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WO1996038396A1 - Agent pour l'impregnation de la pierre et de corps façonnes en pierre, ou pour la production de produits malaxes modelables, ainsi que produits malaxes renfermant ces agents et des matieres solides minerales - Google Patents

Agent pour l'impregnation de la pierre et de corps façonnes en pierre, ou pour la production de produits malaxes modelables, ainsi que produits malaxes renfermant ces agents et des matieres solides minerales Download PDF

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Publication number
WO1996038396A1
WO1996038396A1 PCT/AT1996/000101 AT9600101W WO9638396A1 WO 1996038396 A1 WO1996038396 A1 WO 1996038396A1 AT 9600101 W AT9600101 W AT 9600101W WO 9638396 A1 WO9638396 A1 WO 9638396A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
plasticine
acid
lime
stone
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/AT1996/000101
Other languages
German (de)
English (en)
Inventor
Adolf Goll
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
STONETEC ANSTALT/STONETEC ESTABLISHMENT
Original Assignee
STONETEC ANSTALT/STONETEC ESTABLISHMENT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by STONETEC ANSTALT/STONETEC ESTABLISHMENT filed Critical STONETEC ANSTALT/STONETEC ESTABLISHMENT
Priority to AU58052/96A priority Critical patent/AU5805296A/en
Publication of WO1996038396A1 publication Critical patent/WO1996038396A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/24—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing alkyl, ammonium or metal silicates; containing silica sols
    • C04B28/26—Silicates of the alkali metals
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/5076—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with masses bonded by inorganic cements
    • C04B41/5089—Silica sols, alkyl, ammonium or alkali metal silicate cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/72—Repairing or restoring existing buildings or building materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/91—Use of waste materials as fillers for mortars or concrete

