Advanced periorbital basal cell carcinomas may necessitate orbital exenteration and consequent vision loss, which significantly reduces patients’ life quality. Orbital reconstruction is a demanding surgical procedure due to the complex orbital anatomy and vital structures located in the orbit. In this report, we presented an 83-year-old patient with advanced basal cell carcinoma that had expanded into the orbit. An orbitotomy was performed to remove the tumor completely while preserving the eye function. Orbital reconstruction was performed by a standard surgical method using a titanium mesh modeled according to a natural phantom skull. This maintained the eye function and achieved satisfactory facial esthetics. Basal cell carcinoma (BCC) is the most common malignant skin tumor and accounts for approximately 90% skin cancers , 2. The In this case report, we present a case where we performed lateral orbital wall reconstruction with a titanium mesh previously adapted and modeled using a natural phantom skull and avoided orbital exenteration. Reconstruction of orbital wall defects after tumor resection due to complex anatomy is also a challenge even for experienced maxillofacial surgeons.An 83-year-old patient was admitted in 2018 to our Department of Maxillofacial and Oral Surgery, University Hospital Center Osijek, because of a tumor in the frontozygomatic region on the right side. In 2010, the patient was treated in the surgical department of another institution. According to the pathohistological findings, it was a skin basal cell carcinoma. Due to the irregularity of the preparation, it was not possible to assess the status of the edges of the preparation, so the patient was referred to our department. He neglected that recommendation for next eight years and did not perform the examination in our department. In October 2018, the patient was examined by an ophthalmologist, who performed lower eyelid ectropion correction twice and referred the patient to our department now due to suspected recurrence of the tumor frontotemporally in the right side.Examination revealed a serious impaired general condition of the patient . In the local status, we found a tumorous change of 3 cm × 3 cm in the frontozygomatic region fixed to the right on the base, right eye lower eyelid ectropion, while the regional lymph nodes were not palpable.During the preoperative preparation, a native and postcontrast orbital CT was performed and a lobulated solid expansive formation of the zygomatic region on the right (2.5 cm × 2.3 cm ×  2.1 cm) was determined, which infiltrated and eroded the frontozygomatic extension on the right side 1.8 cm × 1.7 cm long .In the infratemporal space on the right, a solid formation size 1.5 cm × 1.0 cm was differentiated without right eye bulbus infiltration. Tumor had two lobes, one lobe that affected the skin and was fixed to the eroded bone and the other part that was in the infratemporal cavity and penetrated into the orbit through the lateral wall of the orbit, so the tumor was folded over the lateral edge of the orbit.Based on the CT findings, we decided to operate the tumor with resection of the lateral orbital wall while preserving the eyeball. With written informed consent of the patient, under general anesthesia, an incision was made in the skin and subcutaneous tissue around the tumor, with adequate surgical margins . During Bone defect of the lateral orbital wall was reconstructed using a titanium mesh previously adapted and modeled using a natural phantom skull .Once the mesh was fixed in a satisfactory position, a portion of the temporalis muscle and temporal fascia was pulled over it. The entire defect was then covered with a Thiersch skin graft taken from the right thigh. The skin graft was fixed with sutures to the surrounding skin with compression with a cotton ball with Vaseline gauze. The site of Thiersch transplant on the right thigh was covered with a Kaltostat, which was removed after three weeks. Compression of the skin graft and sutures were removed after one week. It should be emphasized that the patient did not agree to local skin flaps, which was good because a thin skin graft allowed more adequate control of the occurrence of possible tumor recurrence. The patient was controlled regularly for two years by a maxillofacial surgeon and an ophthalmologist. A control CT scan was performed without recurrence of the tumor, eye motility was in order, as was the function of eyelids closing . Mild asMalignant primary or secondary tumors that penetrate the orbit from the surrounding skin, maxillary sinus, or neurocranium require surgical treatment. The incidence of malignant tumors of the skin of the periorbital region is constantly increasing, and accordingly, an increased number of indications for orbital exenteration are expected. Kesting et al. in their study reported that 99.3% of patients underwent orbital exenteration due to a malignant tumor, and in 23.8% of cases, the cause was the progression of skin cancer into the orbit . Usually


The novel method of the thermally-induced polarization changes driven power losses (TIPCL) analysis in the complex laser systems has been developed. The measurement has been tested on the amplifier chain of the 100 J / 10 Hz laser system ‘Bivoj’ operated at HiLASE Centre. By the usage of the measured non-uniform Mueller matrix of the amplifier chain, the optimization of the ideal input and output polarization state has been calculated numerically. The results of the optimization have been applied to the laser system, thus reducing the TIPCL from originally observed more than 33% to 7.9% for CW beam and to 9% for pulsed laser beam, respectively. To the best of our knowledge, this result represents the most efficient TIPCL suppression method for complex laser systems so far. The method also allows the definition of the ideal fully polarized non-uniform pre-compensation of input beam consequently suffering from zero TIPCL. Losses in such cases can be as high as 50%. Another deleterious effect of the thermally induced polarization change is the degradation of the beam profile when the beam passes through any diattenuator, typically linear polarizer. It has been shown recently, that the losses can be substantially mitigated by the optimization of input linear or circular polarization state5, by the proper design of the laser amplifiers and their cooling7, by the mutual compensation of thermally induced birefringence realized between multiple passes through the same heated optical elements10, by proper orientation of the input linear polarization in square-shaped amplifiers11, or by the suitable crystal orientation of the amplifiers12. Even so, the methods based on the results referenced above are usually not sufficient to keep the power losses at acceptable values allowing efficient laser system operation. This is due to the presence of many polarization-affecting optical components in the system, due to the differences in optical paths between the single passes through the amplifier head e.g. in geometrical multi-passes and other effects.Laser beams in high energy high average power lasers suffer from non-uniform polarization change during the amplification. This polarization change originates from stress induced birefringence caused by heat load occurring dominantly in the amplifier. Such polarization changes reduce energy available to polarization sensitive experiments such as harmonic conversionFor further reduction of the TIPCL one would need to optimize the output polarization state as well as the input. Moreover, the general elliptical polarization states should be considered for complex amplifier chains. Such optimization process is, however, at least four-parameter optimization , which is experimentally demanding in the terms of time required for finding the optimal set of these parameters. Our proposal is the employment of spatially resolved Mueller matrix polarimetry applied to the whole laser system which allows the transfer of the time consuming four parameter optimization process from large number of experimental measurements into the numerical calculation. Such process can be then very fast and efficient in finding the optimal input polarization state and the output polarization state change leading to the maximal suppression of these non-uniform polarization state changes.2. It is the first kilowatt-class high energy laser14 that recently increased its output power to almost 1.5 kW15.Both the measurement and the optimization process has been applied and tested experimentally on the 100 J/10 Hz laser chain ‘Bivoj’ which is located at HiLASE centre. The laser is operated at 1029.8 nm wavelength with 10 ns pulse duration. The output beam is square-shaped 75 × 75 mm16. Both TIPCL definitions are schematically shown in the Fig. The development of the optimization process has given rise to the novel method of TIPCL reduction. It is based on the generalized definition of TIPCL which is, in terms of power loss, equivalent to the measurement of the power loss of the system placed between two arbitrarily oriented elliptical polarizers. On the contrary, the traditional conception defines the TIPCL  as the throughput of crossed linear polarizersJ is described by non-uniform Jones vector E, Considering that the polarization state after the distorting system mentclass2pt{minim17. However, to the best of our knowledge, it has never been used for the analysis of the polarization properties of the whole laser system amplifier chain in order to study the thermo-optical effects. The measurement method is evaluating the response of the system to several different input polarization states and subsequently quantifies the polarization change obtained in the system by the reconstruction of the complete polarization transmission operator, e.g. Mueller matrix. The optical path through amplifier chain contains approximately 120 optical elements and it is difficult to evaluate their polarization properties separately. Nevertheless, the proposed measurement contains all the phenomena taking part in the formation of the resulting polarization state of the laser beam.The Mueller matrix polarimetry is a method of measurement of a complete set of polarization properties of transmissive or reflective samplesThe experimental setup used in this particular case for the Mueller matrix polarimetry of the laser system is shown in the Fig. 1 and the desired polarization state is then generated by the set of waveplates H1 and Q1. The polarized beam is subsequently propagated through the sample, where it accumulates the information about the polarization properties of the sample. The part of this information is then transformed into the laser intensity in the polarization state analyzer PSA, consisting of two waveplates Q2 and H2 and the vertically oriented high-contrast linear