EP2231544A1 - Procédé d'assemblage basse température de verre et de matériaux analogues pour l'optique et la mécanique de précision - Google Patents

Procédé d'assemblage basse température de verre et de matériaux analogues pour l'optique et la mécanique de précision

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Publication number
EP2231544A1
EP2231544A1 EP08862790A EP08862790A EP2231544A1 EP 2231544 A1 EP2231544 A1 EP 2231544A1 EP 08862790 A EP08862790 A EP 08862790A EP 08862790 A EP08862790 A EP 08862790A EP 2231544 A1 EP2231544 A1 EP 2231544A1
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EP
European Patent Office
Prior art keywords
components
joining
water
joined
solution
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.)
Withdrawn
Application number
EP08862790A
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German (de)
English (en)
Inventor
Manfred Krauss
Gudrun Leopoldsberger
Gerhard Kalkowski
Ramona Eberhardt
Andreas Tuennermann
Charlotte Jahnke
Simone Fabian
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.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Publication of EP2231544A1 publication Critical patent/EP2231544A1/fr
Withdrawn legal-status Critical Current

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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
    • 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
    • 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
    • C03C27/00—Joining pieces of glass to pieces of other inorganic material; Joining glass to glass other than by fusing
    • C03C27/06—Joining glass to glass by processes other than fusing
    • 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
    • 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
    • C04B37/00—Joining burned ceramic articles with other burned ceramic articles or other articles by heating
    • C04B37/003—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts
    • C04B37/005—Joining burned ceramic articles with other burned ceramic articles or other articles by heating by means of an interlayer consisting of a combination of materials selected from glass, or ceramic material with metals, metal oxides or metal salts consisting of glass or ceramic material
    • 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
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/00637—Uses not provided for elsewhere in C04B2111/00 as glue or binder for uniting building or structural materials
    • 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
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/04—Ceramic interlayers
    • C04B2237/06—Oxidic interlayers
    • 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
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/04—Ceramic interlayers
    • C04B2237/06—Oxidic interlayers
    • C04B2237/062—Oxidic interlayers based on silica or silicates
    • 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
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/04—Ceramic interlayers
    • C04B2237/06—Oxidic interlayers
    • C04B2237/064—Oxidic interlayers based on alumina or aluminates
    • 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
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/04—Ceramic interlayers
    • C04B2237/06—Oxidic interlayers
    • C04B2237/066—Oxidic interlayers based on rare earth oxides
    • 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
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/02—Aspects relating to interlayers, e.g. used to join ceramic articles with other articles by heating
    • C04B2237/04—Ceramic interlayers
    • C04B2237/06—Oxidic interlayers
    • C04B2237/068—Oxidic interlayers based on refractory oxides, e.g. zirconia
    • 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
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
    • C04B2237/34—Oxidic
    • 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
    • C04B2237/00—Aspects relating to ceramic laminates or to joining of ceramic articles with other articles by heating
    • C04B2237/30—Composition of layers of ceramic laminates or of ceramic or metallic articles to be joined by heating, e.g. Si substrates
    • C04B2237/32—Ceramic
    • C04B2237/34—Oxidic
    • C04B2237/341—Silica or silicates

