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WO1990011066A1 - Procede de production d'un produit ceramique lie chimiquement et produit fabrique selon ledit procede - Google Patents

Procede de production d'un produit ceramique lie chimiquement et produit fabrique selon ledit procede Download PDF

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Publication number
WO1990011066A1
WO1990011066A1 PCT/SE1990/000124 SE9000124W WO9011066A1 WO 1990011066 A1 WO1990011066 A1 WO 1990011066A1 SE 9000124 W SE9000124 W SE 9000124W WO 9011066 A1 WO9011066 A1 WO 9011066A1
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WO
WIPO (PCT)
Prior art keywords
liquid
binding agent
powder
compact
raw
Prior art date
Application number
PCT/SE1990/000124
Other languages
English (en)
Inventor
Sevald Forberg
Leif Hermansson
Li Jianguo
Original Assignee
Doxa Certex Aktiebolag
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Filing date
Publication date
Application filed by Doxa Certex Aktiebolag filed Critical Doxa Certex Aktiebolag
Publication of WO1990011066A1 publication Critical patent/WO1990011066A1/fr

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Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/15—Compositions characterised by their physical properties
    • A61K6/17—Particle size
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/70—Preparations for dentistry comprising inorganic additives
    • A61K6/71—Fillers
    • A61K6/74—Fillers comprising phosphorus-containing compounds
    • A61K6/75—Apatite
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/70—Preparations for dentistry comprising inorganic additives
    • A61K6/71—Fillers
    • A61K6/77—Glass
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
    • A61K6/813—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising iron oxide
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
    • A61K6/816—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising titanium oxide
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/802—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics
    • A61K6/818—Preparations for artificial teeth, for filling teeth or for capping teeth comprising ceramics comprising zirconium oxide
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/849—Preparations for artificial teeth, for filling teeth or for capping teeth comprising inorganic cements
    • A61K6/851—Portland cements
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/849—Preparations for artificial teeth, for filling teeth or for capping teeth comprising inorganic cements
    • A61K6/853—Silicates
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/849—Preparations for artificial teeth, for filling teeth or for capping teeth comprising inorganic cements
    • A61K6/86—Al-cements
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/849—Preparations for artificial teeth, for filling teeth or for capping teeth comprising inorganic cements
    • A61K6/864—Phosphate cements
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/849—Preparations for artificial teeth, for filling teeth or for capping teeth comprising inorganic cements
    • A61K6/876—Calcium oxide
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K6/00—Preparations for dentistry
    • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
    • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
    • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • A61K6/889—Polycarboxylate cements; Glass ionomer cements