polarizer P2. It should be noted that the sample was in this particular case the whole laser system.An arbitrary polarization state can be generated by the polarization state generator PSG. The probe laser beam is polarized to the vertical linear polarization by the high-contrast polarizer PAll four quartz true zero-order waveplates used in the polarimeter were placed in the motorized mounts which allow precise computer-controlled reorientation.U stands for the unitary Jones matrix representing the combination of waveplates Q2 and H218. The intensity recorded on the CCD (AVT Manta 125B) is in this case given by P2, thus having the same spectrum, but the eigenstates are transformed by the U matrix from the linear ones to general elliptical ones. Therefore, the intensity I is equivalent to Ib derived for the two elliptical polarizers case, even if every scheme produces different output polarization.The experimental scheme shown in the Fig. M is a general spatially non-uniform Mueller matrix characterizing the amplifier chain polarization properties, A and G are the column vectors derived from the Mueller matrices of the PSA and PSG, respectively. Vector A is the first column of the Mueller matrix A describing the PSA P, H, and Q denotes the Mueller matrices of the polarizer, half-wave plate, and quarter-wave plate, respectively. The vector G characterizes the PSG in similar way including the input polarization state characterized by its Stokes vector SinThe intensity profile which can be observed by the camera is given by:G vector given by (3b), while the other couple A given by (2b). Let us organize these values into the G and A 4 × 4 matrix . The advantage of the choice of the Such choice of waveplate angles leads, through the Eqs.  and 3b)3b), to tmentclass2pt{minimTherefore the intensity and the Mueller matrices of the sample are given byThe precision of the phase retardance angle measurement has been estimated from the benchmark measurements for well-known samples and empty polarimeter and established to be better than 1 deg.I has been measured for the 100 J/10 Hz laser chain. The CW alignment beam produced by the Fabri-Parrot laser diode at 1030 nm with polarization maintaining fiber output was expanded and transformed to the flat-top square beam with the dimension of 75 × 75 mm2. This CW alignment beam was subject to the PSG before its expansion and injection into the 100 J amplifier. Then it was propagated throughout all four passes of the 100 J amplifier. At the output of 100 J amplifier, the CW beam was reduced by a de-magnification telescope and analyzed by the PSA.The intensity matrix The Mueller matrix was evaluated by the above-described method at the pump rate of 75% of the usual pump power to better account for the lack of energy extraction from the amplifier as the optical-to-optical efficiency of the amplifier is around 25%. The pumping conditions were 3 kW of average power in 1 ms long optical pulses at repetition rate of 10 Hz.The Mueller matrix of the system can be reconstructed from the intensity matrix measurement using (7). The resulting matrix is shown in the Fig. M11 term is equal to unity over the whole beam cross-section. The normalization has been used in order to suppress the influence of the beam intensity profile. The basic analysis based on the Lu–Chipman polar decomposition 19 of the Mueller matrix provides two clear conclusions from the acquired matrix: (1) it can seen directly from the first row of the matrix M12–M14 , that no measurable diattenuation is present in the studied part of the laser system; (2) similar conclusion can be drawn from the first column of the matrix M21–M41, which contains the elements proportional to both diattenuation and depolarization. Taking advantage from the knowledge of the diattenuation one can read out also the depolarization present in the amplifier chain. Since the first column signal is under the detection threshold, the laser system shows no depolarization, i.e. the decrease of the degree of polarization towards unpolarized state.The Mueller matrix has been normalized so that The information about the birefringence is encoded in the 3 × 3 submatrix located in the right lower corner of the Mueller matrix shown in the Fig. It should be noted that according to the original work of Lu and Chipman on polar decomposition, six equivalent realizations of one Mueller matrix exist and are given by different ordering of the depolarizing matrix, diattenuator and retarder matrix, respectively. In our case, however, the depolarizer and diattenuator matrix are very close to the unit matrices and therefore the retarder matrix decomposition is unique within the measurement precision.M shown in the Fig. Sout for any input polarization state of light Sin as followsM is the non-uniform Mueller matrix obtained from the measurement, Sin stands for the Stokes vector of the input polarization state, also spatially non-uniform in this case, and Sout represents the Stokes vector of the laser beam at the end of the amplifier chain. Sout is desired to be uniformly linearly polarized over the cross-section of the beam. The Eq.  is needed after the laser operation pause e.g. during the night break. However, another polarimetric analysis was not needed so far and the compensation quality is maintained exclusively by these fine tunings. Our experience with the compensation stability is based on the second harmonic generation experiments which are very sensitive to the polarization changes within the beam profile.The thermal phenomena do not change significantly during the laser operation, because they are related to the overall stability of the laser, for which the system is designed. From our own experience, there is no need for any tuning of the compensation during the laser run. The TIPCL changes during the laser run do not exceed 1%, however, taking into account the measurement precision of the in-situ power monitoring, this fluctuation lies within the accuracy of the measurement. Some fine tuning of the output waveplates Q


Many different OPC-AAS-hardened composites benefit from the addition of CuFe2O4 spinel, which increases the composites' resistance to fire and enhances their physicomechanical properties at roughly average curing ages. Synthesized CuFe2O4 spinel was shown to have desirable characteristics by TGA/DTG and XRD. By using these methods, we were able to identify a broad variety of hydration yields, including C–S–Hs, C–A–S–Hs, C–F–S–Hs, and Cu–S–Hs, that enhance the physicomechanical properties and thermal resistivity of OPC-AAS-hardened composites as a whole. The composite material comprising 90% OPC, 10% AAS waste, and 2% CuFe2O4 has several positive economic and environmental outcomes.The major objective of this study was to examine the viability of using 5, 10, or 15 mass% of Activated Alum Sludge waste (AAS) instead of Ordinary Portland Cement (OPC) as a pozzolanic ingredient in concrete. This fundamental inquiry framed the investigation and OPC-AAS-hardened composites were studied to see whether they may benefit from inexpensive nanocomposites in terms of improved physical properties, mechanical strength, and resistance to heat and flame. The investigation set out to see how inexpensive nanocomposite might be put to use and the nanoparticles of CuFe It is essential to dispose of solid wastes, particularly alum sludge (AS), as quickly as is practically practicable to reduce the number of potential threats that may be posed to the environment4. However, processed alum sludge, which is sometimes referred to as TAS, contains significant quantities of silica dioxide and aluminum oxide, which are the primary components of cement5.As a result of the fact that it is regarded as a hazardous waste, alum sludge (AS), which is a by-product of water treatment plants, is unable to be disposed of in a landfill in a typical manner. Instead, the material must be transported to a specialized facility that is built for the express purpose of dealing with hazardous waste6. This is because AS can interact with calcium hydroxide, which is the cause of this phenomenon. Because of the high pozzolanic activity it possesses, calcined water treatment sludge  has recently been the focus of a few research studies7. These studies have investigated the possibility of incorporating calcined WTS as an additional cementitious material in cement-based products and evaluated how doing so would impact the mechanical properties of the cement10.As a result of this, Treated Alum Sludge TAS is a desirable alternative to the more traditional cement. Because of their ability to react with calcium hydroxide that is formed during the hydration of Ordinary Portland Cement (OPC), researchers in the field of concrete are becoming more interested in the practicability of recycling (AS) as a pozzolanic material with Portland cement11. A lot of attention is being paid to the process of incorporating nanoparticles into cement materials. The goal of this process is to inspire new types of construction materials that have high efficiency and endurance under harsh environmental conditions17. These materials can be used in a variety of applications18.The results of the research indicated that the incorporation of drinking water sludge ash (DWSA) into Portland cement resulted in the development of hydrates that included aluminum. Ettringite and calcium aluminate hydrates (C–A–H) are two examples of hydrates that fall into this category since both hydrates may be found in Portland cement. This assertion is supported by the existence of a robust connection between the two variables in question. In recent years, nanotechnology has seen widespread application across virtually all areas of human endeavor to produce fresh uses. The industry of building and construction is particularly good at illustrating this trend's prevalence21. The electronic industry makes substantial use of ferrites, which are among the most important components of the sector's overall inventory. Recent research has been done to explore the effect that Fe3O4 spinel nanoparticles have on the durability of cementing materials. These investigations were carried out to find out more information22.This is something that can be done to produce new varieties of building materials that have these qualities. These components are potentially useful in a broad variety of settings due to their adaptability and versatility. Nano silica, nano iron, nano alumina, nanofibers, nano titania, and carbon nanotubes are some of the nanoparticles that are commonly used. Due to the characteristics that it possesses, ferrite is used in a broad variety of different applications as a magnetic semiconductor. In this context, “applications” refers to things like rotary transformers, noise filters, and multilayer ferrite chip components, among other things3O4 