Definitions

  • the present invention relates to an agent for the impregnation or preservation of stone and of shaped articles made of stone, in particular plastic stone formations which are exposed to the weather, or a means for producing modeling clay for building shaped articles on a mineral basis, which agent comprises one or contains several inorganic silicon compounds.
  • Another object of the present invention is a modeling clay for the restoration of stone material, with the aid of which moldings based on minerals can be built up or additions made to stone moldings.
  • this modeling clay is used to create a material that is suitable for repairing existing moldings as well as for putting creative ideas into practice.
  • Water glass is a relatively inexpensive material based on alkali metal orthosilicates, which is converted into SiO 2 and alkali carbonate after application by the carbon dioxide in the air.
  • the resulting silica gel surrounds the stone surface and provides protection against further attack by the atmospheres.
  • the conversion reaction mentioned proceeds very quickly, so that there is no great depth of penetration of the solution into the stone material. This is partly due to the high viscosity of the water glass solutions.
  • the surface protection is therefore only noticeable to a depth of a few millimeters.
  • the alkali carbonates formed at the same time are formed in relatively large quantities and represent a water-soluble undesirable by-product. Overall, the methods for stone preservation with the aid of water glass solutions were classified as inadequate decades ago.
  • the magnesium salt MgSiFg which has been mainly used up to now, also supplies silica gel, for example in limestone preservation, with calcium fluoride, magnesium fluoride and CO2 as by-products arise. There is no positive assessment of this salt as a stone preservative in the literature.
  • silica esters are used most frequently nowadays, and it is stated that they also disintegrate to form silica gel SiO 2, the alcohols bound as esters being formed as harmless, soluble by-products.
  • the poor depth of penetration observed in water glass solutions and the formation of by-products which damage the building structure - salts - are avoided with this process. Nevertheless, this method is not necessarily recommended by the experts, since a surface seal is created which prevents any breathing of the underlying material.
  • a surface layer forms with the hydrophobic material, which subsequently shows even greater abrasion than before. Preservation over a period of more than about 20 years is not possible in this way.
  • This agent is primarily suitable for the impregnation of silicate stone materials, although the treatment of lime materials such as marble is also possible.
  • the agent according to the invention is colorless and has a surprisingly high penetration depth of up to 3-4 cm.
  • the pore compaction achieved and the associated surface compaction result in an excellent weather resistance on a stone surface treated with the agent according to the invention, which was not previously achievable. Even after a long time, no microcracks are formed, so that the preservation is extremely effective over long periods.
  • the agent primarily contains sodium metasilicate and / or potassium metasilicate, the formulas of which are given as Na2Si ⁇ 3 or ⁇ SK ⁇ .
  • the concentration of the alkali metal silicate is preferably 0.02-0.05 molar.
  • a mixture of sodium and potassium metasilicate has proven to be favorable for the impregnating agent.
  • Fluorosilicic acid, sulfuric acid, hydrochloric acid, nitric acid or formic acid is usually used as the acid.
  • the preferred acid for use in the agent of the invention is fluorosilicic acid.
  • the pH of the resulting solution is generally in the range from 1 to 4, the acidic ranges 1 to 2.5, preferably 1.5 to 2.2 being preferred for certain purposes, but in other cases the values being 2 to 4, especially 2 to 3 lead to better results.
  • the new agent preferably contains one or more alkali salts, for example rock salt, or salts as the electrolyte, which originate from the fact that alkali carbonates or ammonia are added to raise the pH.
  • the agent contains copper sulfate in addition to or instead of alkali salts.
  • the electrolyte concentration is advantageously 0.02-0.1, preferably 0.02-0.08, normal.
  • the new agent is formed by mixing the following three batches in a volume ratio of approximately 1: 1: 1:
  • Batch 2 Aqueous solution of alkali metasilicate with a molarity of 0.09 - 0.13.
  • Batch 3 Aqueous solution of one or more alkali carbonates with a concentration of 1 g / 1 to 2 g / 1 and / or copper sulfate with a concentration of 1 g / 1 to 2 g / 1.
  • batch 3 can be made from a rock salt solution with e.g. There are 8 - 12 g rock salt per liter of water.
  • the agent according to the invention is preferably formed by mixing the following batches in a volume ratio of 1: 1: 0.2: 0.8:
  • Batch 2 Aqueous solution of alkali metasilicate with a concentration of 5 to 15 g / 1.
  • Batch 3 Aqueous solution of copper sulfate with a concentration of 5 g / 1 to 10 g / 1 and / or potassium carbonate with a concentration of 5 g / 1 to 10 g / 1.
  • Batch 4 Aqueous solution of metasilicate, preferably potassium metasilicate with a concentration of up to about 11.5 g / 1 or
  • Batch 2 preferably consists of a sodium metasilicate solution.
  • batch 3 preferably consists of an aqueous solution of copper sulfate with a concentration of 1 g / 1 to 2 g / 1 and / or potassium carbonate with a concentration of 1 g / 1 to 2 g / 1.
  • the agent according to the invention preferably contains fluorosilicic acid, in particular in an amount of 28-34 g / 1, ideally about 31 g / 1.
  • Batch 2 preferably contains about 14 g / 1 sodium metasilicate.
  • a major problem with stone renovation is not only the impregnation and preservation, but above all the build-up of plastic stone formations or the production of additions to them, since often smaller or larger parts of the stone structure are missing and must be replaced during restoration .
  • the invention therefore also relates to a plasticine for the construction of moldings on a mineral basis, which according to the invention consists of an agent mentioned above in a mixture with the following solid constituents:
  • powdery material consisting of quartz powder, limestone powder, powdered Jurassic lime, spade, diatomaceous earth, trass and possibly up to 10% by weight of cement.
  • the amount of sands is reduced by the amount of cement, the ratio of the sands to one another remaining the same.
  • Margaretener Sand has proven to be extremely cheap as a component of the granular material. Margaretener Sand is a material that occurs naturally in St. Margareten, Burgenland, Austria.
  • a modeling clay for building shaped bodies on a mineral basis for hobbyists and artists consists of an above-mentioned agent in a mixture with the following solid components: about 2 parts by weight of granular material with a grain size up to 1 mm, consisting of lime sand, quartz sand and margareten sand and about 1 part by weight of floury material consisting of quartz powder, lime powder, flour from Jurakalk, heavy spar, diatomaceous earth, trass and cement.
  • floury material consisting of quartz powder, lime powder, flour from Jurakalk, heavy spar, diatomaceous earth, trass and cement.
  • Another preferred modeling clay consists of an agent mentioned above in a mixture with the following solid constituents: about 50 to 70% by weight of lime sand with a grain size of up to 2 mm, 5 to 10% by weight of margareten sand with a grain size of up to 1 mm,
  • floury material consisting of lime powder, flour from Jurassic lime, heavy spar, diatomaceous earth, trass and cement.
  • the sands preferably have a grain size of 0-2 mm, or 0-1 mm, in particular 0.5-1.5 mm.
  • the ratio of grain size 0-1 mm to grain size 0-2 mm is preferably about 1: 1, but any other mixing ratios can be selected depending on the requirements.
  • the modeling clay according to the invention can also contain about 2.5% by weight of water glass.
  • the stone moldings obtained from the modeling clay according to the invention are not cement-bound material, as is understood in the construction industry.
  • the liquid agent mentioned is processed with the solids in a weight ratio of about 1 part solution to about 4 to 6 parts solids.
  • a different weight ratio may also be required in order to produce a kneadable mass from which stone structures can be formed or which can be used to build up and supplement missing stone parts.
  • the products can be placed outdoors after a short time to let them dry, where they slowly petrify. The increase in strength lasts for many weeks and reaches its maximum depending on the composition, sometimes only after one to two years. It can be beneficial to moisten the stone products temporarily or occasionally in the first period after shaping.
  • the solids advantageously contain 36-66% by weight of lime sand with a grain size of 0 to 2, 25-28% by weight of quartz sand with a grain size of 0 to 2, 4.5 to 6% by weight of quartz powder, 7 to 13% by weight of lime powder, 1.5 to 2.0% by weight Jurassic lime powder, 2.0 to 2.3% by weight spade powder, 2.2 to 2.8% by weight diatomaceous earth powder, 1.2 to 1.7% by weight % Trass powder, 5 to 9% by weight margareten sand 0-1 mm and optionally 2 to 10% by weight cement.
  • aqueous solution up to about a quarter by an aqueous solution of sodium water glass and / or potassium water glass containing 3 - 3, 6% by weight of sodium water glass and 3 - 3.6% by weight) of potassium water glass.
  • the modeling clay according to the invention was deformed into numerous larger and smaller test specimens, left to harden and analyzed with regard to the mechanical properties which formed. It was found that the bodies formed had an extraordinarily high strength and that they gave a visual impression of natural stone, which suggests that stone blocks were produced in a similar way in prehistoric times. In this way, many puzzles with regard to the origin and transport of stone blocks among the indigenous peoples for whom no clarification has yet been found. Due to the slow hardening, there is no tendency to crack during petrification. This property is particularly important in the production of very large stone blocks and was extremely unexpected. In this way, blocks weighing several tons can be produced without any difficulties arising during curing.
  • the moldings obtained in this way are waterproof and can also be used under water after curing. They can be processed, sanded and cut with the appropriate tools and, depending on the choice of the starting material, have a shade of gray to warm yellow.
  • Batch 1 100 g of 34% by weight commercially available fluorosilicic acid ⁇ SiF ⁇ are added to 1 liter of water. The solution is stable and can remain as an approach.
  • Batch 2 5 to 15 g of commercially available alkali metal silicate are dissolved in 1 liter of water. 14 g of sodium metasilicate are preferably added to 1 liter of water.
  • Batch 3 1-2 g of copper sulfate and 1-2 g of potassium carbonate are dissolved in 200 ml of water.
  • Batch 4 up to 9 g of metasilicate, preferably potassium metasilicate, are dissolved in 800 ml of water or up to 9 g of silica gel, preferably as a silica gel solution, are dissolved in 800 ml of water.
  • metasilicate preferably potassium metasilicate
  • the resulting solution serves as an impregnating agent for the preservation or consolidation of stone formations.
  • Liquid for producing a modeling clay Liquid for producing a modeling clay
  • Batch 2 14 g of sodium metasilicate in 1 liter of water.
  • Batch 3 1-2 g of copper sulfate and 1-2 g of potassium carbonate in 1 liter of water.
  • the pH increase can be carried out in a manner similar to that of the stone consolidation agent mentioned above.
  • a preferred solid mixture for producing a modeling clay has the following composition:
  • test specimens made from this modeling clay quickly become harder at first, but often reach their maximum strength after months or years.
  • the strength measurements initially showed values of up to 8 N / mm, which rose over time (after more than about 2 years) to 25 to 30 N / mm ".
  • the plasticine can contain marble as part of the granular material.
  • It preferably contains 2 to 10% by weight of cement and / or approximately 2.5% by weight of water glass.
  • the solids can preferably contain 36-66% by weight »lime sand 0-2.
  • the solids can contain 25-28% by weight quartz sand 0-2.
  • the solids can contain 4.5 to 6% by weight of quartz powder and / or 7 to 13% by weight of lime powder and / or 2 to 4% by weight of Jurassic lime powder and or 2.0 to 2.3% by weight of spar powder , preferably feldspar or heavy spar and / or 2.2 to 2.8% by weight diatomaceous earth and / or contain 1.2 to 1.7% by weight of trass powder and / or 5 to 9% by weight of margareten sand 0-1.
  • Ash or oxidic pigments may be included to achieve color.
  • the aqueous solution can be up to about a quarter in size by a solution of sodium water glass and / or potassium water glass with a content of 3 - 3.6% by weight sodium water glass and 3 - 3.6% by weight potassium water glass be replaced.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