Definitions

  • the present invention relates to Chemically Bonded Cera ⁇ mics (CBC) , i.e. chemically bonded materials as compared to other advanced ceramics, which usually are made by a si tering process at elevated temperatures. More specifically the invention relates to a method for the production of a chemically bonded ceramic product by a reaction between on or several pulverulent binding agents and a liquid which r acts with these binding agents.
  • the ceramic product can al include one or several aggregates, which essentially do n react chemically with the other components.
  • the invention also relates to the product manufactured according to the method.
  • the CBC-materials are a very large and heterogenous group of materials, which include anything from concrete, based on a conventional Portland cement, to advanced ceramics i the dental field as well as in the orthopaedics, to name few of the fields of application of the CBC-materials.
  • CBC-ma- terial Another example of a material which can be called a CBC-ma- terial is the cement, which is used in the dental field and which is based primarily on zinc oxide and orthophospho ric acid. This cement has been used for temporary filling fastening of crowns etc., but its strength has so far been unsatisfactory and it can not be used as permanent fillings
  • Another type of material used for dental applications are the so called glass polyalkenoate cements and similar mate ⁇ rials.
  • SE-B-381 808, EP-A-0024056 and EP-A-0115058 exempli ⁇ fy this type of material.
  • stiffening substances for dental or general or ⁇ thopedic applications must meet several require ⁇ ments in order to be rated as satisfactory and accepted sub stances, e.g. having hygienic and in the dental field also aesthetic properties. Also, these materials must not contai components, which are toxic or which in their environment can give rise to toxic substances. Furthermore, they must b functional, have mechnical properties designed for their field of use, be corrosion resistant, comfortable to use, be biological compatible, have an acceptable appearance as well as not be too expensive to use. An important property of a stiffening substance for dental applications on human beings is also that it stiffens slowly in order to make it possible to perform the desired application without great speed.
  • Such a stiffening material must comparatively quickly become sufficiently tough and suffi ⁇ ciently fastened in order to allow the treated person to eat a reasonably short time after the application.
  • the abov mentioned hydration materials, zinc oxide-based materials, glasspolyalkeonate cement materials etc. satisfy these re ⁇ quirements for dental materials as regards i.a. hygienic and aesthetic properties, toxicity etc.
  • the stren of these materials is not considered sufficient in contras to amalgams.
  • the strength properties of the CBC-mate ⁇ rials can be improved by various treatments of the compo ⁇ nents of the material or through additives of various typ Reinforcement of concrete by means of reinforcement bars one example of this technique on a macroscale.
  • reinforcement bars one example of this technique on a macroscale.
  • reinforcing fibers which e.g. can be steel fibers, ca bon fibers, glass fibers, organic fibers etc.
  • fe sible dimensions and treatment limitations constitute phy sical limits when choosing reinforcement materials and met ods designed to be used in the dental care and surgery fields.
  • the requirements as to the surface smooth ⁇ ness of the stiffening material, its flow when prepared a applied and - when it is used as a cementum mass, i.e. as an adhesive - its joint thickness of less than 50 um con titute an upper limit for the physical size of the reinfo cing particles in connection with dental and surgical app cations.
  • conventional reinforcing fibers might func tion, as to dental applications, as a footing for bacteri provided they protrude from the surrounding matrix materi and/or are not worn off concurrently with the matrix mate ial.
  • the strength of at least some cement mat rials can be improved by compacting the paste of the pulv rulent binding agent and the reacting liquid, which can b attained by means of a dispersant, more specifically a so called plasticizer (Science, Feb. 1987, pages 235-236 as well as US-4 363 667 ) .
  • a dispersant more specifically a so called plasticizer
  • the mass is homo nized and flaws are expelled through a repeated kneading.
  • the method is statistical and isolated strength-impairing air pores may remain.
  • the general object of the invention is to suggest a method for the improvement of the strength of chemically bonded ce ramic products, so called CBC-products or CBC-materials.
  • a special object of the invention is to prepare the binding agent or binding agents as well as optional aggregates, of v/hich the CBC-product will be composed, in such a way, that the user can have the use of a binding agent product, which is prepared to obtain the required strength and which the user finishes by impregnating the finished binding agent with the liquid either before the application or in situ.
  • one object is to suggest a material, which is suitable for dental applica ⁇ tions, particularly for permanent fillings.
  • one object is to suggest a material, which is suitable as a prosthesis ma terial (implant) for general orthopedic applications.
  • one object is to facilitate an in situ addition of the hydration liquid (e.g. in the form of sea water) for underwater construction
  • the hydration liquid e.g. in the form of sea water
  • a pulverulent body composed of said binding agent (s) and optional aggregates, by exerting the pulverulent body to such a high external pressure and at such a high tempera ⁇ ture, that, without sintering reactions, during the compac tion a well integrated raw compact is obtained, in which the filling density increases to at least 1.3 times the initial filling density, which is defined as that filling density, which is obtained by shaking, vibrating and/or carefully packing of the loose powder in a container, be ⁇ fore the raw compact is impregnated with the liquid.
  • the pulverulent body is preferably exerted to such a high pres sure, that the filling density increases to at least 1.5 and suitably at least 1.7 times the initial filling densit
  • said binding agent consists of one or several hydraulic bin ding agents, the hydration phases of which belong to the group of compounds, which consists of aluminates, silicate phosphates and sulphates, the liquid being a hydration li ⁇ quid, consisting of water and possibly substances dissolve in the water.
  • the preferred aluminate is calcium aluminate which can be present in various proportions between CaO and A1 2 0 3 .
  • the preferred silicate is calcium silicate wit varying proportions between CaO and Si0 2 , which is the mai component of Portland cement, which however contains also other components, e.g. A1 2 0 3 .