improves not only the thermal resistivity of the materials but also their resistivity against the hostile anions that are present in the matrix. This is the case even though the incorporation of spinel nano-Fe3O4 does not improve the thermal resistivity of the materials23. As was just mentioned, many studies have been carried out and published to investigate the effect that nanoparticles have on the various properties that cementitious matrices present. These studies report their findings to better understand the relationship between nanoparticles and cementitious matrices26.According to the findings, the incorporation of spinel nano-Fe2O4 spinel nanoparticles have or merely a very tiny number of studies looking into the effect that these nanoparticles have27. Because of this, the purpose of this research was to utilize low-cost synthesized CuFe2O4 spinel nanoparticles (CFs NPs) as an additive for boosting the mechanical properties and fire resistivity of hardened pastes made from Ordinary Portland Cement replaced by various ratios of activated alum sludge and to investigate the feasibility of the reuse of activated alum sludge for partially replacing Portland cement in construction materials, which helps in minimizing the environmental impact28.On the other side, there is either no research looking into the effect that CuFe29. Carbonation is the process by which carbon dioxide from the air mixes with calcium from the concrete. This process is referred to by the word “carbonation”30. This is evidence that the pH of the concrete is decreasing, which in turn leads the steel to begin corroding31. Chlorides can be transferred from concrete to steel in a process known as chloride-induced corrosion32. This process can result in a significant acceleration of the pace at which corrosion occurs33.When steel is embedded in concrete, the carbonation or chlorides in the concrete are often the agents that cause the steel to corrode over time34. Researchers have spent decades attempting to determine this chloride threshold level; nevertheless, the findings from their investigations have been highly variable35. This is likely the case given the large diversity of experimental conditions that were used, in addition to the fact that steel and concrete of varied quality were used in the experiments36. The amount of moisture that is already present in the concrete is an important factor that needs to be taken into consideration37. It is generally accepted, thanks to the high resistivity of dry concrete, that the rate of corrosion of steel in dry concrete is low38. This is because of the high resistivity of dry concrete. Extremely wet concrete has a corrosion rate that is comparable to that of moderately wet concrete due to the slow rate at which oxygen travels to the surface of the steel39.According to the findings of the study that has been carried out up to this point, it has been postulated that there is a certain chloride threshold level that must be achieved before the start of a high corrosion rate40. One method that might be used to attain this goal is the application of a considerable layer of concrete. Other methods include employing thick forms of concretes that have a low water/cement (w/c) ratio and/or adding additives such as micro silica that may diminish porosity, which in turn slows the chloride transit rate. Both methods are examples of alternative ways since these approaches are instances of different approaches that might be used41.When the moisture condition is intermediate, the rate of corrosion is high because the material has a relatively low resistivity and oxygen moves through it at a quick pace and this causes the rate of corrosion to be high. One strategy that might be used to cut down on the quantity of steel that corrodes in concrete is to make use of concrete that needs a significant amount of time to reach the chloride threshold level. This strategy has the potential to be applied42. The European standard EN 206-1 (Standardization 2000), it is suggested that for concrete that is going to be exposed to the splash/spray zone of seawater, the concrete should have a water-to-cement ratio of 0.45 and a cement content of 340 kg cement by m3 concrete. This is because the ratio of water to cement determines the strength of the concrete, and the cement content determines how much cement is present in the concrete43. Because of this, the w/c ratio is used to determine the proportion of water to cement that is present in the concrete.There are currently several distinct types of cement that can be purchased from retailers. The European standard EN 197-1, which was produced by the European council for standardization in the year 2000, is used to discern between different types of cement based on how their chemical composition varies2/g based on the calculations. The cement that was used by the participants of the study was supplied to them by the El-Sewedy cement company, which is in Al-Ain Al-Sokhna, Suez, Egypt. The processes that were used to purify drinking water ultimately led to the generation of a waste product referred to as water treatment plant sludge (WTPS). The water treatment plant samples (WTPS) that were acquired from the Beni-Suef facility and used in this investigation were obtained there. The WTPS was initially allowed to air-dry for 24 h in an oven set to 105 °C before being crushed. The alum sludge used in this study went through a procedure known as thermal activation, which was a part of the research process. To do this, dried WTPS was first heated in an electric furnace at a temperature of 500 °C for 2 h before being allowed to gradually drop down to room temperature44.The Blaine surface area of Ordinary Portland cement (OPC-type I) is determined to be 3495 cmThis investigation made use of a superplasticizer (SP) that was a modified polycarboxylate-based superplasticizer (PCsp) called Sika Viscocrete 5230 L. It has a specific gravity of 1.08 g/ml and was supplied by Sika Company in El-Obour City, Egypt. The evaluation investigated the effects of using an SP. SP superplasticizer is used not only as an agent for dispersing the nanoparticles but also to achieve the necessary level of workability in a variety of pastes. This is accomplished by utilizing the superplasticizer's dual-functioning ability to both disperse and work with the nanoparticles. The physical properties of the SP superplasticizer are broken out in further since its color is yellow–brown liquid, the percentage of solid residue is about 39.9%, the pH is ranged from 7.51 to 7.53 and finally, its specific gravity is about 1.08 g/ml.3COO)2·FeOH) were thoroughly combined in a ball mill for 6 h with one mole of copper (II) acetate monohydrate ((CH3COO)2·CuH2O)45. Following that, the mixture was dried at a temperature of 150 °C, and the sample was heated on a hot plate so that the acetates could be broken down more easily. To get copper ferrite nanocrystals, the sample was finally subjected to a 2-h-long heating process at a temperature of 100 °C. Using SEM, the CFs NPs that had been produced at a size of 200 nm were subjected to a mechanochemical degradation process, which resulted in the generation of CFs NPs that had an average particle size of less than 50 nm as seen in Fig. To determine whether the mixture was homogeneous, two moles of pure fine powder ferric acetate basic . Following the addition of the CFs NPs, the aqueous solution that contained the superplasticizer (which contained 0.30% of Super Plasticizer (SP) by mass of solid) was combined with the total quantity of mixing water, and the resulting suspensions were sonicated at a temperature of 25 °C for 1 h. After mixing the dry ingredients with 0.27 parts water to 1 part cement, the resultant paste was used in several different testsWhen the dry materials were mixed with the necessary amount of water  and the mixing technique was continued for approximately 4 min, a variety of pastes were produced. Examples of each paste were fabricated with galvanized steel that had been molded into the shape of a cube, and the dimensions of these cubes were 2.25 cm on each side. The freshly molded pastes were kept for 1 day in an environment with a relative humidity that was lower than 100% to achieve the necessary level of final setting. Following that, the specimens in the form of cubes were placed in room-temperature tap water for 3, 7, and 28 days, respectively. During the compressive strength test, an apparatus that was made in West Germany by Ton-industries was used; at each stage, the average value of all three cubes was recorded. According to the method that had been described in the past, the dehydration process of the broken specimens was stopped by using a stopping solvent that was created by combining methanol and acetone in a volume ratio that was equal to 1:1.2) and stored there until the time came for evaluating them. Total porosity (TP), bulk density (BD), and water absorption (WA) values were taken at regular intervals 46 to track the development of various essential physical characteristics. The temperatures at which the samples were stored varied from 75 to 80 °C. The values of total porosity, bulk density, and water absorption were tracked using these measurements after they were collected. According to the standards that have been set by the ASTM (C140 and C150). When a BD, TP, and WA are needed to compute, Eqs.  samples, respectively.After being made, the samples were held at temperatures of 80 °C for 3 h before being moved to a desiccator , thermal gravimetric analysis (TGA/DTG), and scanning electron microscopy (SEM)48:3, A = coupon area (inch2) and t = time (days).The rate of corrosion was determined based on the assumption that it was uniform throughout the whole surface of the coupons. Using the following formula, we were able to determine the corrosion rate in mils per year (mpy) based on the weight loss2), which is one of the primary minerals in AAS. Additionally, the diffractogram reveals the presence of the minerals albite and calcite to a lesser extent, as well as the mineral kaolinite, which demonstrates a pozzolanic property upon calcination. The presence of quartz during the mineralogical investigation carried out by AAS is thus evidence that the substance in question has an amorphous silica structure. Over a wide range of d-spacing , revealing the amorphous structure of aluminum in the AAS, there is no significant crystalline-aluminum-related XRD peak seen. After 7 and 28 days of hydration, the PC, PC–2CFs, PC–10 AAS, and PC–10 AAS–2 CFs  were subjected to thermogravimetric (TGA) and differential thermogravimetric (DTG) analyses, respectively.The XRD patterns previously carried out for activated alum sludge waste changed significantly after being subjected to calcination at a temperature of 500 °C (AAS). The findings of the XRD examination