En vue d'imprégner et de conserver un matériau en pierre, il est prévu un agent aqueux renfermant au moins un composé de silicium inorganique et constitué, conformément à l'invention, par une solution acide, à formulation aqueuse, d'un métasilicate alcalin, et contenant un électrolyte. On utilise de préférence du métasilicate de sodium et, principalement, du métasilicate de potassium. Comme électrolyte, on utilise dans cet agent, des sels de métaux alcalins ou des sels d'ammonium. Comme acide, on utilise un acide fort, de préférence, de l'acide fluosilicique. Le pH est porté de préférence à 2,5 par addition d'une solution d'ammoniaque. Pour la constitution de corps façonnés à base minérale, une solution appropriée est additionnée de matières solides minérales granulaires et pulvérulentes et transformée en un produit pâteux durcissant lentement en le laissant reposer.
PCT/AT1996/000101 1995-06-02 1996-06-03 Agent pour l'impregnation de la pierre et de corps façonnes en pierre, ou pour la production de produits malaxes modelables, ainsi que produits malaxes renfermant ces agents et des matieres solides minerales Ceased WO1996038396A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU58052/96A AU5805296A (en) 1995-06-02 1996-06-03 Agent for impregnating stone and shaped stonework or for the production of modelable compounds and compounds containing said agent and mineral solids

