Co-Author retains patent, trademark and other intellectual property rights to the Chapter.
\n\n2.3 All rights granted to IntechOpen in this Article are assignable, sublicensable or otherwise transferrable to third parties without the Corresponding Author's or any Co-Author’s specific approval.
\n\n2.4 The Corresponding Author (on their own behalf and on behalf of each Co-Author) will not assert any rights under the Copyright, Designs and Patents Act 1988 to object to derogatory treatment of the Chapter as a consequence of IntechOpen's changes to the Chapter arising from translation of it, corrections and edits for house style, removal of problematic material and other reasonable edits.
\n\n3. CORRESPONDING AUTHOR'S DUTIES
\n\n3.1 When distributing or re-publishing the Chapter, the Corresponding Author agrees to credit the Book in which the Chapter has been published as the source of first publication, as well as IntechOpen. The Corresponding Author warrants that each Co-Author will also credit the Book in which the Chapter has been published as the source of first publication, as well as IntechOpen, when they are distributing or re-publishing the Chapter.
\n\n3.2 When submitting the Chapter, the Corresponding Author agrees to:
\n\nThe Corresponding Author will be held responsible for the payment of the Open Access Publishing Fees.
\n\nAll payments shall be due 30 days from the date of the issued invoice. The Corresponding Author or the payer on the Corresponding Author's and Co-Authors' behalf will bear all banking and similar charges incurred.
\n\n3.3 The Corresponding Author shall obtain in writing all consents necessary for the reproduction of any material in which a third-party right exists, including quotations, photographs and illustrations, in all editions of the Chapter worldwide for the full term of the above licenses, and shall provide to IntechOpen upon request the original copies of such consents for inspection (at IntechOpen's option) or photocopies of such consents.
\n\nThe Corresponding Author shall obtain written informed consent for publication from people who might recognize themselves or be identified by others (e.g. from case reports or photographs).
\n\n3.4 The Corresponding Author and any Co-Author shall respect confidentiality rights during and after the termination of this Agreement. The information contained in all correspondence and documents as part of the publishing activity between IntechOpen and the Corresponding Author and any Co-Author are confidential and are intended only for the recipient. The contents may not be disclosed publicly and are not intended for unauthorized use or distribution. Any use, disclosure, copying, or distribution is prohibited and may be unlawful.
\n\n4. CORRESPONDING AUTHOR'S WARRANTY
\n\n4.1 The Corresponding Author represents and warrants that the Chapter does not and will not breach any applicable law or the rights of any third party and, specifically, that the Chapter contains no matter that is defamatory or that infringes any literary or proprietary rights, intellectual property rights, or any rights of privacy. The Corresponding Author warrants and represents that: (i) the Chapter is the original work of themselves and any Co-Author and is not copied wholly or substantially from any other work or material or any other source; (ii) the Chapter has not been formally published in any other peer-reviewed journal or in a book or edited collection, and is not under consideration for any such publication; (iii) they themselves and any Co-Author are qualifying persons under section 154 of the Copyright, Designs and Patents Act 1988; (iv) they themselves and any Co-Author have not assigned and will not during the term of this Publication Agreement purport to assign any of the rights granted to IntechOpen under this Publication Agreement; and (v) the rights granted by this Publication Agreement are free from any security interest, option, mortgage, charge or lien.
\n\nThe Corresponding Author also warrants and represents that: (i) they have the full power to enter into this Publication Agreement on their own behalf and on behalf of each Co-Author; and (ii) they have the necessary rights and/or title in and to the Chapter to grant IntechOpen, on behalf of themselves and any Co-Author, the rights and licenses expressed to be granted in this Publication Agreement. If the Chapter was prepared jointly by the Corresponding Author and any Co-Author, the Corresponding Author warrants and represents that: (i) each Co-Author agrees to the submission, license and publication of the Chapter on the terms of this Publication Agreement; and (ii) they have the authority to enter into this Publication Agreement on behalf of and bind each Co-Author. The Corresponding Author shall: (i) ensure each Co-Author complies with all relevant provisions of this Publication Agreement, including those relating to confidentiality, performance and standards, as if a party to this Publication Agreement; and (ii) remain primarily liable for all acts and/or omissions of each such Co-Author.
\n\nThe Corresponding Author agrees to indemnify and hold IntechOpen harmless against all liabilities, costs, expenses, damages and losses and all reasonable legal costs and expenses suffered or incurred by IntechOpen arising out of or in connection with any breach of the aforementioned representations and warranties. This indemnity shall not cover IntechOpen to the extent that a claim under it results from IntechOpen's negligence or willful misconduct.
\n\n4.2 Nothing in this Publication Agreement shall have the effect of excluding or limiting any liability for death or personal injury caused by negligence or any other liability that cannot be excluded or limited by applicable law.