performed on the AAS's various components and minerals. The diffractogram reveals the presence of a significant quantity of the mineral quartz  as supplemental cementitious materials (SCM) with qualities equal to those of a typical active pozzolanic material. In addition, the standard suggests the fact that XRF analysis was performed on the AAS brings this point home very clearly.The XRF for the chemical oxide compositions of OPC, the mineralogical phase compositions of OPC, and the oxide composition of AAS are outlined in Fig. 2O4 spinel nanoparticles (CFs NPs) with a nanoparticle size of 200 nm were measured by using SEM and created following the previously described approach as follows: utilizing commercial types of reagents and beginning components to lower the economic cost.CuFe2O4 spinel nanoparticles are studied since their crystallite size is about 49 nm, the remnant magnetic flux density is about 4.002 Br (emu/g), as well as the saturated magnetic flux density, is about 39.11 Bs (emu/g), and finally, its high coercivity is about 85.56 Hc (Oe). (CFs NPs). The design and the percentage composition of the different mixtures are outlined in Table The material was ball milled for 40 h to achieve this result, and then it was subjected to 2 h of progressive heating in a muffle furnace at temperatures ranging from 300 to 500 °C. The CFs NPs that were obtained had a size of 50 nm and a value of 39.1 emu/g for their saturated magnetic flux density (Bs), and 4.002 emu/g for their remnant magnetic flux density (Br), and 85.56 Oe for their high coercivity. Additionally, the CFs NPs had a value of 39.1 emu/g for their remnant magnetic flux density (Br) (Hc). The investigation revealed that it preserves a purity level of at least 99.0% throughout its operation. The characteristics and the general properties of CuFe3 for the BD test; 35.12% for the TP test; and 12.99% for the WA test after 28 days of hydration)45.The results of this experiment are depicted in Fig. 3) of a variety of various mixtures. The values of the bulk density (BD) during the hydration process indicated a steady increase from day 1 to day 28 for each composite that was put through the test. These findings might be explained by the gradual stuffing of pores with accumulated hydration products over time, which allowed for the formation of a dense and thick framework. This occurred as a direct consequence of the buildup of hydration-related compounds. As can be seen in Fig. Figure The BD values of the composites that were made from Mixes B0 and C0 increased because of the excessive amount of hydration products that were formed because of the pozzolanic reaction between calcium hydroxide that was liberated from cement clinker hydration and AAS waste. This is a consequence of the pozzolanic reaction that took transpired, which may be explained because these products are piled in most of the open spaces (pores) along with the hardened cement matrix, and the overall porosity of the hardened composites is reduced, which is a topic that will be covered in the subsequent section. At the same time, the BD values of the hardened composites are increased. In the case of the composite built from Mix D0, the number of extra hydration products generated because of the pozzolanic interaction between the available CH and AAS is lower than it is in the case of the composite built from Mixes B0 and C0 for the parameters that were previously indicated and listed in the section on compressive strength.2·3H2O], CASH, CAH [calcium aluminate hydrate 3CaO·AlO3·6H2O] (CuSH)49.Because of this, the DB values of this mix were lower than those of (Mixes B0 and C0), but they were still comparable to those of the blank (Mix A) and the most significant discovery is that the hardened nanocomposites, which contain CFs NPs, have higher bulk density values than the materials that served as controls , and that the densification effect, which is characterized by high bulk density values, increases as the concentration of CFs NPs does as well mentioned in Fig. These extra chemicals congregate in the pores that are accessible, which results in the formation of a structure that is denser, more compact, and with a greater BD. The results of the analysis of the total porosity of the different composites that were tested are presented graphically in Fig. 50.In addition, the incorporation of CFs NPs resulted in a discernible reduction in the total porosity of all the created nanocomposites in comparison to their control, and Fig. It was investigated what would happen if hardened composites made from OPC, OPC-AAS, and OPC-AAS-CFs were heated to higher temperatures  for 28 days. Figure 2O vapors molecules generated from the evaporation of physically adsorbed water inside different pores along with tetrahydrofuran molecules. This reaction takes place between this interaction takes place between the molecules of H2O vapors that are produced as a result of the evaporation of water that has been physically adsorbed inside of various pores as well as the hardened cement.The compressive strength values of all composites increased significantly when compared to those of the following is an example of one explanation that might be correct for these results. The high upgrading of the CS values after being subjected to 300 °C could be attributed to the hydrothermal reaction  that takes place between the HThe perfect dispersion of CFs NPs within the composite matrix can be attributed to the obvious improvement in the thermal resistivity of a variety of nanocomposites  at 300 °C. This improvement can also be attributed to the composite matrix's efficiency in inducing the formation of large quantities of a variety of hydration products via its nucleation effect and activation of the internal autoclaving. Mix D3 exhibited the greatest degree of improvement in the thermal resistivity mixture. The nanocomposite known as D3 is the one that has demonstrated the largest increase in its thermal resistivity. These products get lodged in the easily accessible gaps (both macropores and micropores) along with the hardened composite, which supports the creation of the hardened matrix, which possesses a high level of resistance to the damaging effects of fire. The decrease in CS values that were observed for all composites after being exposed to 600 °C can be primarily attributed to the thermal degradation of nearly all fundamental products such as CSH composites after firing at 800 °C can be attributed to the complete thermal degradation for all binding centers, in addition to the induction of several cracks along with the composite matrix. This was observed after the composites had been subjected to the temperature.After exposing the composites to the temperature, this was the resultant observation was made. Figure The significant reduction in CS can be attributed to the formation of several cracks as well as the enlargement of the already generated crack (micro-cracks induced during the firing), both of which occurred because of the thermal shock that occurred during the rapid cooling process. Both events took place because of the rapid cooling that took place. In addition, the fact that the micro-cracks were caused by the firing process can be credited for the substantial drop in CS that was seen because of this action. When the temperature was raised from 300 to 600 °C, there was a discernible decline in the compressive strength of every composite that was evaluated, and this decline persisted until it reached 0 °C when the temperature was raised to 800 °C. Despite this, the degree to which loss of strength occurs in blended samples, whether they include CFs NPs, is larger than that which happens in neat Portland cement pastes, whether they contain CFs NPs.This is the case regardless of whether the blended samples contain CFs NPs. After a certain amount of time has passed, the percent relative compressive strength (RCS) (relative to their CS after 28 days) is displayed in Fig. 51. The comparative study between TGA and DrTGA is represented in Fig. The RCS percent values for these composites are as follows: 95.17, 95.29, 95.79, and 91.12 for Mixes A–D0, respectively, 96.75, 97.45, and 97.62 for Mixes A1–A3, respectively, 96.77, 97.51, and 97.63 for Mixes B1–B3); respectively. After being fired at 300 °C then rapidly cooled. As a result of these observations, the idea is that CFs have a good effect on strengthening the fire resistance of a range of OPC–AAS blended pastes, such as CSHI and CSHII, CAH, CASHs, AFM, AFT, CFSH, and CH, receive additional support. Finally, a noticeable drop in CS levels was observed across the board for all the samples that were analyzedTG–DTA analysis is being used to investigate the thermal resistivity of the FBS. TG–DTA curve for the FBS sample. The initial endothermic peak shown on the DTA curve has its minimum at 85 °C; this is related to a weight loss of about 1% and is caused by the release of hygroscopic water from the FBS. The broad exothermic peak at 315 °C is due to the oxidation of organic matter, and the corresponding weight loss at 425 °C is around 3.27%. We find that the amount of weight loss reflected by the TG curve agrees with the value of volatile matter stated above. It is possible to see a second endothermic peak at a temperature of around 685 °C, the principal cause of which is the oxidation of inorganic compounds and the transition between crystalline phases. Total weight loss at 990 °C is 9.12%, which is quite close to the loss on ignition figure.To undertake an examination of the treated specimens' ensuing mechanical qualities, the compressive strength (CS) values of the specimens were measured at various points throughout the hydration process. This was done so that the values could be compared with one another. In Table This continuous increase in the strength values can be generally attributed to the hydration of different phases that are present in Portland cement clinker and the formation of hydration products, primarily in the form of calcium silicate hydrates, calcium aluminate hydrates, alumino ferrite monosulfate hydrate, calcium aluminosilicate hydrate, and calcium ferrite trisulfate, also known as ettringite C6AŠ3H32. In addition, when contrasted with the control (pure OPC) paste, the compressive strength values recorded by the pastes generated by substituting OPC with 5 and 10% of AAS  recorded the highest values possible at each testing hydration time. These values were determined by comparing the values recorded by the control paste to the values recorded by the pastes generated by substituting OPC with 5 and 10% of AAS  causes the CS values to become comparable to, or even lower than, those of blank after 28 days. This occurs because the CS values are affected by the amount of AAS waste. This is since the waste from the AAS gets diluted (Mix A) and