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
AT94895 1995-06-02
ATA948/95 1995-06-02
AT51796 1996-03-20
ATA517/96 1996-03-20

Publications (1)

Publication Number Publication Date
WO1996038396A1 true WO1996038396A1 (fr) 1996-12-05

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PCT/AT1996/000101 Ceased WO1996038396A1 (fr) 1995-06-02 1996-06-03 Agent pour l'impregnation de la pierre et de corps façonnes en pierre, ou pour la production de produits malaxes modelables, ainsi que produits malaxes renfermant ces agents et des matieres solides minerales

Country Status (2)

Country Link
AU (1) AU5805296A (fr)
WO (1) WO1996038396A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU689429B3 (en) * 1997-10-27 1998-03-26 McDonald, Gordon Kenneth Colouring cementitious products
EP1004636A3 (fr) * 1998-11-27 2000-06-14 Garcia Asensio, Julian Composition et procédé de restauration de surfaces autres que le bois
WO2000058236A1 (fr) * 1999-03-25 2000-10-05 No-Pintatekniikka Oy Utilisation de quartz et de materiaux du type silicate pour le traitement de ceramique et de mineraux naturels
US7451760B2 (en) 2000-02-11 2008-11-18 Respironics (Uk) Ltd. Controlling drug delivery apparatus
US11629059B2 (en) 2019-08-29 2023-04-18 Covia Holdings Llc Ultra-white silica-based filler