  • Other phases are e.g.
  • the above-mentioned substances may exist as natural minera or be produced synthetically. Irrespective of their origin they must be preliminarily treated according to conventio nal technique, which however does not constitute any part of the present invention.
  • a powder is obtained, in which the pulverulent grains have a size ranging from a submicron-size up to a maximum size of 100 urn in the largest extension of the grains.
  • An ordinary medium grain size can be as high as about 15 urn , i.e. 50 percent by weight of the grains have a size larger than abo 15 urn.
  • the shape is very irregular.
  • the pulverulent grains generally form large porous agglomerates.
  • TAP-density also called Bulk-density or Loose-dens ty for a calcium aluminate cement, e.g. of grade SECAR 71
  • a normal so called TAP-density is 32 %.
  • This can be elevated to about 39 % by shaking the powder, vibrating it or exerting it to a careful packing i the container, used to store the powder .
  • the filling dens ty in the latter condition i.e. subsequently to a vibrati a shaking or a careful compaction, which is seen as the in tial filling density as regards the method according to th invention.
  • the same can be additionally increased somewhat by impregnating the powder with a non-reacting li quid, which subsequently is removed previous to the very heavy compaction according to the invention.
  • the invention has been developed for hyd ⁇ ration materials, e.g. aluminates, silicates, phosphates and sulphates, but the invention's principal features pro ⁇ bably can be utilized also in other systems.
  • the invention can e.g. be utilized in case the binding agents mainly are one or seve ral oxides, e.g. zinc oxide, while said liquid is one or several acids, e.g. a phosphorus-based acid, preferably and mainly orthophosphoric acid.
  • an aggregate material i.e. a material which does not participate in th chemical reactions between the binding agent and the liqui but v/hich is present as a solid phase in the finished, so ⁇ lid final product.
  • agg regate materials can be reinforcements of various types, e.g. fibers of metals, carbon, glass or organic materials etc.
  • the reinforcement advantageously can be obtained by introducing long crystals, so called whiskers, e.g. of SiC Si 3 N. and/or A1 2 0 3 .
  • the CBC-material accordi to the invention can include aggregate materials, provided they meet certain requirements. Thus, they must not be tox ic, they must be biocompatible, must not cause irritations in the oral cavity in the case of dental applications, mus not corrode etc.
  • a small amount of boron nitride can e.g. added to be used as a solid lubricant in connection with the compaction of the dry pulverulent material, preferably an amount of 5-15 percent by volume of the dry substance previous to the compaction and the impregnation with said liquid.
  • the aggregate material can also be e.g. hydroxylapa tite or solid solutions thereof and/or oxides of one or se veral of titanium, zirconium, zinc and aluminum and/or som prehydrated phase of the binding agent or binding agents. It is particularly advantageous " to use as aggregates out ⁇ wardly projecting, needle-shaped crystals, preferably of titanium dioxide, which are biocompatible and chemically inert in all the systems considered here, i.e. also to 8
  • Said titaniu dioxide aggregate suitably comprises three-dimensionally oriented and star-shaped, needle-shaped crystals, the thick ness of which can be a few tenths of a micrometer but the length of which normally is several times larger.
  • These cry tals are agglomerated to larger particles or agglomerates having a size of several micrometers.
  • the reinforcement ef ⁇ fect of the agglomerates in the hardened product is due to the nature of the agglomerates.
  • the bond between the setting phase and the agglomerates of titanium dioxide crys tals is improved and strengthened when the agglomerates are etched, e.g. in 0.5-10 M, particularly 1-3 M, sodium hydrox ide or in another etch solution, e.g. a mineral acid such a phosphoric acid.
  • a superplasticizer can also be admixed in a dry condition or by means of a water-free solu tion, subsequent to which the raw compact is produced.
  • a su table superplasticizer is e.g. 79 % hydrolysed polyvinyl ac tate.
  • the mean value of the liquid content in the moistened raw compact has to be low, but also within every small sub- volume the liquid content has to be low. Nevertheless, the liquid content has to be sufficient in order to dissolve th binding agent to such a high degree, that it will not be pr sent in large continuous bands throughout the finished CBC- material.
  • the binding agent is an aluminate or ano ⁇ ther hydration material and in case the material is used as tooth fillings, then long continuous bands of non-reacted ca cium aluminate would result in, when the filling gradually is v/orn off, a reaction between the aluminates and the wate in the oral cavity in a not desirable way.
  • the agg regates can be used as not only mainly reinforcement materi ⁇ als but also as agents conducive to an optimal distribution, a sufficient but not too high liquid content being available in every sub-volume for reaction with the binding agent, and consequently long continuous bands of non-reacted binding agent substance mainly being avoided.
  • the aggregate particles or the agglomerates of aggregate particles preferably have a particle size of 0.5-10 urn. It is particularly advantageous to let such particles have a mean particle size, which is considered smaller than the mean grain size of the binding agent, because then a somewhat higher initial filling densi ⁇ ty can be obtained.
  • the amount of aggregate material is pre ⁇ ferably 3-25 percent by weight of the finished CBC-material or 4-30 percent by volume of the mixture of the binding agen powder and the aggregate material in the raw compact.
  • a fine-grained binding agent phase and a somewhat coarser aggregate mate ⁇ rial phase in the powder body are used instead.
  • the main portion of the powder grains in the binding agent phase can have grain sizes of 1-20 um
  • v/hile the main portion of the grains of the aggregate materi al phase have a size distribution of 5-50 um.
  • This choice of particle size distribution betv/een the binding agent phase and the aggregate material phase will facilitate an almost total "consumption", i.e. a reaction between the binding agent phase and said liquid during the impregnation.
  • the final CBC-product will be composed of compara ⁇ tively large aggregate material particles, surrounded by completely hydrated areas and areas reacted in a correspon ⁇ ding way respectively.
  • Such a material can be particularly suitable for wear applications in wet and preferably in hydration-environments.
