Mixed Zirconium Phosphate Bis-Phosphonomethyl Glycine from Nanocrystalline α-Zirconium Phosphate: A Tailored Suite for Gold Nanoparticles.

A novel synthetic approach was investigated for the preparation of nanoplatelets of mixed zirconium phosphate bis-phosphonomethyl glycine, ZPGly, by the reaction of a gel of nanocrystalline α-type zirconium phosphate with N,N-bis-phosphonomethyl glycine, H3Gly. The syntheses were carried out in the absence of hydrofluoric acid by changing both the reagent relative amounts and temperature. An H3Gly/Zr molar ratio >2 did not significantly improve the degree of crystallinity of the materials, while an increase of temperature from 80 °C to 120 °C improved the crystallinity; the best result was obtained with H3Gly/Zr molar ratio = 2 and with a temperature reaction of 120 °C. The sample consisted of nanoplatelets with the size in the range 20-40 nm, and it was successfully exfoliated by treatment with a solution of methylamine. By treatment of the ZPGly colloidal dispersions with HAuCl4, a color change from white to red-violet was observed, indicating the formation of gold nanoparticles. The size and morphology of the gold particles were affected by the degree of crystallinity and, in turn, by the composition of the ZPGly support. As a matter of fact, large micrometric Au particles with a cubo-octahedral morphology were obtained by using the less crystalline ZPGly_R2-80 sample, while interconnected Au particles, with a size of about 16 nm, were obtained by using ZPGly_R2-120. The samples exhibited an absorption maximum in the visible region due to the surface plasmon resonance of gold nanoparticles.

Agronomic potential of two different glass-based materials as novel inorganic slow-release iron fertilizers.

BACKGROUND: Large amounts of chemical fertilizers are still currently used to compensate the soil nutrients scarcity in order to increase and sustain crop yield with consequent rising of environmental pollution and health problems. To mitigate these environmental risks, fertilizers with slow-release behaviours have been developed. The aim of this study was to assess the agronomic potential of two different glass-based materials (by-products from the ceramic sector) as inorganic slow-release iron (Fe) fertilizers. RESULTS: The X-ray powder diffraction confirmed the presence of amorphous structure and the richness in Fe of the investigated materials. The solubility analysis highlighted the slow Fe release from the glassy network and that the maximum of the Fe release was at alkaline pH suggesting their potential use as slow-release Fe fertilizers, especially in calcareous soils. The pot and leaching experiments demonstrated that although the glass-based materials increased the amount of soil available Fe, we did not observe Fe leaching and plant toxicity. This fact would suggest their reliability to increase soil fertility without negative effects on the environment. CONCLUSION: The use of glass-based materials, specifically by-products from the ceramic sectors, as inorganic slow-release Fe fertilizers can be sustained. The tests performed at three different pH conditions testified the slow-release behaviour of the tested materials and underlined that the Fe release increases at alkaline environment. Therefore, the present study pointed out the glass-based materials by products from the ceramic sector as novel slow-release and environmental-friendly fertilizers in agriculture. © 2021 The Authors. Journal of The Science of Food and Agriculture published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

In†Situ X-ray Diffraction Investigation of the Crystallisation of Perfluorinated CeIV -Based Metal-Organic Frameworks with UiO-66 and MIL-140 Architectures*.

We report on the results of an in situ synchrotron powder X-ray diffraction study of the crystallisation in aqueous medium of two recently discovered perfluorinated CeIV -based metal-organic frameworks (MOFs), analogues of the already well investigated ZrIV -based UiO-66 and MIL-140A, namely, F4_UiO-66(Ce) and F4_MIL-140A(Ce). The two MOFs were originally obtained in pure form in similar conditions, using ammonium cerium nitrate and tetrafluoroterephthalic acid as reagents, and small variations of the reaction parameters were found to yield mixed phases. Here, we investigate the crystallisation of these compounds, varying parameters such as temperature, amount of the protonation modulator nitric acid and amount of the coordination modulator acetic acid. When only HNO3 is present in the reaction environment, only F4_MIL-140A(Ce) is obtained. Heating preferentially accelerates nucleation, which becomes rate determining below 57 °C. Upon addition of AcOH to the system, alongside HNO3 , mixed-phased products are obtained. F4_UiO-66(Ce) is always formed faster, and no interconversion between the two phases occurs. In the case of F4_UiO-66(Ce), crystal growth is always the rate-determining step. A higher amount of HNO3 favours the formation of F4_MIL-140A(Ce), whereas increasing the amount of AcOH favours the formation of F4_UiO-66(Ce). Based on the in situ results, a new optimised route to achieving a pure, high-quality F4_MIL-140A(Ce) phase in mild conditions (60 °C, 1 h) is also identified.