this decrease in the CS can be attributed to the dilution effect of PC as a result of its replacement with high percentages of AAS waste, which in turn reduces the amount of Ca(OH)2 liberated as a secondary hydration product from C3S and -C2S phases that required activating the AAS waste. In other words, the amount of Ca(OH)2 liberated as a secondary hydration product from C3S and –C2S phases53.The higher strength values that were reported for these composites are linked to the presence of excessive amounts of nearly amorphous and illcrystalline CSH as the main product. This was obtained through the pozzolanic interaction between AAS waste  and calcium hydroxide, which was obtained from the hydration of cement clinkerThe substitution of PC with significant percentages of AAS waste is to blame for the diluting impact since PC this discovery is compatible with the findings that have previously been published by many studies, and the results of the CS revealed that the optimal replacement ratio of OPC by AAS is 10%; this finding was also verified by the results of the CS. Table 2/g, a nano dimension of 50 nm, and, finally, the good distribution of it along with the cement matrix. These characteristics enable it to fill the nano- and micropores existing among different hydration products, which results in a dense and compact structure with higher strength values than those of their control samples (Mix A). Additionally, CFs nanoparticles perform the function of active nucleation centers, which has the effect of accelerating the hydration process of cement grains to produce new and increased quantities of a variety of hydrated phases54.This can be seen by comparing the values of the composite material to the values of their references. These findings can be attributed to the nanoparticle characteristics of CF spinel, which include a large specific surface area of 66 m3AH6), calcium aluminosilicate hydrate (Ca–(A)–SH), and calcium ferrosilicate hydrate  are some examples of the hydrated phases that may be found here CFs nanoparticles since it has been shown that the enforcement impact of CFs NPs increases as the quantity of addition of these NPs increases (from 0.5 to 2%), which is represented as an increase in the CS values for all investigated mixtures. This is a general observation that can be made because of the finding that the quantity of addition of these NPs increases. This improvement can be due to the filling influence that the CFs NPs had on the cement matrix, which led to a decrease in the porosity of the material. In other words, the CFs NPs filled the pores in the cement matrix. In addition to this, the high alkalinity of the composite matrix, which had a pH of more than 12, encouraged the partial ionization of CFs NPs into Cu2+ and ferric anion.Calcium aluminate hydrates 4·nH2O (CuSH), calcium ferrosilicate hydrate , (CFSH), which strongly findings will be supported by the XRD analysis that was performed on a variety of different composites that were put through their paces. In conclusion, the research showed that composite material known as Mix C3, which is comprised of 90% PC, 10% AAS, and 2% CFs NPs, could be regarded as the most advantageous option for use in applications relating to general construction55.These ions have an interaction with Ca(OH)2 and NOx) and other air pollutants emitted. There is no question that this composite (90 OPC–10AAS–2 CFs) provides a multitude of benefits, from the point of view of both the economy and the environment56.This was why it demonstrated the highest CS values when compared to all the other nanocomposites that were tested at nearly all ages. This was the case since it was tested on almost all ages. The substitution of 90% of the OPC with 10% of the AAS contributes to the reduction of costs associated with the disposal of waste (landfill tax), the provision of an alternative use for recycled water-treated plant sludge, without making any assumptions about either its cost or its quality, and the protection of the environment through the conservation of energy and the reduction of the number of harmful gases ; however, 15% mass substitution of AAS waste has minimal effect on hardened composites. When included in OPC pastes, CuFe2O4 spinel nanoparticles have the potential to increase the hardness of the paste, which in turn improves the physicomechanical characteristics and thermal resistance of the resulting nanocomposites. The study results support the usage of OPC, AAS waste, and CFs composite materials in common construction settings. Its CS values were the highest of all nanocomposites studied, and as a consequence, its hydration phases also had the highest average values. Most experts agree that the most cost-effective and ecologically friendly choice for construction that will be exposed to high temperatures is a nanocomposite consisting of 85% OPC, 15% AAS waste, and 2% CFs. TGA/DTG and XRD analyses showed that CuFe2O4 spinel NPs promoted the synthesis of CFSH, AFt, AFM, CASH, and CAHs at elevated concentrations. This was made feasible by the discovery of the NPs with these other chemicals. The NPs' co-location with the predicted locations of these elements provided conclusive evidence of their reality. SEM images demonstrated improved microstructure and mechanical features of the OPC-10 AAS composite after it was heated to 300 °C and CFs NPs were added. To do this, it will be necessary to create a variety of hydration products, including rod crystals, etherate fibers, CASH plates, hexagonal CH sheets, and CuSH gels. Thermal deterioration occurred when the OPC was burned at 800 °C, however it was less severe for most hydration products and micro/micro-cracks than when the OPC was in its pristine condition. Corrosion testing demonstrated that the blended materials' mild steel showed enhanced resistance to corrosion due to the presence of an excessive quantity of sludge.The physical, mechanical, microstructural, and deteriorating features of a green composite made from OPC and AAS waste were investigated after being subjected to minute amounts of CuFe


We find that the structural and magnetic properties of films grown from targets containing CoO or Co3O4 are similar and can be mapped on to each other by assuming that the films made from CoO require some additional oxygen to make them the same as those grown from Co3O4. The data suggest that the magnetism in these films is due to oxygen vacancies. Radically different properties are seen for the films grown with metallic Co in the target. In this case, there is structural evidence for the production of Zn vacancies as oxygen was added during deposition and this was accompanied by a strong increase of the magnetisation. In contrast, there was very little difference seen between the magnetic properties of the targets, which were all found to be paramagnetic, even after further annealing in air.We have investigated the magnetic properties of ZnCoO thin films grown by pulsed laser deposition from targets made from pure ZnO combined with metallic Co, CoO or Co The properties of laser ablated films of ZnCoO depend on the cobalt precursor used to make the target. Hence there have been many proposed applications in spintronics, optoelectronics and medicine.3,4Transition metal doped ZnO films, nanoparticles and nanowires have been studied intensively since the first theoretical predictions that they should be ferromagnetic if they were n-type5 Magnetism was also found in films, if they were sufficiently thin, so that surface states can support magnetism.6 Ion implantation introduces many lattice defects including vacancies and interstitials that are also effective in producing magnetism, as has been shown with implantation of As and Kr.7,8 There have also been studies where specific defects have been formed by growing the samples away from stoichiometry.There have been studies that show that the doping with transition metals is not essential; pure ZnO can support a considerable magnetism, provided it contains sufficient structural or stoichiometric defects; however, the magnetism is enhanced by the addition of transition metals. Grain boundaries are one such lattice defect and films of ZnO have been shown to be magnetic if the grain size is sufficiently small (less than ∼20 nm).2O3, TiO2, SnO2, HfO2, are magnetic if grown oxygen deficient9 and this has also been shown to occur for the surface of a ZnO crystal.10 This magnetism is attributed to oxygen vacancies. However, ZnO is unusual in showing magnetic properties when it is grown oxygen-rich, as it was found that magnetism was present when the film was very thin (∼50 nm); however this would disappear after the film was annealed in vacuo.11 A film made by sol–gel techniques, which was rich in oxygen, also showed strong magnetism that was attributed to Zn vacancies.12 It is worth noting that these non-stoichiometric samples have surface effects due to being either very thin films or having small grains; thus, it has not always been easy to separate the effect of Zn or oxygen vacancies from the effects due to grain boundaries or surfaces.Many other oxides, In13 who observed that such behaviour occurs in Stoner magnets where the moment is entirely due to a polarised band and the Curie temperature, Tc, which is related to the Fermi energy so is well above room temperature. This contrasts with materials where the magnetism is due to a local moment with spin S where the transition temperature is of the order of U/kB loge(2S + 1) where U is the ground-state energy. Transition temperatures of dilute local moment magnets, for example GaMnAs, are typically below room temperature.The behaviour of the saturation magnetic moment of most of these defective oxides drops rather slowly, if at all, between low temperature and room temperature. This was first explained by Coey0 magnetism when it is both oxygen poor and oxygen rich.It appears that narrow defect bands associated with both donors and with acceptors can occur in ZnO with properties such that the Stoner criterion for spontaneous magnetism can be met. In most oxides, that are only magnetic when grown sufficiently oxygen poor, this means that the conditions can only be met for donor bands associated with oxygen vacancies. A donor band requires that coherent transport occurs between defect sites, which means that the wave functions of the electrons in the defect states should have a radius that is larger or comparable to the separation between defects. This requires a small effective mass and a high dielectric constant. However, the defect states must be sufficiently deep so that the defect bands do not overlap the conduction or the valence band, because this would lead to a wider band and hence a lower density of states. This combination of a relatively narrow band-gap and deep defect levels appears to occur for ZnO alone. It