  • the wear may be ac ⁇ celerated due to the fact that a release from a non-hydrated phase is larger than for a thoroughly hydrated phase.
  • a cor ⁇ responding situation may exist, v/hen the binding agent is a non-hydration binding agent and the final product is de ⁇ signed for an environment, wich contains a liquid of the same type as is used as a reaction-liquid for the hardenin of the product.
  • the initial filling density i.e. the filling density be ⁇ fore the compaction according to the invention in a dry condition, is normally not higher than 40 %.
  • the filling density can be in ⁇ creased to a maximum of 50-55 %.
  • the compaction according to the invention is carried out by a cold isostatic compaction.
  • a cold isostatic compaction is an isostatic compaction carried out at such a low tempera ⁇ ture, that no sintering reactions take place, normally at ambient temperatures.
  • other types of mechanical pressing e.g. cold-rolling or forging, preferably gradual forging, can also be used.
  • the agglomerates of binding agent grains and possibly or preferably also the agglomerates of the used aggregate materials are disintegrated or crushed and the fragments are redistributed, the porosity decrea ⁇ sing and the material being homogenized.
  • the process is fa cilitated, if the used powders are treated in a non-polar liquid, e.g. petroleum ether (light petrol) , the binding force for the resulting agglomerates after the removal of the liquid being small, i.e. soft agglomerates being ob ⁇ tained.
  • a non-polar liquid e.g. petroleum ether (light petrol)
  • the powder body When a cold isostatic compaction is used, the powder body is placed in an impermeable shell, suitably a plastic shel subsequent to which the enclosed powder body is subjected to an external pressure in a liquid volume surrounding the shell, preferably a pressure higher than 200 MPa, preferab not less than 250 MPa.
  • Another method of carrying out the cold compaction of the binding agent and the optional aggregates according to the invention is by means of injection molding or extrusion, t powder also containing a solid lubricant, i.e. a polymer i an amount, which roughly is equivalent to the pore volume o the raw compact.
  • a solid lubricant i.e. a polymer i an amount, which roughly is equivalent to the pore volume o the raw compact.
  • the co paction is carried out in such a way that raw compacts are obtained having a geometrical shape adapted to the intende field of application.
  • the raw compact can e.g., when it is designed for dental applications, be a thin string, possib subdivided into easily separable sections, or small granul
  • the compaction is carried out as a cold isostatic compaction in a plastic shell
  • the raw compact suitably is kept encased in this shell up to the moment of application particularly if the raw compact contains hydration-type bi ding agents, which compact otherwise would require a packi to prevent it from being unintentionally subjected to mois ture during its transport and storage.
  • a few suitable pro ⁇ duct embodiments are shown in the accompanying drawings, i which:
  • Fig. 1 shows a string of a raw compact in a plastic shell according to a first embodiment
  • Fig. 2 shows a series of granule-shaped raw compacts in a long continuous plastic shell
  • Fig. 3 shows a section III-III in Fig. 2; and Fig. 4 shows a longitudinal section through a third possib embodiment of a raw compact in a impermeable plastic shell
  • raw compact 1 simply comprises a straight even rod, which can have a cir cular or another cross-section and a thickness of e.g. 3-7 mm, if the material is designed for dental applications.
  • the shell comprises a folded plastic film 2, which is lon ⁇ gitudinally sealed along one of the sides of " the shell, at 3a, and at its ends displays end seals 3b.
  • the length of rod 1 can be e.g. 30-200 mm.
  • Granules 4 according to Fig. 2 and 3 have a more or less spherical shape and are placed in a plastic shell 5, which e.g. can be shrink-sealed around granules 4 before the cold isostatic compaction.
  • raw compact 6 is instead designed as a rod, subdivided into sections 7 and v/eakenings 8 between the sections.
  • An impermeable plastic shell 9 is used.
  • shells 3a, 5 and 9 respectively made of a plastic material it is possible to use shells made of another po ⁇ lymer, e.g. rubber.
  • the intermediate product obtained in this way, has developed a considerable bending strength and compression strength. Consequently, it is not easy to smash or break loose pieces of the raw compact.
  • its size corresponds to the vo ⁇ lume of the desired final product or that the individual raw compacts are sufficiently small or that the raw compact has been designed with indications of fracture, so that smal pieces can be broken loose and.so that the final product can be easily reconstructed from a plurality of small raw compacts subsequent to the admixture of said liquid.
  • the impregnation with said liquid which will react with the binding agent, is done precisely when the CBC-product is to be used.
  • the raw compact is then impregnated with the chosen liquid by moistening the raw compact with the liquid or by immersing the raw compact in the liquid.
  • the pores of the raw compact now will function as capillaries, which suck in a suitable amount of the liquid. Due to the partial disintegration of the binding agent the strength o the raw compact decreases drastically; from a compression strength of about 10 MPa to a compression strength of abou 3 MPa. Consequently, the wet raw compact can now be broken and shaped into smaller pieces, if that is desirable. Con ⁇ sequently,, due to its initial disintegration its workabili ty v/ill be acceptable and it can e.g. be used as a tooth filling material.
  • a pluralit of raw compacts can be impregnated and subsequent to the impregnation be joined together to large units.
  • the inven ⁇ tion particularly facilitates an in situ-adding of the li ⁇ quid, particularly a hydration-liquid in case the binding agent is one or several hydration-binding agents.
  • the li ⁇ quid can in this case be e.g. sea water or water from lake and streams for underwater constructions, the impregnation v/ith water being carried out directly on the site of appli cation.
  • the powder in the raw compact entirely comprises a binding agent, e.g. a cement material
  • a binding agent e.g. a cement material
  • 30-60 % of the binding agent is dissolved by said liquid and is hardened by known reactions .
  • the total dissolved amount depends on several factors, e.g. the size of the pulverulent grains, their shape and distribution, but also on the degree of co paction and the size of the raw compact are important in this respect, since the hydrates which are slowly formed will constitute diffusion barriers against additional wa ⁇ ter.
  • the used aggregates can in this regard be utilized ac tively in order to maximize the hydration and the correspo ding reaction respectively in case other binding agents than hydration-materials are used. If it is assumed that the filling density in the raw compact is e.g.