"Shake 'n Bake" Route to Functionalized Zr-UiO-66 Metal-Organic Frameworks.

We report a novel synthetic procedure for the high-yield synthesis of metal-organic frameworks (MOFs) with fcu topology with a UiO-66-like structure starting from a range of commercial ZrIV precursors and various substituted dicarboxylic linkers. The syntheses are carried out by grinding in a ball mill the starting reagents, namely, Zr salts and the dicarboxylic linkers, in the presence of a small amount of acetic acid and water (1 mL total volume for 1 mmol of each reagent), followed by incubation at either room temperature or 120 °C. Such a simple "shake 'n bake" procedure, inspired by the solid-state reaction of inorganic materials, such as oxides, avoids the use of large amounts of solvents generally used for the syntheses of Zr-MOF. Acidity of the linkers and the amount of water are found to be crucial factors in affording materials of quality comparable to that of products obtained under solvo- or hydrothermal conditions.

Development of a Smart Leg Splint by Using New Sensor Technologies and New Therapy Possibilities.

Nowadays, after suffering a fracture in an upper or lower limb, a plaster cast is placed on the affected limb. It is a very old and efficient technique for recovery from an injury that has not had significant changes since its origin. This project aims to develop a new low-cost smart 3D printed splint concept by using new sensing techniques. Two rapidly evolving Advanced Manufacturing (AM) technologies will be used: 3D scanning and 3D printing, thus combining engineering, medicine and materials evolution. The splint will include new small and lightweight sensors to detect any problem during the treatment process. Previous studies have already incorporated this kind of sensor for medical purposes. However, in this study it is implemented with a new concept: the possibility of applying treatments during the immobilization process and obtaining information from the sensors to modify the treatment. Due to this, rehabilitation treatments like infrared, ultrasounds or electroshock may be applied during the treatment, and the sensors (as it is showed in the study) will be able to detect changes during the rehabilitation process. Data of the pressure, temperature, humidity and colour of the skin will be collected in real time and sent to a mobile device so that they can be consulted remotely by a specialist. Moreover, it would be possible to include these data into the Internet of Things movement. This way, all the collected data might be compared and studied in order to find the best treatment for each kind of injury. It will be necessary to use a biocompatible material, submersible and suitable for contact with skin. These materials make it necessary to control the conditions in which the splint is produced, to assure that the properties are maintained. This development, makes it possible to design a new methodology that will help to provide faster and easier treatment.

Development of a Smart Splint to Monitor Different Parameters during the Treatment Process.

For certain musculoskeletal complex rupture injuries, the only treatment available is the use of immobilization splints. This type of treatment usually causes discomfort and certain setbacks in patients. In addition, other complications are usually generated at the vascular, muscular, or articular level. Currently, there is a really possible alternative that would solve these problems and even allows a faster and better recovery. This is possible thanks to the application of engineering on additive manufacturing techniques and the use of biocompatible materials available in the market. This study proposes the use of these materials and techniques, including sensor integration inside the splints. The main parameters considered to be studied are pressure, humidity, and temperature. These aspects are combined and analyzed to determine any kind of unexpected evolution of the treatment. This way, it will be possible to monitor some signals that would be studied to detect problems that are associated to the very initial stage of the treatment. The goal of this study is to generate a smart splint by using biomaterials and engineering techniques based on the advanced manufacturing and sensor system, for clinical purposes. The results show that the prototype of the smart splint allows to get data when it is placed over the arm of a patient. Two temperatures are read during the treatment: in contact with the skin and between skin and splint. The humidity variations due to sweat inside the splint are also read by a humidity sensor. A pressure sensor detects slight changes of pressure inside the splint. In addition, an infrared sensor has been included as a presence detector.

Experimental Comparison on Dental BioTribological Pairs Zirconia/Zirconia and Zirconia/Natural Tooth by Using a Reciprocating Tribometer.

