WO2015087345A1 - Bioactivité de verres fluorophosphatés et leur procédé de fabrication - Google Patents

Bioactivité de verres fluorophosphatés et leur procédé de fabrication Download PDF

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WO2015087345A1
WO2015087345A1 PCT/IN2014/000757 IN2014000757W WO2015087345A1 WO 2015087345 A1 WO2015087345 A1 WO 2015087345A1 IN 2014000757 W IN2014000757 W IN 2014000757W WO 2015087345 A1 WO2015087345 A1 WO 2015087345A1
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calcium
glass
composition
glasses
fluoride
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PCT/IN2014/000757
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English (en)
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Rajkumar GURUSAMY
Pugalanthipandian SANKARALINGAM
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Pandian Bio-Medical Research Centre
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Publication of WO2015087345A1 publication Critical patent/WO2015087345A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/12—Silica-free oxide glass compositions
    • C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
    • C03C3/247—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron containing fluorine and phosphorus
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/10—Ceramics or glasses
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02—Inorganic materials
    • A61L27/12—Phosphorus-containing materials, e.g. apatite
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/0007—Compositions for glass with special properties for biologically-compatible glass
    • C03C4/0014—Biodegradable glass
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/0035—Compositions for glass with special properties for soluble glass for controlled release of a compound incorporated in said glass
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2430/00—Materials or treatment for tissue regeneration
    • A61L2430/02—Materials or treatment for tissue regeneration for reconstruction of bones; weight-bearing implants

Definitions

  • the present invention describes the composition of fluorine added phosphate based glasses by melt quenching technique for different bio-medical applications.
  • autologous bone remains the preferred material in bone graft and regenerative procedures.
  • This bone taken from a secondary site within the body is often excised and reimplanted. It contains both the inorganic mineral hydroxyapatite as well as the cell characteristics of bone. Even this is not a living material, but can remodel into new and functional bone.
  • Autografts may be combined with supplementary agents such as growth factors or synthetic bone replacement materials.
  • the disadvantage of autologous bone usage is the creation of a secondary trauma site that has to heal. Further, its usage is limited by availability.
  • the materials taken from cadavers (allograft) are not constrained by supply. The above material is often demineralized, leaving behind a collagenous scaffold for the growth of new bone. Further, it fails to function as an osteoinductive but only as osteoinductive material. These materials always carry the risk of disease transmission with them.
  • bioactive glass The third generation of materials used for the regeneration of new bone is bioactive glass. These materials have the unique ability to form a chemical bond with the host tissue when implanted. Thus, it allows to retain the structural integrity and to resist movement at the implantation site. The chemical bond that occurs through the formation of hydroxyapatite on the glass surface converts the glass into bone rich material. The beneficial effects of bioactive glasses on cellular growth also substantiate to their use.
  • Fluorine molecule is used to promote bone formation and this fact is well known by years of clinical experience and hence is used in medical practice. As per the guidelines from environmental protection agency (EPA), India, 4 ppm of fluorine is the permitted level in water. Consuming excess amount of fluorine above that for a long period of time is known to cause fluorosis, a disease of abnormal bone formation even in soft tissues in the body. This observation is taken into consideration to induct fluorine in an optimal nontoxic dose as a component for higher rate of bone growth to produce a specific type of glass, namely fiuorophosphate glass, which is having higher rate of apatite forming ability than the available bioglasses and bioactive glasses.
  • EPA environmental protection agency
  • Fiuorophosphate glasses so far made have been put into several industrial applications. US patents such as 20130135714, 20130134362, 20120258848, 20120090358, 20090325774, 20040023786 etc. are few examples for the use of fiuorophosphate glasses in laser amplification, optical fiber, battery electrode applications. To the best of our knowledge, no study has been done on fiuorophosphate glasses for bone tissue engineering. To develop a better composition of fiuorophosphate glasses which is having higher biological conversion and less toxic to biological tissues for different biomedical application is the objective of the present invention.
  • Fluoride added phosphate based glasses and methods of making and the use thereof are disclosed.
  • a rich layer of hydroxyapatite (HAp) is formed on the surface of fluorophosphate glasses during in vitro studies.
  • the ex vivo cell culture studies confirmed that the prepared glasses are non-toxic and exhibit better cell viability with the addition of fluoride molecule up to 10 mol% in glass composition.