  • the aggre ⁇ gate material preferably comprises needle-shaped titanium dioxide crystals, agglomerated to large particles having a size of 1-5 um , which has been described above.
  • This aggre gate material has a very high whiteness, opacity and albedo. Also, it is completely stable to light, chemically inert, biocompatible and does not cause irritations or other types of discomfort in the oral cavity as regards dental applica ⁇ tions.
  • This material comprises particles of pure titanium dioxide, comprising three-dimensional needle-shaped crystal having a star-shaped orientation. This material can be bough from e.g.
  • TIL Central Laboratories, Stockton-on-Tees in Great Britain, under the trade name "Tilcom” .
  • the thickness of the crystals is a few hundredths of a nanometer, but their length is several times larger. They are agglomerated to particles having a grain size of 0.5-10 um.
  • a calcium aluminate cement, grade Secar 71 (manufactured by Lafarge) was used as a binding agent phase.
  • Secar 71 is a mixture of CaOxAl 2 0 3 and CaOx2Al 2 ⁇ > 3 .
  • the medium grain size was about 15 um.
  • An amount of about 5 cm of said binding agent powder was isostaticly compacted in a cold condition at a pressure of 300 MPa in an impermeable plastic shell to obtain parallelepiped-shape. The filling density of the raw compact was measured to 67.5 % efter the cold isostatic com paction.
  • the plastic shell was removed and distilled water was added and the specimen was subsequently kept at 35°C and a relative humidity (RH) of 100 % for 24 hours.
  • Secar 71 according to Example 1 was isostaticly compacted in a cold condition as a block with the dimensions 4x4x8 cm at 320 MPa, and a raw compact having a density of 2.10 g/cm was obtained, which corresponds to a filling density of 70 .
  • the block compacted isostaticly in a cold condition was cut up into a few test rods with the dimensions 40x3x3 mm. Distilled water was added, and substantially half of the specimens were kept in a moist environment (100% RH - relative humidity) and the rest in water at 37°C for vary ⁇ ing periods of time. Results as to the obtained medium ben ⁇ ding strength xn MPa, the open porosity (OP) and shrinkage (K) are given in the following table.
  • cement material called OPC was used- (Ordi nary Portland Cement) .Consequentl , the cement material mainly comprised calcium silicates, CaOxSi0 2 and a small portion aluminum oxide, iron oxide etc.
  • the cement powder had a medium grain size of about 10 um .
  • the powder was isostaticly compacted in a cold condition at-
  • Example 3 a calcium aluminate of a type which is calle Fondu (trade name) was used.
  • the powder was isostaticly com ⁇ pacted in a cold condition in the same way as in Example 3.
  • the storage time in water was 7 days.
  • the raw compact was impregnated with tap water, and subse ⁇ quently the specimen was treated in the same way as in Example 3, with the following results:
  • Cement powder of grade Secar 71. i.e. of the same type as i Example 1
  • Synthetic calcium aluminate cement CaOxAl 2 0 3
  • About 40 g of the powder were isosta ticly compacted in a cold condition at 300 MPa.
  • an a superplasticizer grade Gohsenol; 79 % hydrolysed polyvi- nyl acetate
  • a portion of the speci ⁇ men cube was added, while another portion of the specimen cube was centrifuged in the solution of water and superplas cizer at 6000 RPM.
  • the specimen cube was not satisfactorily moistened v/ithout a centrifugation.
  • the centrifuged specime was crushed to small granules and was treated subsequently in the same way as in Example 5.
  • the resulting compressing strength of the final specimen cube was measured to 230 MPa
  • a superplasticizer agent (grade Gohsenol) was added to an aluminate according to Example 6 and an admixture was carri out, partly in a dry condition and partly in a light petrol solution.
  • Raw compacts were made of the powders by an isost tic compaction in a cold condition in a polymer tube. Water subsequently was forced through the tube. The tube was re ⁇ moved and the participattened mass was pounded to a parallelepip with the dimensions 40x3x3 mm. The obtained bending strengt in the hardened specimens was measured to 49 + 7 MPa in the tv/o cases.
  • grade Secar 71 To a cement raw material, grade Secar 71 (see Example 1) , boron nitride (of a type which is sold under the name HC
  • the boron nitride was a very fine pov/der, its grain fineness corresponding to
  • the mean strength of seven test rods was 61 MPa (the lo est value 42 MPa, the highest 93 MPa) , which shows that a substantial amount of a fine-grained aggregate phase can be added without a substantial decrease in the bending strengt (compare Example 1) and that the resulting strength mainly is not influenced by the degree of purity of the water, as far as this has been tested.
  • Secar 71 To a calcium aluminate cement of the same grade as in Example 1, Secar 71, was added 35 percent by volume of a po lymer binding agent for injection molding, comprising a mix ture of polyethylene and ethyl vinyl acetate.
  • the mixture o aluminate cement and polymer powder was homogenized in a mixer, type Brabender, and was injection molded at a pres ⁇ sure of 1200 bars to a parallelepiped.
  • the polymer was sub ⁇ sequently vaporized by heating to 400 C. The filling densi ty was then 65.5 %.
  • the porous raw compact obtained in thi way subsequently was impregnated with distilled water, ad ⁇ mixed v/ith 0.035 moles of a chloride salt and the moistene body was placed in water at ambient temperature. After a p riod of 24 hours its compression strength was 210 MPa. The rupture toughness of the material was measured by the i -
  • the raw compact obtained in this way can be impregnated with a hydration liquid in the way de ⁇ scribed in the examples above.
  • the water which is sucked i to the body essentially corresponds to the volume of the po system and reacts with the non-hydrated calcium aluminate cement phase to the extent that after 24 hours essentially no non-reacted phase remains. In this way a volume increas due to a diffusion of additional water and consequently an additional hydration is prevented, which would mean a hyd ⁇ ration above the available pore volume.
  • a gypsum powder - CaSO.x ⁇ H- j O - was compacted by an iso ⁇ static compaction in a cold condition at 300 MPa.
  • the raw compact obtained a density corresponding to 66 % of the theoretical density.
  • Water was subsequently added to it an it was hydrated for 24 hours.
  • Ten specimen rods (35x3x3 mm were cut. The strength was measured by the three-point ben ding test to 34 MPa (mean value; the lowest value 28 MPa and the highest 39 MPa) . This strength exceeded the streng of ordinary gypsum more than five-fold.
  • the density was 2.