The application of tribology in dentistry is growing rapidly, intense research has been conducted to develop an understanding of dental tribology for better selection of artificial materials and dental implant design. Dental biotribology, has been one of the most important branches in biotribology in recent years. The aim of this research is to investigate the tribological performances in the tooth-to-tooth contact and material-to-natural tooth contact (zirconia vs. zirconia and natural tooth vs. zirconia). The presented research was carried out by testing the above mentioned tribological pairs with the use of a reciprocating tribometer under lubricated conditions (artificial saliva). The normal force used in the tests was 20 N the time for each test was of 60 min. The stroke length was 2 mm, according to the range of displacement used in scientific literature. The wear mass loss evaluation was evaluated by using a gravimetric method. In order to characterize the wear mechanisms, present in the worn surfaces after each of tribo-tests, a topographic analysis was carried with a 3D non-contact optical profiler. The results show that the minimum value of the COF is obtained in the case of Zirconia vs. Zirconia tribo-couple. The results on the wear mass loss show a very low wear rate when coupling in tribological condition natural tooth with a ceramic restoration (a mean value of 0.5 mg was found). This rate is even lower when the contact is between two artificial zirconia teeth.

Oral appliance for Obstructive Sleep Apnea: Prototyping and Optimization of the Mandibular Protrusion Device.

Obstructive Sleep apnea is a public health problem. This disease is associated with daytime sleepiness, increased motor vehicle accidents, heart failure and stroke. Treatment options include weight loss, positive airway pressure, pharyngeal and orthognatic surgery. However, selected patients have good response to oral appliances devices that intended to protrude and stabilize the mandible mechanically during the night in order to reduce the collapsibility of the upper airway. Selection of patients includes primary snoring, mild, moderate and positional apnea. The perfect mandibular advance device has not yet been designed. For these reasons, the objective of this paper is to present a new thermoadjustable chair-side oral appliance. Device integrates the best characteristics of custom made and boils and bite previous designs and minimizes inconveniences and possible side effects. The device is a titratable mandibular advancement appliance. It consists of two independent prefabricated trays adaptable to the shape of adult dental arch and linked to each other by a protrusion mechanism. Each tray contains a hard outer shell and a soft thermoplastic resin inner body. The position of the jaw can be adjusted by moving an aluminum rack into, or out from, the guide so the ratchet may get locked into a certain position ensuring the length of the mechanism. The protrusion mechanism is fixed to the splint using small rings that are articulated over a "t" button. Our prototype satisfies the requirements of an effective oral appliance, in terms of retention, comfort, safety and efficacy. It is easy to fit, durable, low cost, quickly titratable, not bulky and easy cleaning. Thermoplastic appliances are specially used like a predictor of treatment response in apnea patients. The device described is a cost-effective introduction to mandibular advancement technology. A qualified dentist or trained sleep doctor could mitigate dental side effects and reduce their incidence.

Novel Technique Based on Fused Filament Fabrication (FFF) and Robocasting to Create Composite Medical Parts.

The purpose for this study is to obtain a new composite manufacturing system based on Additive Manufacturing techniques that allows the creation of parts for the medical industry. These pieces will be resistant, lightweight and may have geometries more complex than those created with traditional systems of composite material. The new system is based on the union of two heads on a 3D Rep-Rap printer. One of the heads is an extruder head of thermoplastic Fused Filament Fabrication (FFF) and the other is a dosing head, based on the Robocasting technique, designed to be assembled on the 3D printer. Thermoplastics material and epoxy resin will be used. The alternate printing of both materials generates a piece of composite material. This new technique will allow to increase the structural properties of the piece in the XY plane. The new additive manufacturing system allows to obtain mechanical improvements both in the modulus of elasticity and in the tensile strength. Increase the modulus of elasticity of a value between 50 and 80% depending on the thermoplastic filament used. In the same way the tensile strength has increased between 50 and 60%. The improvement in the strength / weight ratio allows to this new additive manufacturing system to create medical pieces in which the lightness and resistance are its main characteristic, such as orthopedic prostheses.The results show that the use of FFF together with Robocasting, as a manufacturing process for end-use parts, generates an additional advantage that had not been considered until now. The combination of a thermoplastic and an epoxy resin opens a new path in the additive manufacturing since it allows creating pieces with new qualities without being conditioned by the design.

Design of a Functional Splint for Rehabilitation of Achilles Tendon Injury Using Advanced Manufacturing (AM) Techniques. Implementation Study.