thus appears to be the only oxide in the ‘Goldilocks zone’ for d14,15 There have been conflicting theoretical predictions as ZnCoO has been predicted to be ferromagnetic if it is p-type2,16 and n-type if it is due to being oxygen deficient or doped with Al.1,17 There are many works that discuss the relevance of magnetic polarons based on Co2+ ions.18 However, there have been measurements using XMCD that have shown that the Co ions are paramagnetic even if the sample is ferromagnetic.19There have been many studies of ZnO doped with transition metals. We consider particularly the results obtained with Co. One of the problems with ZnCoO is that metallic Co is strongly magnetic, so there is a challenge to separate intrinsic effects from those arising from Co nanoparticles; this is particularly critical if the films were grown oxygen-deficient as this makes the precipitation of Co nanoparticles more favourable.20 It was also found that high quality ZnCoO films were not magnetic, thus indicating that crystalline defects are playing a role here as in the case of pure ZnO.21,22In some cases it has been useful to correlate the behaviour of ZnCoO with that of pure ZnO; in these cases it is generally found that the effect of adding Co is to enhance the effect that was already present for pure ZnO, for example, it was shown that there was a critical grain size for ZnCoO to be magnetic, but that this occurred for larger grains than were required for pure ZnO.23–26 There have been studies of the effect of changing the carrier concentration on the magnetic properties, by co-doping with Al or Ga and by growing with various amounts of oxygen.25,27–30 The majority of samples have been grown such that they were n-type conductors and it was reported that the magnetism disappeared as the amount of oxygen in the films was increased, thus supporting the hypothesis that oxygen vacancies or Zn interstitials were necessary for the observation of room temperature magnetism.26,27 However, there have also been reports of substantial magnetism being observed when the films were grown oxygen-rich.24,28Films have been made by Pulsed Laser Deposition (PLD), reactive sputtering, annealed sol–gel and by ultrasonic assisted solution chemical vapour deposition.3O4 as the precursor,23,27 however CoO and metallic Co have also been used.31,32 In this study, we compare the results of using three different precursors: Co metal, CoO and Co3O4, to make the PLD targets and also grow films at different oxygen pressures. This enables us to study to what extent adding oxygen to the target is equivalent to adding oxygen during ablation in the PLD chamber.Most of the authors who report work on films grown by PLD have used a ceramic target of ZnCoO that has been fabricated using solid state reaction techniques. In most cases the Co has been introduced by using Co33 There is also an important difference between the films studied. In the earlier letter the ablation was carried out for a given time that was the same for all targets and all oxygen pressures. As a result the films described in the APL were thick when grown at base pressure and much thinner when grown in an oxygen atmosphere. Hence, there was the possibility that some of the difference between the films grown at different oxygen pressures might have been due to the different film thicknesses.This paper is a longer and much more detailed account of these films than that which we had given in an earlier letter.3O4 at different oxygen pressures are also included in detail. Magnetic studies of the targets are also included and this data is contrasted with that obtained for the films. Optical absorption and carrier concentration data are also included here. We show data that demonstrates that the effects of using different targets persist for all the values of oxygen pressure in the PLD chamber.In this work films, of similar thickness, were made from all three targets at all oxygen pressures. Hence results from the films made with the CoO and Co2.0.95Co0.05O, were prepared from high-purity ZnO powder combined with powders of metallic Co, CoO, or Co3O4. All the powders, which had purities of 99.999% for ZnO, 99.998% for metallic Co 99.998% for CoO, and 99.998% for Co3O4, were purchased from Alfa Aesar. In each case, the process of first grinding and then sintering the mixture in air for 12 hours was repeated for annealing temperatures of 400 °C, 600 °C, and 800 °C, before finally pressing into a target mould and sintering at 1000 °C for more than 12 hours.33 The targets all appeared similar and were green in colour, which indicates that similar amounts of the Co had been incorporated into the ZnO lattice during the solid state reaction to form the compound Znx1−CoxO, which is known as cobalt green (or Rinmann's green). In what follows, the ablated films will be referred to by the precursor used in the target's preparation, i.e. as Co, CoO and Co3O4 films.Targets of the same nominal composition, Znca. 3.5 cm. All the films were deposited on double-sided, polished, sapphire substrates that had been heated to 450 °C. The substrates had been purchased from PI-KEM Ltd and were single-crystal c-cut Al2O3. Five films were grown from each target: one at base pressure of 2 × 10−5 torr and four at higher oxygen pressures of 1 × 10−4, 1 × 10−3, 1 × 10−2 and 1 × 10−1 torr. The deposition times were varied so that the thicknesses of all the films were comparable and lay between 100 nm and 130 nm.A Lambda Physik LEXTRA 200 XeCl excimer laser with an operating wavelength of 308 nm and using a 10 Hz repetition rate was used for the ablation of the target. The separation between the target and the substrate was λ = 1.5406 Å) and the chemical state and physical environment of the Co ions were studied using X-ray absorption techniques, XANES and EXAFS.The lattice constants of the films and the grain sizes were measured using X-ray diffraction using CuKα radiation (The magnetic properties of both the films and the targets have been studied using a SQUID magnetometer. The magnetisations of the films were measured with the applied magnetic field in the plane of the sample. Measurements were made of the magnetisation as a function of temperature in field-cooled (FC) and zero-field-cooled (ZFC) conditions. Hysteresis loops were also measured at room temperature and at low temperatures. The magnetisation of the sapphire substrate was also measured and this contribution was subtracted from the measurements of all the samples shown here.L is defined as the difference in absorption of right and left circularly polarised light. This is a powerful technique because it is sensitive to the spin polarisation in either, or both, the initial and final states that are involved in the transition.32,34,35 The carrier concentration of the films was measured using a Quantum Design Physical Property Measurement System, PPMS.The nature of the states located in the energy gap of ZnO were investigated using optical absorption and magnetic circular dichroism (MCD) which is measured in Faraday geometry in the presence of a magnetic field parallel to the direction of light propagation. The MCD signal from a film of thickness 3.3O4 target grown at different oxygen pressures are shown in c-axis out of plane orientation with only (002) and (004) ZnO diffraction peaks observed. The (006) diffraction peak is from the sapphire substrate. No secondary phases were detected within the detection limit of the XRD for any of the films. The lattice constant is expected to contract as the concentration of vacancies rises and, conversely, to expand with increasing numbers of interstitials.33Typical XRD plots for films made from Co3O4 targets; this is consistent with the films having a large number of oxygen vacancies when grown at low oxygen pressure and that these vacancies are removed at higher oxygen pressure causing the lattice to expand. The lattice constants shown in 3O4 target compared with CoO is very roughly equivalent to increasing the oxygen pressure in the PLD chamber by a factor of 10. This behaviour, namely that the effect of using different targets could be off-set by changing the oxygen pressure in the PLD chamber, was also seen for films of (InFe)2O3.36The lattice constant increases as oxygen is added to the PLD chamber for the films made from CoO and Co33Very different behaviour is observed for the film made from metallic Co as the lattice constant decreased when the oxygen pressure was increased, as is seen in 20 The grain sizes increased with the amount of oxygen pressure in the chamber for all the films, as shown in 3O4 target.The enlarged ZnO (002) diffraction peaks, as shown in 3O4 was obtained from an analysis of K-edge XANES and EXAFS spectra. The measurements were made using beamline 20-BM at the Advanced Photon Source. A Si (111) monochromator was used providing 1 eV energy resolution at the Co K edge. The measurements were made at room temperature at a glancing angle of ∼5° with the X-ray polarization normal to the surface of the films. Typically, 4–8 scans were averaged for an improved signal-to-noise ratio and the data were analysed using the Demeter analysis package.37A more accurate estimate of the presence of defect phases, particularly to identify metallic Co and the precursors CoO and Co−5 torr, and the standard valence states of pure metallic Co and a sample of ZnCoO which is known to be fully Co substitutional in the Zn2+ sites. The near edge region ∼7712 eV is most sensitive to the metal and an examination of this region shows clearly that all Co-doped ZnO films that were deposited at base pressure from all three targets contain some metallic Co. The fraction of Co ions found to be in a metallic environment was estimated using the Athena and Artemis interface program packages,14,37 indicating that a percentage of such ions to be ∼28%, 16%, and 14% for Co-doped ZnO thin films grown at base pressure from the Co, CoO, and Co3O4 targets, respectively. No sign of metallic Co was seen in any of the films that were grown in an oxygen pressure of 10−4 torr, or any higher oxygen pressure.This measurement can detect the existence of metallic Co and any secondary oxide phases. 