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4819203B1 (fr) * 1970-01-31 1973-06-12
DE2911599A1 (de) * 1979-03-24 1980-10-02 Reinhold Drees Verfahren und stein zur abdichtung eines mauerwerkes gegen feuchtigkeit und wasser mit einer sperre
FR2533579A1 (fr) * 1982-09-29 1984-03-30 Magyar Tudomanyos Akademia Procede pour consolider et rendre etanche a l'eau des constructions d'infrastructures et de batiments, des objets de construction, en particulier des canaux et des canalisations, des elements de construction, des roches et des terrains
JPS6040189A (ja) * 1983-08-16 1985-03-02 Nippon Chem Ind Co Ltd:The 溶液型土質安定化剤
DD284211A5 (de) * 1987-04-02 1990-11-07 Univ Schiller Jena Verfahren zur herstellung von kieselgel mit durch modifizierung des hydrogels waehlbaren strukturellen eigenschaften
CH684796A5 (fr) * 1992-06-17 1994-12-30 Sarrasin Ingenieurs S A Procédé de protection pour assurer la longévité des constructions en béton.

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4819203B1 (fr) * 1970-01-31 1973-06-12
DE2911599A1 (de) * 1979-03-24 1980-10-02 Reinhold Drees Verfahren und stein zur abdichtung eines mauerwerkes gegen feuchtigkeit und wasser mit einer sperre
FR2533579A1 (fr) * 1982-09-29 1984-03-30 Magyar Tudomanyos Akademia Procede pour consolider et rendre etanche a l'eau des constructions d'infrastructures et de batiments, des objets de construction, en particulier des canaux et des canalisations, des elements de construction, des roches et des terrains
JPS6040189A (ja) * 1983-08-16 1985-03-02 Nippon Chem Ind Co Ltd:The 溶液型土質安定化剤
DD284211A5 (de) * 1987-04-02 1990-11-07 Univ Schiller Jena Verfahren zur herstellung von kieselgel mit durch modifizierung des hydrogels waehlbaren strukturellen eigenschaften
CH684796A5 (fr) * 1992-06-17 1994-12-30 Sarrasin Ingenieurs S A Procédé de protection pour assurer la longévité des constructions en béton.

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, vol. 103, no. 12, 23 September 1985, Columbus, Ohio, US; abstract no. 92155a, XP000064368 *
DATABASE WPI Section Ch Derwent World Patents Index; Class E37, AN 73-34771U, XP002014001 *
DATABASE WPI Section Ch Week 9115, Derwent World Patents Index; Class E36, AN 91-102733, XP002014002 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU689429B3 (en) * 1997-10-27 1998-03-26 McDonald, Gordon Kenneth Colouring cementitious products
EP1004636A3 (fr) * 1998-11-27 2000-06-14 Garcia Asensio, Julian Composition et procédé de restauration de surfaces autres que le bois
ES2147532A1 (es) * 1998-11-27 2000-09-01 Restacris S L Composicion y metodo para la restauracion y/o renovacion de superficies sin base de madera.
WO2000058236A1 (fr) * 1999-03-25 2000-10-05 No-Pintatekniikka Oy Utilisation de quartz et de materiaux du type silicate pour le traitement de ceramique et de mineraux naturels
US7451760B2 (en) 2000-02-11 2008-11-18 Respironics (Uk) Ltd. Controlling drug delivery apparatus
US8967140B2 (en) 2000-02-11 2015-03-03 Profile Respiratory Systems Limited Controlling drug delivery apparatus
US11629059B2 (en) 2019-08-29 2023-04-18 Covia Holdings Llc Ultra-white silica-based filler

Also Published As

Publication number Publication date
AU5805296A (en) 1996-12-18

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