The use of conventional immobilization splints can cause a lot of mishaps and discomfort in patients. In addition, it is common the generation of muscle, joint and vascular complications arising from the application of classic restraint devices in this phase of treatment. Currently, it is being observed that these problems could be solved with the use of Advanced Manufacturing techniques based on Additive Manufacturing (AM), industrial digitalization and reverse engineering for the realization of individualized immobilization splints. The present study proposes to give these splints a functional character in their design adapting them to a specific pathology, in this case to the partial rupture of Achilles tendon. It also provides a comparison against the use of conventional plaster splints as an improvement factor for their definitive implementation considering the initial sanitary use for which they were designed. In this way, there have been created therapeutic windows that allow the application of rehabilitation techniques, being the treatment that would be carried out developed in parallel. The designed splint has been made in FilaFlex and Polycarbonate, materials that guarantee comfort and resistance at the same time. In addition, an optimization in terms of material has been executed, lightening the splint and reducing environmental impact and manufacturing costs. As a result of this preliminary study, a prototype on scale printed in PLA has been generated.

Geometric Model for the Postural Characterization in the Sagital Plane of Lumbar Raquis.

The individual's posture is the physical expression of his body. It is modified throughout life and it is determined by the particular anatomical characteristics that directly affect the biomechanics of the spine. The typing of the spinal curvature is important for the knowledge of body posture. The possibility of having a method for the systematic postural characterization of the spine is an essential objective resource in order to obtain normal or control patterns of the spinal morphology of the population. A widely accepted methodology of morphological characterization of the spine is a necessary requirement for the establishment of preventive criteria for spinal pathologies based on epidemiological population studies. It also represents a necessary requirement for the classification of individuals, based on the biomechanical, orthopaedic or ergonomic criteria necessary for disciplines such as sports, industrial design or sports performance. The present study proposes the development of a morphological postural model of the spine in the lumbar region. The model is based on a system of measurement of objective and comparable parameters by means of X-ray analysis, in order to characterize its morphology in the sagittal plane. The comparison of the results in a population of 47 individuals allowed the possibility to carry out a statistical study on three morphological parameters: sacral angle (α1); reversal angle (α2) and degree of lordosis (DL). The statistical hypothesis that the results behave according to a normal distribution with p < 0.05 is relevant and allows the systematization and postural modelling of the individual.

Behavior under Load of A Human Shoulder: Finite Element Simulation and Analysis.

Most musculoskeletal injuries occur during the work routines in different areas, due to repetitive and sustained movements, they are often located in the shoulder. For workers in the building sector, the repetitive movements and displacements occur under load and unnatural postures of the shoulder joint. For this reason, this study aims to model in 3D the biological components which form the shoulder joint for the later finite element analysis. Three cases with different loads have been considered for this study. Due to a linear and isotropic joint approach it has been possible to evaluate the tensions in the main components of the shoulders: muscles, tendons and ligaments. The methodology used allowed obtaining an improved mesh of the shoulder joint to analyse real situations with finite element method analysis with applications in the field of sports medicine, work, etc. Furthermore, the simplification adopted for modelling the joint muscles, as 1D elements in the finite element model has made it possible to establish different positions of human joint without mesh again each of the studied positions. The results are consistent with the states of applied loads. In fact, the maximum stresses in bones are in the insertion areas of the ligaments. Due to the static positions of the joint under study, the muscles do not support high stresses. According to the stresses distribution, the maximum values are in the zones of tendons. From the result analysis, it is observed how the stresses distribution in the cartilage area maintains coherence with reality since the maximum stresses appear in the lower half of the cartilage. In this area in which the Humerus-scapula contact is greater, the compression tensions are greater.

Monitoring an Analysis of Perturbations in Fusion Deposition Modelling (FDM) Processes for the Use of Biomaterials.

During an FDM production process, there are different external disturbances to the characteristics of the machine that can affect to the production process. These disturbances will cause the final result differs from the desired one. Moreover, these disturbances, such as temperature or chamber humidity, are extremely important in case of using biocompatible materials. The use of these kind of materials with not controlled environment, can cause them to modify or loss of their properties; what will make the product unusable. Apart from these external disturbances, the conditions of the machine to which the material is subjected must also be considered, such as temperature, vibrations or extrusion speed. The monitoring of all these data will allow to know the conditions to which the product was exposed during the process. In this way, it will be able to verify the validity of the final product. For these reasons, the purpose of this work is to monitor the conditions of production of structures with biocompatible materials by fused deposition modelling (FDM) technique. This monitoring will allow us to obtain a report that guarantee the technical and geometrical characteristics of the model and the biomaterial properties. The parameters chosen to be monitored are: Diameter of filament use, temperature in extrusion nozzle, ambient temperature in closed chamber, ambient humidity in closed chamber. The obtained results, after collected and analysing the data, present variations of up to 3% in the temperature of the nozzle of the extruder with respect to set temperature. In the case of the filament diameter the difference with respect to the value provided from the filament supplier is of 13,7%. In addition, the results show how the ambient humidity in closed chamber has changed by 2 percentage points and the ambient temperature in closed chamber has been increased 6,52 °C with respect to the set values.