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  • Health & Medical Sciences (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Veterinary Medicine (AREA)
  • Epidemiology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Chemical & Material Sciences (AREA)
  • Plastic & Reconstructive Surgery (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Electrical Discharge Machining, Electrochemical Machining, And Combined Machining (AREA)
  • Water Treatment By Sorption (AREA)
  • Vending Machines For Individual Products (AREA)
  • Materials For Medical Uses (AREA)
  • Containers And Packaging Bodies Having A Special Means To Remove Contents (AREA)
  • Dental Preparations (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

L'invention concerne un procédé de production d'un produit céramique lié chimiquement, par réaction entre un ou plusieurs agents de liaison pulvérulents, et un liquide réagissant avec lesdits agents de liaison. Ledit produit céramique peut également comprendre une ou plusieurs matières d'agregat ne participant pas essentiellement aux réactions chimiques de durcissement. Selon l'invention on rend compact un corps de poudre, comprenant le ou lesdits agents de liaison et éventuellement des matières d'agregat sans addition dudit liquide, en soumettant, avant que l'ensemble compact brut ne soit imprégné dudit liquide, ledit corps de poudre à une pression extérieure élevée telle que l'on obtient un ensemble compact brut complètement intégré, dans lequel la densité de remplissage a augmenté jusqu'à au moins 1,3 fois la densité de remplissage initiale, laquelle est définie commme étant cette densité de remplissage , obtenue par secouage, vibration et/ou compactage minutieux de la poudre déliée dans un récipient.
PCT/SE1990/000124 1989-03-20 1990-02-22 Procede de production d'un produit ceramique lie chimiquement et produit fabrique selon ledit procede WO1990011066A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SE8900972-4 1989-03-20
SE8900972A SE463493B (sv) 1989-03-20 1989-03-20 Saett vid framstaellning av en kemiskt bunden keramisk produkt samt enligt saettet framstaelld produkt

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WO1990011066A1 true WO1990011066A1 (fr) 1990-10-04

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EP (1) EP0463118A1 (fr)
AT (1) ATE127040T1 (fr)
AU (1) AU5345890A (fr)
DE (1) DE69021914T2 (fr)
ES (1) ES2089005T3 (fr)
SE (1) SE463493B (fr)
WO (1) WO1990011066A1 (fr)