3O4, were present in the films and this was done best with EXAFS. −3 torr with a film where the Co was known to be substitutional  with the signals from metallic Co, CoO and Co3O4 are shown in comparison. This figure demonstrates that any residual concentration of CoO or Co3O4 is below the detection limit.It was important to ascertain if either of the oxide precursors, CoO or Co3O4. The variation of the lattice constant with pressure is the most revealing of the structural measurements as it shows that the films grown from a target formed from metallic Co are significantly different from those grown from a CoO or Co3O4 target.The films grown from the target made with metallic Co contain the most metallic Co when grown at base pressure, which is not surprising. It was significant that none of the films grown at higher oxygen pressures showed any evidence for the presence of the oxides CoO or Co4.The magnetic properties of both the films and the targets have been measured using the procedures described in Section 2.3O4; this may be because of nano-particles of CoO which have been found to show weak ferromagnetism at room temperature.38 The lowest susceptibility was found with films prepared from the Co target and this showed no evidence of Co nanoparticles. Powders from the targets which were annealed in air at 600 °C for 1 hour were studied in order to investigate if similar behaviour occurred for the targets as was seen for films ablated in an oxygen atmosphere. However relatively little difference was seen after the anneal as shown in These measurements, made in a magnetic field of 100 Oe, were performed for the three targets, both as used for the deposition and after annealing in air; the results are shown in 32 The size of the nanoparticles is deduced to be ∼5.1 nm, when we used the magnetic anisotropy constant for bulk Co metal, K ∼ 2.7 × 105 J m−3. This can be compared with the work of Ying et al.33 who did not find clear evidence for such nanoparticles in thicker films, 730 nm, grown under the same conditions from a Co target. The XANES data showed that the films made from the CoO and Co3O4 targets at base pressure contain some metallic Co, 16% and 14% respectively, but the magnetisation plots shown in 3O4 target showed an onset to hysteretic behaviour at a similar temperature as was seen for this target.The FC/ZFC plots for the films grown at base pressure are shown in χ = C/(T + θ) indicating antiferromagnetic interactions. The value of θ was found to be ∼10 K for all the targets. The value of the effective magnetic moment, peff, was found for all the targets from the Curie constants. The values of peff, all increased when the powders from the targets were annealed in air, which contrasts strongly with the magnetism observed for different values of films ablated at different oxygen pressures shown in Hysteresis loops of small quantities of powders taken from the targets showed paramagnetic behaviour without any evidence for ordered magnetism for any of the targets down to 10 K. A comparison of the susceptibilities measured at 10 K and 300 K indicated that the data could be fitted to a Curie-Weiss law, −5 torr, and the four higher oxygen pressures 1 × 10−4, 1 × 10−3, 1 × 10−2, and 1 × 10−1 torr. The magnetic data for the films shown in 2 pressure, for 5 K and 300 K in Magnetic hysteresis loops measurements at 5 K and 300 K were taken for the films that were deposited at base pressure, 2 × 10peff ≃ 3.4 ± 0.3 for all the films. This is close to the value of 3.8 expected for free spins of Co2+ and is in agreement with the work of Tietze et al.19 who showed that the Co2+ ions are all paramagnetic, even in ferromagnetic samples. This is much larger than the value of peff for all targets that was found to be 1.1 ± 0.3; this difference is probably due to antiferromagnetic interactions between Co ions in the targets.The paramagnetic contributions found at 5 K and 300 K indicated Curie law behaviour. The Curie constant was used to evaluate the value of the effective moment, M (300 K)/M (5 K) ≥ 0.8, for all the samples indicating that donor band states rather than local moments may be involved.13The saturation magnetisation of the samples deposited at base pressure was strongly temperature dependent because of the existence of small nanoparticles that contributed to the magnetisation in a field of 1 T at 5 K, but not at 300 K. The saturation magnetism for the films grown in oxygen showed little temperature dependence, 3O4 targets shows that the extra oxygen in the target made from Co3O4, compared with those made from CoO, is adding to the effects of the oxygen in the PLD chamber in determining the magnetisation of the film. The grain size increased with oxygen pressure, as shown in A comparison between the magnetic data for the films grown from the CoO and Co5.3O4 in spite of the fact that it contained the smallest percentage of metallic Co and also had the largest grains.Full and empty energy bands do not contribute to the magnetisation so the observed magnetic moments must be due to polarised defect states lying in the band gap of 3.4 eV. The absorption spectrum and the MCD for the films grown at base pressure are shown in 2+ ions34 which is superimposed on the broad negative signal from metallic Co embedded in ZnO.32,39 . The negative signal dominates the spectrum at 2.5 eV so the magnitude of this signal is plotted in the inset to The MCD shows the expected dispersive signal between 1.9 eV and 2.1 eV which is characteristic of the d to d* transition for Co35 The positive sign observed here indicates that the transition is from a partially occupied spin polarised acceptor band to unoccupied band states.The MCD spectra from the films that were grown in an oxygen-rich environment are very different; this is because they did not include a signal from metallic Co. ms = 0 and Δml = ±1 in Faraday geometry. Thus an MCD signal can only be observed if the spin and orbital states are mixed by spin–orbit coupling. In a partially filled orbital with positive spin polarisation, the induced orbital polarisation will be negative. This means that for transitions where the initial state is a polarised acceptor band and the final state is in the (unpolarised) conduction band, the intensity of the σ+ transition will be higher than that for σ− leading to a positive MCD. The magnitude of the MCD at 2.5 eV for all the films is shown in −4 torr measured as shown in Optical transitions occur between magnetically quantized electronic states with Δ6.3O4, the effects of having extra oxygen from the Co3O4 precursor has added to the effects of adding oxygen in the PLD chamber, as might have been expected from similar studies on In2O3.36 The effect was seen clearly in measurements of both the lattice constant and the saturation magnetisation. The effect of adding oxygen has been to reduce the fraction of oxygen vacancies and it was this that caused the lattice constant to increase and the magnetisation to decrease. It seems surprising that the effects of the precursor in the targets should be so important, even though the constituent powders were ground and sintered in air prior to being compressed into targets.The results obtained here demonstrate that, for the targets CoO and Co33 This was in spite of the fact that there were very little significant differences in the properties of the targets. Hall effect measurements have shown that all the films, apart from one grown in an oxygen pressure in the PLD chamber, had densities of ∼1018 to 1019 n-type carriers per cm3 this was in agreement with the earlier deduction that a carrier density less than 1019 per cm3 was favourable for magnetism.29 . This agreed with the earlier work where a film of ZnO grown heavily oxygenated still had sufficient oxygen vacancies to give n-type carriers even though Zn vacancies were present.12 DFT calculations have shown that magnetism in undoped ZnO would be due to Zn rather than oxygen vacancies.12,40 However previous theory for Co doped ZnO has indicated that magnetism occurs due to oxygen vacancies as was seen here for the samples made from the CoO and Co3O4 targets.41 The experimental results included here show that the theories of Zn vacancy magnetism may also be applicable when Co2+ ions are present.The results obtained when the precursor was metallic Co were dramatically different; in agreement work earlier work.7.3O4, in the films and no evidence of metallic Co in any of the films, including the one made with metallic Co in the target, provided that they were ablated in an oxygen pressure of 10−4 torr or higher. In addition, the targets themselves had similar magnetic properties with no obvious relation to those of the films made from them. The magnetic susceptibility of the powders, taken from the bulk targets, that were annealed at 600 °C for 1 hour in air, increased significantly. This must have been a surface effect since the whole target had previously been sintered at 1000 °C for 12 hours during fabrication. However, the effect of the exposure of the target powders to air during the anneal did not affect the target material in a way that bore any relation to the effects of adding small quantities of oxygen to the PLD chamber.The measurements taken here indicate some of the subtleties of the PLD process. The physical properties and the magnetisation of the films depended on the precursor Co material used with ZnO to make the target. This occurred in spite of the fact that there was no evidence for either of the oxide precursors, CoO and Co42Any intrinsic magnetism that is observed in ZnCoO occurs due to the presence of Co ions and defects. Native defects that are discussed most widely in the context of magnetism are O and Zn vacancies. Their properties have been studied extensively.3O4, rather than for the films ablated from the Co target, where single ions of Co, Zn and O predominate.In this work, we have shown that the defects that occur for oxygen-poor and oxygen-rich samples can both give rise to magnetic properties for ZnCoO but that the type of defect magnetism observed depended on the precursor used to fabricate the target. In both cases, there is some evidence supporting the view that the magnetisation is due to correlated electrons in narrow defect bands rather than local moments associated with the Co or other defects. Furthermore, the type of defect in the films depends in a subtle way on the preparation of the target used for the PLD. A possible reason for the different behaviour of the films is that it is more likely that Co–O ion pairs are present in the laser-plumes of targets made from the oxides CoO and Co2O3.36 We hypothesise that this is related to the fact that pure ZnO is unique among the transition metal oxides in becoming magnetic when it is grown strongly either oxygen-rich or oxygen-poor. This work offers new challenges for the understanding of the way that films grow following ablation from targets that differ in subtle respects.The anomalous magnetic and structural behaviour seen for a target made from metallic Co and ZnO was all the more unusual as such behaviour did not occur when metallic Fe was used as the target with InOur work shows that there are considerable advantages in using metallic Co as the precursor in targets to be used for the fabrication of ZnCoO films by PLD. The role of the Co precursor is to facilitate the production of a narrow defect band based on Zn vacancies in films that were ablated in an oxygen atmosphere.The authors have no conflict of interest.