Filament Advance Detection Sensor for Fused Deposition Modelling 3D Printers.

The main purpose of this paper is to present a system to detect extrusion failures in fused deposition modelling (FDM) 3D printers by sensing that the filament is moving forward properly. After several years using these kind of machines, authors detected that there is not any system to detect the main problem in FDM machines. Authors thought in different sensors and used the weighted objectives method, one of the most common evaluation methods, for comparing design concepts based on an overall value per design concept. Taking into account the obtained scores of each specification, the best choice for this work is the optical encoder. Once the sensor is chosen, it is necessary to design de part where it will be installed without interfering with the normal function of the machine. To do it, photogrammetry scanning methodology was employed. The developed device perfectly detects the advance of the filament without affecting the normal operation of the machine. Also, it is achieved the primary objective of the system, avoiding loss of material, energy, and mechanical wear, keeping the premise of making a low-cost product that does not significantly increase the cost of the machine. This development has made it possible to use the printer with remains of coil filaments, which were not spent because they were not sufficient to complete an impression. Also, printing models in two colours with only one extruder has been enabled by this development.

Determination of changes in the concentration and distribution of elements within olive drupes (cv. Leccino) from Se biofortified plants, using laser ablation inductively coupled plasma mass spectrometry.

BACKGROUND: Biofortification of food crops has been used to increase the intake of Se in the human diet, even though this may change the concentration of other elements and modify the nutritional properties of the enriched food. Selenium biofortification programs should include routine assessment of the overall mineral composition of enriched plants. RESULTS: Laser ablation inductively coupled plasma mass spectrometry (LA ICP-MS) was used for the assessment of mineral composition of table olives. Olive trees were fertilized with sodium selenate before flowering. At harvest, the edible parts of drupes proved to be significantly enriched in Se, delivering 6.1 µg g-1 (39% of the RDA for five olives). Such enrichment was followed by significant changes in the concentrations of B, Mg, K, Cr, Mn, Fe and Cu in edible parts, which are discussed for their impact on food quality. CONCLUSION: The biofortification of olive plants has allowed the enrichment of fruits with selenium. Enrichment with selenium has caused an increase in the concentration of other elements, which can change the nutritional quality of the drupes. The analytical technique used well as a valuable tool for routinely determining the chemical composition of all fruit parts. © 2018 Society of Chemical Industry.

Design of an Orthopedic Product by Using Additive Manufacturing Technology: The Arm Splint.

The traditional fabrication process of custom-made splints has hardly undergone any progress since the beginning of its use at the end of the eighteenth century. New manufacturing techniques and the new materials can help to modernize this treatment method of fractures. The use of Additive Manufacturing has been proposed in recent years as an alternative process for the manufacture of splints and there has been an increase in public awareness and exploration. For this reason, in this study a splint model printed in 3D, that replaces the deficiencies of the cast maintaining its virtues, has been proposed. The proposed methodology is based on three-dimensional digitalization techniques and 3D modeling with reverse engineering software. The work integrates different scientific disciplines to achieve its main goal: to improve life quality of the patient. In addition, the splint has been designed based on the principles of sustainable development. The design of splint is made of Polycarbonate by technique of Additive Manufacturing with fused deposition manufacturing, and conceived with organic shapes, customizing openings and closing buttons with rubber. In this preliminary study the final result is a prototype of the 3D printed arm splint in a reduced scale by using PLA as material.

Analysis and Fem Simulation Methodology of Dynamic Behavior of Human Rotator Cuff in Repetitive Routines: Musician Case Study.