  • the physical properties of the fluoride added phosphate based glasses were assessed using ultrasonic velocity measurements, x-ray diffraction (XRD) patterns, Fourier transform infrared spectra (FTIR), pH variation of the sample glasses soaked 21 days in the laboratory prepared simulated body fluid (SBF) solution, scanning electron microscope (SEM) images, energy dispersive x-ray spectra (EDS) and x-ray photo electron spectrographs (XPS).
  • XRD x-ray diffraction
  • FTIR Fourier transform infrared spectra
  • SBF laboratory prepared simulated body fluid
  • SEM scanning electron microscope
  • EDS energy dispersive x-ray spectra
  • XPS x-ray photo electron spectrographs
  • Fig. 1 shows the flow chart for synthesis protocol.
  • Figs. 2, 3a and 3b show the density variations and elastic moduli of the prepared glass samples as a function of added CaF 2 .
  • Fig. 4 shows the XPS spectrograph of the glass sample FP3.
  • Fig. 5 and 6 show respectively the SEM image and EDS spectrum of the prepared glass sample FP3; Fig.
  • FIG. 7 shows the pH variations of the glass samples FP1, FP2, FP3, FP4 and FP5 during 21 days of in vitro studies.
  • Fig. 8 and Fig. 9 show respectively the FTIR spectrograph XRD pattern of all the glass samples after 21 days immersion in SBF solution.
  • Figs. 10 and 11 show the SEM image, EDS spectrum of the glass sample FP3 after in vitro studies;
  • Fig. 12 shows the optical microscope image of cell viability test of the sample FP3.
  • Figs. 13a, 13b and 13c show the SEM images of un-decalcified section of the femoral condyle of the rabbit bone after 10 weeks implanting.
  • Figs. 14a and 14b show the CLSM images of the un- decalcified section of the implant FP3. Description of invention
  • Fluorophosphate glass composition P2O5— CaO— Na 2 0— CaF 2 methods of preparation and use thereof are disclosed.
  • the glasses can be used for different bio-medical applications such as bone substitute, prosthetic implants, stents, screws, plates, tubes, controlled drug delivery etc. Fluorine was added in incremental pattern in various compositions, keeping the P/Ca ratio as constant.
  • the fluorophosphate glasses were prepared in the mentioned compositions include various salts in mol% within the following ranges:
  • CaO Calcium sulphate, calcium carbonate, calcium fluoride, calcium fluorophosphate, calcium chloride, calcium caseinate, calcium bicarbonate etc.
  • CaF 2 Calcium di fluoride, calcium tri fluoride, calcium fluorophosphate, sodium fluoride etc.
  • fluorine on phosphate glass system is studied in terms of density measurement, ultrasonic velocity measurement, SEM image, EDS spectra, XRD pattern and pH variations during in vitro studies and by in vivo studies using animal model.
  • the structural role of fluorine is noticed in the form of loose packing of glass network.
  • the hydroxyapatite (HAp) forming ability of prepared glasses is carried through in vitro studies in simulated body fluid (SBF).
  • SEM scanning electron microscopy
  • SEM scanning electron microscopy
  • fluorophosphate glasses are found to be more suitable for synthetic bone graft material.
  • Fluorophosphate glasses were prepared by melting the homogeneous mixture of phosphate, calcium, sodium and fluoride salts followed by sudden quenching of the melt.
  • the derivatives of phosphate, calcium, sodium and fluoride salts were weighed accurately and ground using mortar and pestle/ planetary ball mill .
  • the mixture was fed into alumina crucible and then preheated at a temperature ranging from 140 °C to 190 °C for 1 h in a closed furnace and cooled to room temperature at a rate of 1 °C per minute.
  • the preheated mixture was ground using mortar and pestle/ planetary ball mill.
  • the mixture was taken in a platinum crucible and melted at the temperature ranging from 1050 °C to 1400 °C for 1 h.
  • the temperature in the furnace was kept constant throughout the process.
  • the melt was poured in a preheated graphite/ steel mould and cooled to room temperature. In this method, the entire synthesis protocol is successfully done without the usage of any
  • the method for preparing fluorophosphate glasses comprises the following steps:
  • the obtained solid glass sample is annealed at 300 °C - 500 °C for 1 h and cooled at the rate of 0.5 °C - 2 °C per minute.
  • the prepared glass sample was annealed at 300 °C- 500 °C for 1 h and then cooled at the rate of 0.5 °C - 2 °C per minute to release the stress in the glass sample.
  • the prepared glass sample was cut into required size and shape using a diamond cutter.
  • the code for the present sample is called as FP1.