\n\n5. TERMINATION
\n\n5.1 IntechOpen has a right to terminate this Publication Agreement for quality, program, technical or other reasons with immediate effect, including without limitation (i) if the Corresponding Author or any Co-Author commits a material breach of this Publication Agreement; (ii) if the Corresponding Author or any Co-Author (being an individual) is the subject of a bankruptcy petition, application or order; or (iii) if the Corresponding Author or any Co-Author (being a company) commences negotiations with all or any class of its creditors with a view to rescheduling any of its debts, or makes a proposal for or enters into any compromise or arrangement with any of its creditors.
\n\nIn case of termination, IntechOpen will notify the Corresponding Author, in writing, of the decision.
\n\n6. INTECHOPEN’S DUTIES AND RIGHTS
\n\n6.1 Unless prevented from doing so by events outside its reasonable control, IntechOpen, in its discretion, agrees to publish the Chapter attributing it to the Corresponding Author and any Co-Author.
\n\n6.2 IntechOpen has the right to use the Corresponding Author’s and any Co-Author’s names and likeness in connection with scientific dissemination, retrieval, archiving, web hosting and promotion and marketing of the Chapter and has the right to contact the Corresponding Author and any Co-Author until the Chapter is publicly available on any platform owned and/or operated by IntechOpen.
\n\n6.3 IntechOpen is granted the authority to enforce the rights from this Publication Agreement, on behalf of the Corresponding Author and any Co-Author, against third parties (for example in cases of plagiarism or copyright infringements). In respect of any such infringement or suspected infringement of the copyright in the Chapter, IntechOpen shall have absolute discretion in addressing any such infringement which is likely to affect IntechOpen's rights under this Publication Agreement, including issuing and conducting proceedings against the suspected infringer.
\n\n7. MISCELLANEOUS
\n\n7.1 Further Assurance: The Corresponding Author shall and will ensure that any relevant third party (including any Co-Author) shall, execute and deliver whatever further documents or deeds and perform such acts as IntechOpen reasonably requires from time to time for the purpose of giving IntechOpen the full benefit of the provisions of this Publication Agreement.
\n\n7.2 Third Party Rights: A person who is not a party to this Publication Agreement may not enforce any of its provisions under the Contracts (Rights of Third Parties) Act 1999.
\n\n7.3 Entire Agreement: This Publication Agreement constitutes the entire agreement between the parties in relation to its subject matter. It replaces and extinguishes all prior agreements, draft agreements, arrangements, collateral warranties, collateral contracts, statements, assurances, representations and undertakings of any nature made by or on behalf of the parties, whether oral or written, in relation to that subject matter. Each party acknowledges that in entering into this Publication Agreement it has not relied upon any oral or written statements, collateral or other warranties, assurances, representations or undertakings which were made by or on behalf of the other party in relation to the subject matter of this Publication Agreement at any time before its signature (together "Pre-Contractual Statements"), other than those which are set out in this Publication Agreement. Each party hereby waives all rights and remedies which might otherwise be available to it in relation to such Pre-Contractual Statements. Nothing in this clause shall exclude or restrict the liability of either party arising out of its pre-contract fraudulent misrepresentation or fraudulent concealment.
\n\n7.4 Waiver: No failure or delay by a party to exercise any right or remedy provided under this Publication Agreement or by law shall constitute a waiver of that or any other right or remedy, nor shall it preclude or restrict the further exercise of that or any other right or remedy. No single or partial exercise of such right or remedy shall preclude or restrict the further exercise of that or any other right or remedy.
\n\n7.5 Variation: No variation of this Publication Agreement shall be effective unless it is in writing and signed by the parties (or their duly authorized representatives).
\n\n7.6 Severance: If any provision or part-provision of this Publication Agreement is or becomes invalid, illegal or unenforceable, it shall be deemed modified to the minimum extent necessary to make it valid, legal and enforceable. If such modification is not possible, the relevant provision or part-provision shall be deemed deleted.
\n\nAny modification to or deletion of a provision or part-provision under this clause shall not affect the validity and enforceability of the rest of this Publication Agreement.
\n\n7.7 No partnership: Nothing in this Publication Agreement is intended to, or shall be deemed to, establish or create any partnership or joint venture or the relationship of principal and agent or employer and employee between IntechOpen and the Corresponding Author or any Co-Author, nor authorize any party to make or enter into any commitments for or on behalf of any other party.
\n\n7.8 Governing law: This Publication Agreement and any dispute or claim (including non-contractual disputes or claims) arising out of or in connection with it or its subject matter or formation shall be governed by and construed in accordance with the law of England and Wales. The parties submit to the exclusive jurisdiction of the English courts to settle any dispute or claim arising out of or in connection with this Publication Agreement (including any non-contractual disputes or claims).
\n\nLast updated: 2020-11-27
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