Non‐invasive prenatal testing (NIPT) identifies the risk of abnormalities in pregnancy, potentially reducing the risk of miscarriage associated with invasive tests. This study aimed to understand the preferences of current and future mothers about the content, format and timing of information provision about NIPT.An online discrete choice experiment was designed comprising four attributes: when in the pregnancy information is provided (4 levels); degree of detail (2 levels); information format (6 levels); cost to women for gathering information (5 levels). Respondents included women identified by an online‐panel company in Sweden. The mathematical design was informed by D‐efficient criteria. Choice data were analysed using uncorrelated random parameters logit and latent class models.One thousand Swedish women (56% current mothers) aged 18–45 years completed the survey. On average, women preferred extensive information provided at/before 9 weeks of pregnancy. There was heterogeneity in preferences about the desired format of information provision  in the population.Women had clear preferences about the desired content, format and timing of information provision about NIPT. It is important to tailor information provision to enable informed choices about NIPT. What's already known about the topic?Non‐invasive prenatal testing (NIPT) is an emerging approach that detects fetal DNA from a maternal blood sample to identify the risk of abnormalities in pregnancy.Parents must be given the correct type and amount of information in an appropriate format. The information is needed to provide consent for undergoing NIPT.What does the study add?A discrete choice experiment was used to quantify the preferences of current and future mothers for content, format and timing of the provision of information about NIPT.Women had a strong preference for extensive information provided early in pregnancy using a variety of formats .Substantial heterogeneity in preferences was identified suggesting a tailored approach to effectively provide information about NIPT is required. Although pre‐test counselling and information provision is recommended in published guidelines,2An online survey comprising a DCE with additional supplementary questions was used to quantify the preferences of a sample of women living in Sweden. Data were collected between August and September 2019. The DCE was designed, analysed and reported in line with published guidelines.2.1The survey was programmed using HTML for online administration using SSI Web 8.3.8 Sawtooth software.2.2The DCE was framed to ask respondents to make a choice between two unlabelled alternatives of receiving NIPT information (options A and B) and an opt‐out alternative representing ‘no information’. Including an opt‐out alternative allows the analysis to estimate the probability of women choosing to have ‘no information’.Table 2.3Training materials were used at the start of the survey to ‘set the scene’ and explain key concepts to respondents. An interactive Prezi presentation was created to use as training materials and inserted at the start of the survey (see Supplementary Appendix 2.4n = 32) by generating a mathematical design while minimising the D‐error. In line with published evidence supporting the maximum number of choice sets one respondent can complete,The experimental design informs the specific combinations of attributes and levels that respondents evaluate in the choice questions and number of choice questions.2.5etc); degree to which a person engages with information provision or is apprehensive about using health information ; experiences of pregnancy and screening .2.7The relevant study population was (current or future) mothers who might be in a position to make the decision about NIPT. This was because it changes the risk of procedure related to injury to the mother and/or child and the decision and results are ultimately the mother's choice.A sample of women, currently with and without children, between the ages of 18 and 45 years, living in Sweden were recruited by Dynata. The target sample size of 1000 was chosen to allow analysis of the preferences of different subgroups. The amount of compensation received by the respondents completing the survey through the online panel provider was in line with Dynata policies and was not determined by the University of Manchester researchers. The survey link shared by the panel provider with participants included an anonymised ID number which was recorded by the researchers and passed back to the panel provider when a participant completed the survey in order for them to be reimbursed.Potential respondents were sent a link to the online survey and no reminders were used. The start of the survey contained two screening questions to remove men and also women aged 46 years or older.2.8An analysis plan was specified that respondents who did not complete the whole survey will be excluded. Stata 14 was used for all analyses.Choice data were analysed using regression‐based econometric methods using two steps. Step one used a conditional logistic regression model (CLM) to estimate the aggregate preferences of the whole sample completing the survey. A series of analysis were then run  regression model to characterise potential sources of heterogeneity in the preferences in the sample of women. LCA identifies groups (classes) of respondents within the sample who have similar preferences. The final stage in LCA then involves adding demographic factors to the LCA regression model to predict which types of people tended to belong to each of the identified class. The optimum number of classes and membership of each class was identified using log‐likelihood, AIC, BIC and the size of the standard errors of the estimated coefficients (aiming to minimise the size of the standard errors).2.9The outputs of the uncorrelated RPL analysis can be used to calculate the balance of benefits and harms for the included attributes in the DCE. This ratio of benefits: harms represents the amount of one attribute a respondent is willing to give up for a unit change in another and is generated by calculating the marginal rate of substitution (MRS). The MRS is calculated by dividing the estimated coefficient of interest by an attribute used as a ‘common’ denominator . Using the cost attribute as the denominator means that the willingness‐to‐pay (WTP) for the format, timing and level of detail of information can be calculated.3The final sample comprised 1000 women  to four (high engagement). Respondents also demonstrated a relatively low level of information apprehension with a mean score of 1.89 on a scale from zero (no apprehension) to four (high apprehension).Few respondents always made their choices based on a single attribute. Only 28 (2.8%) of the 1000 respondents always chose the NIPT information with the lower cost, while four (0.4%) always chose the profile with the higher cost. Only 15 (1.5%) respondents always chose to receive more detailed information while only five (0.5%) always chose to receive simple information.3.1Table Women preferred information before or at 9 weeks of pregnancy and were averse to information after 12 weeks. Extensive information was preferred to simple information and women wanted to receive information via a text‐based website, a discussion with their midwife, or through an app but not in a group discussion.All attribute level coefficients were statistically significant predictors of choice at the 5% level except information provided between 9 and 12 weeks, via an interactive website or leaflet and information that cost women over 1000 SEK in out‐of‐pocket costs. This indicated that respondents considered most information provided to them when making a choice. Women expressed the largest WTP for information being provided at 9 weeks of pregnancy, followed by extensive information being provided .3.2The LCA identified three classes as the optimal model (see Table Around one‐third (34%) of the sample were predicted to belong to class 2. Women in this class had a high intrinsic value for information and lower sensitivity to cost compared with those in class 1, resulting in higher WTP values. These women wanted information before 9 weeks and valued information provided in discussions with their midwife. They did not want information to be provided via a text‐based website. Women in this class were more likely to state that they believed they were at higher risk of having a child with Down's syndrome, were more likely to say they found the choice tasks difficult and were more likely to agree with the statement ‘I believe that terminations should be allowed for all different reasons’ (see Table Just under one‐fifth (18%) of the sample were predicted to belong to class 3. Women in this class had a low intrinsic value for information, generally preferring to receive no information. When they did choose to receive information, they had similar preferences for how that information was delivered as the women in class 1. Women in class 3 were more likely to report that they believed their risk of having a child with Down's syndrome was low, more likely to state that completing the choice tasks was easy and more likely to disagree with the statement ‘I believe that terminations should be allowed for all different reasons’ .The presence of subgroups of women with specific preferences about information provision was identified. Examining the preferences of these subgroups uncovered three distinct groups of women who prefer to receive information about NIPT in different ways. The predominant subgroup represented women who were cost‐sensitive and would like information but potentially only as a useful addition to their maternity care. Around a third of the sample formed another subgroup, who perceived their risk of having a child with Down's syndrome to be high and placed a greater intrinsic value on information provision. A third subgroup comprised women who were more likely to be against termination, perceived themselves to be at low risk of having a baby with Down's syndrome, or found the decision of whether to participate in NIPT easy to make. This subgroup of women did not want information about NIPT but would rather read extensively about NIPT in their own time. They also did not value pre‐scheduled face‐to‐face group discussions or individual discussions with a midwife. One reason for this could be that women in this subgroup would like to have the information to hand when discussing NIPT with friends or family.The preferences identified in this sample of women indicate that although some women value discussions with a midwife, this is not the case for all; some would prefer to receive information through other sources. This echoes findings from previous studies conducted in Sweden which found that pregnant women and high school students would prefer to receive or seek information about prenatal testing on the Internet, through written materials or a combination of oral and written communication.While many DCEs have been conducted in the areas of screening and diagnosis, few have investigated preferences for information to inform patients' decision‐making around these interventions. The finding that women prefer to receive information through individual discussions, and that they prefer extensive information, has previously been reported for a newborn bloodspot screening programme in the UK.The findings from this study may be generalisable to other countries with similar healthcare systems. For example, NIPT provision is broadly similar in some European countriesThere are some limitations associated with this study. Although the sample size of 1000 women may be considered large, the results may not be generalisable to the wider population of women in the position of deciding whether to receive information about NIPT. Our study also had a limited mix of ethnicities which may influence the generalisability of the findings. Future work could explore the preferences of different ethnic groups and cultures as they may have a different set of beliefs which may influence the decision of whether, when and how to seek information about NIPT.A key strength of this study was the use of a questionnaire survey of antenatal care units in Sweden to inform training materials and attribute development. Training materials are an important part of a DCE survey as they provide an introduction to the clinical area and help the respondent understand the context of the choice questions. When designing a DCE survey, it is also important to ensure that the attributes and attribute levels are realistic and based on what would occur in practice. The relatively large sample size completing the survey made it possible to explore the data, assess the validity of the survey, and identify subgroups of women who may have different preferences. The trading behaviour aligned with a priori expectations and only a few women (∼0.4%) preferred higher cost alternatives, suggesting the survey was generally well understood by respondents. The WTP values enable a monetary valuation of different aspects of NIPT information provision. These can be useful for comparing across different classes or subgroups of women (as shown here) but also to understand the potential demand of a healthcare programme with certain characteristics. Specifically, the WTP values could be used in a cost‐benefit analysis to understand the feasibility and acceptability of a mobile app to provide NIPT information.Future work is needed to understand the economic impact of different service models of information provision related to NIPT testing in Sweden. A previous systematic review of economic evaluations of NIPT suggested that the impact of information provision, in terms of cost and the effect on parents' wellbeing, is rarely accounted for in such studies.5The findings from this study showed that women living in Sweden have a strong preference for receiving extensive information about NIPT via individual discussions with a midwife, text‐based websites and mobile apps before or at 9 weeks of pregnancy. Importantly, this study identified there were subgroups of women with specific preferences about information provision can be used to design tailored leaflets, text‐based websites and mobile apps about NIPT.The authors have no conflict of interest to declare.Ethical approval (reference: DNR 2019‐04122) for this study was granted by the Swedish Regional Ethics Board.Supporting Information S1Click here for additional data file.