  • the powdered mixture was melted in platinum doped with 10% Rhodium crucible and heated at the temperature range of 1050 °C - 1400 °C for 1-4 h then quenched in a preheated stainless steel/ graphite mould of temperature 300 °C - 600 °C and then cooled.
  • the prepared glass sample was annealed at 300 °C- 500 °C for 1 h then cooled at the rate of 0.5 °C - 2 °C per minute to release the stress in the glass sample.
  • the prepared glass sample was cut into required size and shape using a diamond cutter.
  • the code for the present sample is called as FP2.
  • the powdered mixture was melted in platinum doped with 10% Rhodium crucible and heated at the temperature range of 1050 °C - 1400 °C for 1-4 h then quenched in a preheated stainless steel/ graphite mould of temperature 300 °C - 600 °C and then cooled.
  • the prepared glass sample was annealed at 300 °C- 500 °C for 1 h and then cooled at the rate of 0.5 °C - 2 °C per minute to release the stress in the glass sample.
  • the prepared glass sample was cut into required size and shape using a diamond cutter.
  • the code for the present sample is called as FP3.
  • Example 4 The code for the present sample is called as FP3.
  • the powdered mixture was melted in platinum doped with 10% Rhodium crucible and heated at the temperature range of 1050 °C - 1400 °C for 1-4 h then quenched in a preheated stainless steel/ graphite mould of temperature 300 °C - 600 °C and then cooled.
  • the prepared glass sample was annealed at 300 °C- 500 °C for 1 h and then cooled at the rate of 0.5 °C - 2 °C per minute to release the stress in the glass sample.
  • the prepared glass sample was cut into required size and shape using a diamond cutter.
  • the code for the present sample is called as FP4.
  • the powdered mixture was melted in platinum doped with 10% Rhodium crucible and heated at the temperature range of 1050 °C - 1400 °C for 1-4 h then quenched in a preheated stainless steel/ graphite mould of temperature 300 °C - 600 °C and then cooled.
  • the prepared glass sample was annealed at 300 °C- 500 °C for 1 h then cooled at the rate of 0.5 °C - 2 °C per minute to release the stress in the glass sample.
  • the prepared glass sample was cut into required size and shape using a diamond cutter.
  • the code for the present sample is called as FP5.
  • the density of the prepared glass samples was measured using Archimedes' principle
  • W b is the weight in water
  • p b is the density of water.
  • _, longitudinal and U s , shear) measurements were carried out using pulse echo method and cross-correlation technique.
  • the measurement system consists of an ultrasonic process control system (model FUII050; Fallon Ultrasonics Inc. Ltd., ON, Canada), a 100-MHz digital storage oscilloscope (model 54600B; Hewlett Packard, Palo Alto, CA), and a computer.
  • the measurements were carried out by generating longitudinal and shear waves using X- and Y- cut transducers operated at a fundamental frequency of 5 MHz.
  • Elemental analysis of the prepared glass sample was done using X-ray photo electron spectroscopy (model AXIS Ultra DLD; Kratos, Kyoto, Japan) with Al Ka source operating at 210 W.
  • the glass sample was ground using planetary ball mill (model PM 100; Retsch, Haan, Germany) and the powdered glass sample was used for XPS analysis.
  • a survey spectrum (0-1200 eV) was recorded and high-resolution spectra for Cls and Nls band were obtained.
  • X-ray as the excitation radiation was used for the XPS measurements.
  • the spectra were collected in a fixed retarding ratio mode with a bandpass energy of about 10 eV.
  • XRD studies were carried out on each glass sample.
  • An X-ray diffractometer (model PW 1700; Philips, Eindhoven, The Netherlands) was used with CuKa as a radiation source to obtain the XRD pattern in the range of a scanning angle between 20° and 80°.
  • the glass samples were removed from SBF solution after 21 days in vitro studies and then washed gently with double distilled water. The washed glass samples were dried at room temperature. The dried glass was subjected to obtain the XRD pattern as discussed above.
  • the prepared glass samples were soaked for 21 days in laboratory prepared SBF solution and kept in C0 2 incubator at the temperature of 37 °C in 6% C0 2 .
  • the variation in pH values of simulated body fluid (SBF) solutions was measured on all the 21 days using a pH meter (model 3-star; Thermo Orion, Beverly, MA) for all glasses under identical conditions.
  • the pH electrode was calibrated using the standard buffer solution with a pH value of 4.01, 7.00, and 10.01 before taking the measurements.
  • the percentage error in the measurement of pH is ⁇ 0.005.
  • the surface morphology of the prepared glass sample was explored using SEM studies.