Cited By (17)

* Cited by examiner, † Cited by third party
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EP0559627A2 (fr) * 1992-02-03 1993-09-08 Doxa Certex Aktiebolag Procédé de production d'un produit céramique chimiquement lié, outil employé et partie interchangeable sur cet outil
WO2000021489A1 (fr) * 1998-10-12 2000-04-20 Doxa Certex Aktiebolag Systemes d'agents liants possedant une stabilite dimensionnelle
WO2000071082A1 (fr) * 1999-05-25 2000-11-30 Albert-Ludwigs-Universität Freiburg Matiere ceramique pour la medecine, son utilisation et son procede de production
WO2001076534A1 (fr) * 2000-04-11 2001-10-18 Doxa Aktiebolag Procede de production d'un materiau ceramique a liaisons chimiques
WO2001076535A1 (fr) * 2000-04-11 2001-10-18 Doxa Aktiebolag Produit ceramique a liaison chimique, procede de production, outil utilise dans l'execution du procede, et pieces de l'outil pouvant etre remplacees
EP1321447A1 (fr) * 2001-12-21 2003-06-25 MTF MediTech Franken GmbH Procédé et appareil pour mouiller de matière brute
JP2006502106A (ja) * 2002-06-20 2006-01-19 ドクサ アクティボラグ 粉体材料とその製造方法、粉体材料の圧密原料及びその装置
JP2006502939A (ja) * 2002-06-20 2006-01-26 ドクサ アクティボラグ 化学的に接合されたセラミック材料のためのシステム、かかるセラミック材料のための粉末材料および水和水、その製造方法および装置
US7025824B2 (en) 2001-12-27 2006-04-11 Cerbio Tech Ab Ceramic material and process for manufacturing
US7074223B2 (en) 2001-12-27 2006-07-11 Cerbio Tech Ab Coating method and coated devices
EP1778163A1 (fr) * 2004-08-18 2007-05-02 Doxa AB Materiau ceramique lie chimiquement
US7351281B2 (en) 2001-09-26 2008-04-01 Doxa Aktiebolag Powdered material and ceramic material manufactured therefrom
US7402202B2 (en) 2001-09-26 2008-07-22 Doxa Aktiebolag Method for the manufacturing of a powdered material, the powdered material and a ceramic material manufactured there from
US7506759B2 (en) 2002-06-04 2009-03-24 Mtf Meditech Franken Gmbh Method and device for wetting a medical implant or transplant
US7594577B2 (en) 2002-06-04 2009-09-29 Mtf Meditech Franken Gmbh Method and device for moistening non-biological medical implant material
US7867329B2 (en) 2007-08-23 2011-01-11 Doxa Ab Dental cement system, a powdered material and a hydration liquid therefor, and ceramic material formed therefrom
WO2016005822A1 (fr) 2014-07-07 2016-01-14 Aduro Material Ab Systèmes de ciment, ciments durcis et implants

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* Cited by examiner, † Cited by third party
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SE0201052D0 (sv) * 2002-04-04 2002-04-04 Cerbio Tech Ab Biocompatible cement compositions and method of manufacturing
SE524334C2 (sv) * 2002-09-30 2004-07-27 Cerbio Tech Ab Värmegenererande biokompatibla keramiska material och förfarande för dess framställning
KR20060115398A (ko) 2003-10-29 2006-11-08 독사 악티에볼락 개선된 생체 재료의 초기 및 최종 특성을 위한 2단계시스템

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US4353746A (en) * 1979-12-03 1982-10-12 Imperial Chemical Industries Limited Hydraulic cement composition
US4353747A (en) * 1979-06-29 1982-10-12 Imperial Chemical Industries Limited Hydraulic cement composition
US4363667A (en) * 1980-04-11 1982-12-14 Imperial Chemical Industries Limited Cementitious composition and cement produced therefrom
US4689080A (en) * 1985-07-24 1987-08-25 Haruyuki Kawahara Base material composition for dental treatment

Patent Citations (4)

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US4353747A (en) * 1979-06-29 1982-10-12 Imperial Chemical Industries Limited Hydraulic cement composition
US4353746A (en) * 1979-12-03 1982-10-12 Imperial Chemical Industries Limited Hydraulic cement composition
US4363667A (en) * 1980-04-11 1982-12-14 Imperial Chemical Industries Limited Cementitious composition and cement produced therefrom
US4689080A (en) * 1985-07-24 1987-08-25 Haruyuki Kawahara Base material composition for dental treatment