The majority of musculoskeletal injuries located in the shoulder are often due to repetitive or sustained movements that occur in work routines in different areas. In the case of musicians, such as violinists, who have long and daily training routines, the repetitive movements they perform are forced and sometimes the postures are not natural. Therefore, this article aims to study and simulate the dynamic behavior of the glenohumeral joint under repetitive conditions that represent the different postures assumed by a violinist during his daily training. For this purpose, the criteria provided by the RULA (rapid upper limb assessment) method have been used. Subsequently, by using as a reference geometry that of the articulation under study generated and modeled in CATIA®[VERSIÓN 5R21], a FEM analysis has been proposed with the software ANSYS®[VERSIÓN 17.1] simulating the short and cyclic movements of the Humerus of the violinists. With the analysis carried out, thanks to linear and isotropic approximations of the joint, it has been possible to know the approximate dynamic behavior of tissues, muscles and tendons, and the response of the joint in terms of fatigue.

Integration of Error Compensation of Coordinate Measuring Machines into Feature Measurement: Part I-Model Development.

The development of an error compensation model for coordinate measuring machines (CMMs) and its integration into feature measurement is presented. CMMs are widespread and dependable instruments in industry and laboratories for dimensional measurement. From the tip probe sensor to the machine display, there is a complex transformation of probed point coordinates through the geometrical feature model that makes the assessment of accuracy and uncertainty measurement results difficult. Therefore, error compensation is not standardized, conversely to other simpler instruments. Detailed coordinate error compensation models are generally based on CMM as a rigid-body and it requires a detailed mapping of the CMM's behavior. In this paper a new model type of error compensation is proposed. It evaluates the error from the vectorial composition of length error by axis and its integration into the geometrical measurement model. The non-explained variability by the model is incorporated into the uncertainty budget. Model parameters are analyzed and linked to the geometrical errors and uncertainty of CMM response. Next, the outstanding measurement models of flatness, angle, and roundness are developed. The proposed models are useful for measurement improvement with easy integration into CMM signal processing, in particular in industrial environments where built-in solutions are sought. A battery of implementation tests are presented in Part II, where the experimental endorsement of the model is included.

Integration of Error Compensation of Coordinate Measuring Machines into Feature Measurement: Part II-Experimental Implementation.

Coordinate measuring machines (CMM) are main instruments of measurement in laboratories and in industrial quality control. A compensation error model has been formulated (Part I). It integrates error and uncertainty in the feature measurement model. Experimental implementation for the verification of this model is carried out based on the direct testing on a moving bridge CMM. The regression results by axis are quantified and compared to CMM indication with respect to the assigned values of the measurand. Next, testing of selected measurements of length, flatness, dihedral angle, and roundness features are accomplished. The measurement of calibrated gauge blocks for length or angle, flatness verification of the CMM granite table and roundness of a precision glass hemisphere are presented under a setup of repeatability conditions. The results are analysed and compared with alternative methods of estimation. The overall performance of the model is endorsed through experimental verification, as well as the practical use and the model capability to contribute in the improvement of current standard CMM measuring capabilities.

Layered metal(IV) phosphonates with rigid pendant groups: new synthetic approaches to nanosized zirconium phosphate phenylphosphonates.

Single phase mixed zirconium phosphate phenylphosphonates, ZrP(PP)x, were prepared by two different synthetic approaches: reaction of gels of nanosized α-zirconium phosphate in propanol with solutions of phenylphosphonic acid (H2PP), leading to the topotactic exchange of monohydrogen phosphate groups with phenylphosphonate groups, and precipitation from propanol solutions of H2PP, phosphoric acid, and zirconyl propionate. In both cases, propanol intercalated compounds were obtained. The x values of the ZrP(PP)x materials prepared by topotactic anion exchange ranged from 0.37 to 0.56 for (H2PP/Zr) molar ratios in the range 0.52-4.16 and [H2PP] = 0.1 M, while a maximum x value of 0.73 was only reached at 60 °C, with (H2PP/Zr) = 4.16 and [H2PP] = 0.31 M. Direct precipitation of ZrP(PP)x provided samples with 0.13 ≤ x ≤ 1.54, for H2PP molar fractions in the range 0.05-0.5 and (P/Zr) molar ratio = 6. At 90% relative humidity, the (H2O/Zr) molar ratio for the precipitated ZrP(PP)x powder samples increased in the range 1.3-3.0 with increasing x and resulted in being higher than that of nanosized ZrP (0.8). The analysis of the X-ray diffraction patterns of the gel and powder samples, together with the hydration data of the powder samples, suggested a structural model in which the random distribution of the phosphate and phenylphosphonate groups creates cavities which can accommodate propanol molecules in the gel samples and water molecules in the hydrated powder samples.