  • the glass samples were gently washed with double-distilled water and dried at room temperature.
  • a thin layer of a gold film was coated on the surface of glass sample using sputtering technique.
  • the SEM (model Ultra 55; Zeiss, Oberkochen, Germany) was used to obtain a surface image of all glass samples before and after in vitro studies to explore their surface morphology.
  • EDS Energy dispersive X-ray spectrograph
  • Nontoxic nature of the selected glass sample was assessed using cytotoxicity study in cell culture lines.
  • Human gastric adenocarcinoma (AGS) cell line (ATCC-1739) was obtained from the National Centre for Cell Science, Pune, India. The cells were grown and maintained in Dulbecco's modified Eagle's medium (DMEM)/nutrient mixture F-12 HAM (1 : 1) with 2mM L "1 glutamine supplemented with 10% fetal bovine serum, 45 IU ml "1 penicillin and 45 IU ml "1 streptomycin. Growth ingredients were also added and incubated in a humidified atmosphere at 37 °C in 5% C0 2 .
  • DMEM Dulbecco's modified Eagle's medium
  • F-12 HAM (1 : 1) with 2mM L "1 glutamine supplemented with 10% fetal bovine serum, 45 IU ml "1 penicillin and 45 IU ml "1 streptomycin. Growth ingredients were also added and incubated in a humidified atmosphere
  • the pure confluent AGS cell lines were obtained and cells at a density of 10 3 were used to evaluate the cytotoxicity at a concentration of 100 mg ml 1 for the selected bioactive glass samples.
  • the morphology of AGS cell lines was observed regularly under binocular inverted microscope.
  • MTT 3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide
  • the percentage of cell viability from triplicates of the bioactive glass treated and non-treated cells was calculated using optical density (OD 590 nm) as follows:
  • I.600 Kg were purchased from King Institute, India as per CPCSEA guidelines. Under ketamine anaesthesia, one centimetre incision was made over the medical epicondyle of femur under image control. Under microscopic magnification, Periosteum was opened and a 2 mm drill hole was made. The selected sample of fluorophosphate glass rod of diameter 2 mm was pegged into the hole. After saline wash, wound was closed using single layer 3-0 ethilon sutures and then 250 mg of ceftriaxone was given intra-muscularly.
  • Calcein fluorescence was used to examine the newly formed bone using a confocal laser scanning microscope (model Fluoview-IX70; Olympus, Tokyo, Japan). The excitation wavelength was set at 488nm (Ar laser). Calcein fluorescence was detected through a BP 515 -565 nm bandpass filter.
  • the un-decalcified section of the implant was dried at room temperature using desiccator.
  • a thin layer of a gold film was coated on the surface of glass sample using sputtering technique.
  • SEM and EDS studies were done on the dried slice to find the formation of HAp at the glass-bone interface. Details obtained from the Figures:
  • Fig. 1 illustrates the protocol used for the synthesis of phosphate based glass samples with different contents of fluorine.
  • Fig. 2 The density variation of the prepared glass samples as a function of added CaF2 content is shown in Fig. 2.
  • Further addition of calcium fluoride leads to increase in the density up to 2636.6 kgm 3 for 2.5 mol% of CaF 2 .
  • the observed behaviour explains the alteration of glass network by fluorine atom.
  • Fig. 3a and 3b shows the variation of elastic moduli of all .
  • the prepared glass samples as a function of CaF 2 content Elastic moduli such as longitudinal, shear, young's and bulk modulus shows the same trend with the initial addition of CaF 2 .
  • Further addition of CaF 2 increase all the elastic constants.
  • the glass containing 2.5 mol% of CaF 2 showed the maximum moduli value than the other CaF 2 added glasses.
  • Fig. 4 shows the elemental composition of the glass sample FP3 using XPS.
  • the observed intensity at the binding energies at 437.6 eV, 348 eV, 135.2 eV, 1072.5 eV, 534.8 eV, 684.8 eV shows respectively the presence of CaO, CaF 2 , P205, Na20, O and F in the glass sample FP3.
  • SEM image of the prepared glass sample FP3 is showed in Fig. 5.
  • the smooth surface of the glass sample FP3 obtained from SEM image exhibits the amorphous nature of the sample.
  • Fig.6 shows EDS spectrograph of the glass sample FP3. A close observation is noted between experimental and nominal composition of the glass sample FP3.
  • Fig. 5 and Fig. 6 confirm the presence of fluorine atom in the glass network.
  • FTIR spectrograph of all the prepared glass samples after in vitro studies is shown in the Fig. 8.