Cited By (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0559627A3 (fr) * 1992-02-03 1994-01-19 Doxa Certex Ab
EP0559627A2 (fr) * 1992-02-03 1993-09-08 Doxa Certex Aktiebolag Procédé de production d'un produit céramique chimiquement lié, outil employé et partie interchangeable sur cet outil
JP2002527366A (ja) * 1998-10-12 2002-08-27 ドクサ セルテクス アクティボラグ 寸法的に安定な結合剤システム
WO2000021489A1 (fr) * 1998-10-12 2000-04-20 Doxa Certex Aktiebolag Systemes d'agents liants possedant une stabilite dimensionnelle
US6620232B1 (en) 1998-10-12 2003-09-16 Doxa Aktiebolag Dimension stable binding agent systems for dental application
WO2000071082A1 (fr) * 1999-05-25 2000-11-30 Albert-Ludwigs-Universität Freiburg Matiere ceramique pour la medecine, son utilisation et son procede de production
KR100854161B1 (ko) * 2000-04-11 2008-08-26 독사 악티에볼락 화학 결합된 세라믹 제품을 제조하는 방법 및 제품
WO2001076535A1 (fr) * 2000-04-11 2001-10-18 Doxa Aktiebolag Produit ceramique a liaison chimique, procede de production, outil utilise dans l'execution du procede, et pieces de l'outil pouvant etre remplacees
KR100757566B1 (ko) 2000-04-11 2007-09-10 독사 악티에볼락 화학적으로 결합된 세라믹 제품을 생산하기 위한 로우 컴팩트, 이의 생산을 위한 방법, 이 방법을 실행에서 사용되기 위한 도구, 및 상기 도구를 위한 컴팩트 바디
WO2001076534A1 (fr) * 2000-04-11 2001-10-18 Doxa Aktiebolag Procede de production d'un materiau ceramique a liaisons chimiques
JP2003530239A (ja) * 2000-04-11 2003-10-14 ドクサ アクティボラグ 化学結合セラミック製品の作成方法、および製品
JP2003530286A (ja) * 2000-04-11 2003-10-14 ドクサ アクティボラグ 化学結合セラミック生成物、その製造方法、方法の実施に使用するツールおよびツールの互換部品
AU2001247019B2 (en) * 2000-04-11 2005-04-07 Doxa Aktiebolag Method for producing a chemically bound ceramic product, and product
US6969424B2 (en) 2000-04-11 2005-11-29 Doxa Aktiebolag Method of producing a chemically bound ceramic product, and product
US7402202B2 (en) 2001-09-26 2008-07-22 Doxa Aktiebolag Method for the manufacturing of a powdered material, the powdered material and a ceramic material manufactured there from
US7351281B2 (en) 2001-09-26 2008-04-01 Doxa Aktiebolag Powdered material and ceramic material manufactured therefrom
EP1321447A1 (fr) * 2001-12-21 2003-06-25 MTF MediTech Franken GmbH Procédé et appareil pour mouiller de matière brute
WO2003053881A1 (fr) * 2001-12-21 2003-07-03 Mtf Meditech Franken Gmbh Procede et dispositif d'humidification d'une matiere brute
US7074223B2 (en) 2001-12-27 2006-07-11 Cerbio Tech Ab Coating method and coated devices
US7025824B2 (en) 2001-12-27 2006-04-11 Cerbio Tech Ab Ceramic material and process for manufacturing
US7506759B2 (en) 2002-06-04 2009-03-24 Mtf Meditech Franken Gmbh Method and device for wetting a medical implant or transplant
US7594577B2 (en) 2002-06-04 2009-09-29 Mtf Meditech Franken Gmbh Method and device for moistening non-biological medical implant material
JP2006502939A (ja) * 2002-06-20 2006-01-26 ドクサ アクティボラグ 化学的に接合されたセラミック材料のためのシステム、かかるセラミック材料のための粉末材料および水和水、その製造方法および装置
JP2006502106A (ja) * 2002-06-20 2006-01-19 ドクサ アクティボラグ 粉体材料とその製造方法、粉体材料の圧密原料及びその装置
EP1778163A1 (fr) * 2004-08-18 2007-05-02 Doxa AB Materiau ceramique lie chimiquement
EP1778163A4 (fr) * 2004-08-18 2010-02-24 Doxa Ab Materiau ceramique lie chimiquement
US7867329B2 (en) 2007-08-23 2011-01-11 Doxa Ab Dental cement system, a powdered material and a hydration liquid therefor, and ceramic material formed therefrom
WO2016005822A1 (fr) 2014-07-07 2016-01-14 Aduro Material Ab Systèmes de ciment, ciments durcis et implants
US10292791B2 (en) 2014-07-07 2019-05-21 Psilox Ab Cement systems, hardened cements and implants

Also Published As

Publication number Publication date
EP0463118A1 (fr) 1992-01-02
DE69021914T2 (de) 1996-03-14
AU5345890A (en) 1990-10-22
ES2089005T3 (es) 1996-10-01
SE8900972D0 (sv) 1989-03-20
DE69021914D1 (de) 1995-10-05
ATE127040T1 (de) 1995-09-15
SE8900972L (sv) 1990-09-21
SE463493B (sv) 1990-12-03

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