  • the FTIR absorption assignment band at 470 cm “1 , 530 cm “1 , 720 cm “1 , 893 cm “1 , 1000 cm “1 , 1116 cm “1 , 1275 cm “1 , 1630 cm “1 , 3640 cm “1 are respectively of vibration bands of P0 3" , HAp, P-O-P (asymmetric mode), P-O-P (asymmetric mode), P0 3 2" , P-0 (stretching mode), hydrogen bending mode vibration of water and water associated in HAp.
  • the presence of HAp confirms the bone bonding ability of all the glass samples.
  • XRD patterns of all the glass after in vitro studies are shown in Fig. 9.
  • Fig. 10 shows the SEM image of the glass sample FP3 after in vitro studies.
  • the SEM image confirms the rich deposit of Ca-P layer on FP3 glass surface.
  • the size of the deposited particles is in the order of 20-100 nm.
  • Fig. 11 shows the elemental composition of the deposited precipitate using EDS.
  • the Ca/P ratio of the deposit is about 1.6 indicating the deposit is HAp.
  • the presence of fluorine molecules in the surface precipitate confirms the existence of fluoroapatite.
  • the EDS spectrograph clearly indicates the presence of hydroxyapatite and fluoroapatite on the surface of the glass sample FP3.
  • Fig. 12 shows the optical microscope image of cell viability test for the sample FP3. The image clearly shows there is no cytotoxicity observed in the glass sample FP3.
  • Fig. 13a shows the SEM image at 100X magnification of un-decalcified section of the femoral condyle of the rabbit after 10 weeks of glass implanting. The micrograph shows bone conversion morphology of the glass sample FP3 in femoral condyle of the rabbit. A uniform change in glass size and structure of the implanted glass is well observed on the entire circumference.
  • Fig 13b at 200X magnification the differential layering between the glass and bone in the form of an interface, binding the glass to bone is clearly shown.
  • Fig. 13c shows the EDS spectrum of the glass-bone interface.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
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  • Organic Chemistry (AREA)
  • Transplantation (AREA)
  • Epidemiology (AREA)
  • Inorganic Chemistry (AREA)
  • Dermatology (AREA)
  • Medicinal Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
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  • Animal Behavior & Ethology (AREA)
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Abstract

La présente invention concerne un procédé de fabrication de verres à base de phosphates additionnés de fluor de composition variée, ainsi que leur utilisation. Les propriétés physiques desdits verres à base de phosphates additionnés de fluor ont été évaluées par des mesures de densité, des mesures de vitesse des ultrasons, des schémas de diffraction des rayons X sur poudre, des spectres FT-IR, des variations du pH au cours de 21 jours d'études in vitro dans une solution de SBF, sur des images MEB, des spectres EDS et au moyen d'un spectrographe XPS. Une couche enrichie en HaP est formée à la surface de verres fluorophosphatés durant des études in vitro. Les études de cultures de cellules ex vivo ont confirmé que les verres ainsi fabriqués ne sont pas toxiques. La bioconversion a été confirmée par des études sur des animaux in vivo consistant à implanter ce verre dans le condyle fémoral de lapins adultes pendant 10 semaines, comme visualisé sur des images MEB, des spectres EDS et des images CLSM. De toutes les combinaisons, c'est l'échantillon de verre FP3 qui s'est révélé le plus adapté à de futures applications cliniques.
PCT/IN2014/000757 2013-12-12 2014-12-09 Bioactivité de verres fluorophosphatés et leur procédé de fabrication WO2015087345A1 (fr)

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WO2018118762A1 (fr) * 2016-12-23 2018-06-28 Ecolab Usa Inc. Inhibiteurs de tartre solides à libération contrôlée
US10081758B2 (en) 2015-12-04 2018-09-25 Ecolab Usa Inc. Controlled release solid scale inhibitors
US10865339B2 (en) 2016-05-16 2020-12-15 Championx Usa Inc. Slow-release scale inhibiting compositions

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KNOWLES J C: "Phosphate based glasses for biomedical application", JOURNAL OF MATERIALS CHEMISTRY, ROYAL SOCIETY OF CHEMISTRY, GB, vol. 13, 14 August 2003 (2003-08-14), pages 2395 - 2401, XP002633096, ISSN: 0959-9428, [retrieved on 20030814], DOI: 10.1039/B307119G *

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WO2018118762A1 (fr) * 2016-12-23 2018-06-28 Ecolab Usa Inc. Inhibiteurs de tartre solides à libération contrôlée
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