Definitions

  • the joining of at least two components made of glass, ceramic and / or glass ceramic in optical production by inorganic bonding at low temperatures is known.
  • the respective base solution additionally contains, individually or in combination, special inorganic and / or organic compounds of the following elements: Ti, B, Al, Y, Zr or Zn.
  • the corresponding solutions are made of the same and / or different materials between the surfaces to be joined of the components reacted.
  • the additives can be used to optimize the reaction time needed to adjust the components;
  • compounds with high strengths are realized with the inventive ironing solutions, the materials do not change and there are few limits to potential applications at elevated temperatures, moisture fluctuations and under vacuum.
  • Low temperature bonding also known as "low-temperature bonding” (LTB)
  • LTB low-temperature bonding
  • these mean compounds which are typically prepared in the range from room temperature to about 100 ° C.
  • Methods for joining workpieces at low temperatures through the use of solder glasses are known in the art. However, the necessary temperatures are above 150 0 C.
  • inorganic and inorganic-organic networks eg. T. prepared via the sol-gel process, the compounds of components is listed for example in the document EP 0414001 A2.
  • Two or more components of the same and different classes of materials, chemical composition, structure and / or properties (glass, glass ceramic, possibly also ceramic) according to the invention by inorganic low-temperature joining for optics and precision mechanics at low temperatures ( ⁇ 150 0 C) are produced mechanically precisely, so that mechanically very strong connections arise and / or only small optical losses occur in the transition zone.
  • one of these materials to be joined is a material with extremely low thermal expansion (so-called zero-expansion material).
  • the surfaces to be joined are usually to be cleaned before joining, which should be done in the simplest possible way and without special chemicals. In addition or additionally, they should be treated in such a way that a favorable contact angle with the joining solutions is created.
  • This contact angle should in many cases be small (i.e., less than 45 °) so that good wetting of the joining surfaces occurs. However, the contact angle must not be too low, so that the joining process is technically feasible, the joining and adjustment times can be made variable and no air is trapped between the joining surfaces. In special cases, however, the contact angle should be relatively large (50 ° up to about 75 °, in extreme cases even 90 °).
  • the object of the invention is to control the speed of the chemical reaction of the joining process and to make it variable according to the complexity of the joints. So can the process of curing the
  • the joining time i. the period in which a shift or (re) adjustment of the components to each other is possible
  • the joining time can be changed by a change in the pH, in a simple manner by the addition of Ti, B, AI, Y -, Zr or Zn-containing inorganic or organometallic solutions to Fügeansen from conventional - usually commercial - water glasses or silica sols can be achieved.
  • Nathum silicate solutions sodium water glass, eg Na2SisO 7 from Riedel-de Haen
  • lithium silicate solutions lithium water glass, eg Betol Li22 from Woellner
  • potassium silicate solutions can be used as base fuser solution
  • silica sols eg LEVASIL® 300/30%, 200A / 40% from Bayer. These are solidified with said additives at joining temperatures of preferably ⁇ 150 0 C to mechanically stable and temperature-stable joints of two or more components.
  • the forming networks between the joining surfaces are each composed of silicon, oxygen and the cation (s) added to the waterglass solution or the silica sol prior to the addition.
  • the speed of the chemical reaction of the joining process can be controlled by varying the composition of the bridging solution by means of suitable additives containing the ions to be used according to the invention, so that e.g. the necessary longer adjustment times (usually significantly more than 1 min) can be achieved when assembling complex components with optical and mechanical functions.
  • the material surfaces to be joined are preferably provided with high quality "optical polish” by grinding and polishing.
  • the geometric requirements on the surfaces are generally such that a high surface quality, the lowest possible joint gap and the most homogeneous possible layer thickness can be achieved.
  • the aim is to achieve joint gaps of ⁇ 2 ⁇ m, preferably ⁇ 160 nm.
  • the flatnesses in the initial state should be adjusted accordingly by pre-processing accordingly.
  • z. B. from BK7 or ULE typically reaches a flatness of ⁇ / 4 to ⁇ / 10 (about 160 nm to 60 nm) and roughness of 5 nm to 1 nm.
  • the high demands on the geometry of the joining surfaces must be met in order to achieve a sufficient approximation of the contact surfaces.
  • Typical materials that can be added at low temperatures are listed in Table 1. These are glasses (flat glasses, silica glasses, optical glasses) and a glass ceramic (Zerodur). Of course, the materials given in the table are pure examples to which the invention is not limited. Table 1 . Add materials
  • a suitable cleaning of the materials to be joined takes place before the low-temperature joining.
  • This is especially the RCA hot cleaning (basic standard cleaning method for silicon wafers, 1960, W. Kern, Radio Corporation of America) of the two surfaces to be joined (clean, hydrophilic, activation of the joining surfaces, approaches to reduce the defects, water, Acids / alkalis, cleaning agents, ultrasound) in question.
  • organic and metallic impurities are removed from the surfaces to be joined (complexing of, for example, Cu, Ag, Au, Zn, Cd, Ni, Co, Cr by NH 3 , formation of insoluble hydroxides and / or oxides or soluble chlorides, eg B. with the ions Al 3+ , Fe 3+ ).
  • the contact angle between Joining surfaces and joint solution is by this method less than 45 °, preferably between 1 ° and 20 °.
  • the so-called “bath cleaning” is carried out, in which special surfactants (eg Optimal 9.9 and GS10 from Olschner / Gottplingen) and with ultrasound support are used to clean Zerodur specimens can not be removed without corrosion
  • the cleaning of the Zerodur samples is therefore preferably carried out with a modified RCA method (without the HF HF cleaning step) or by bath cleaning.
  • the joining surfaces are additionally activated. This is done for example with a nitric acid treatment, for example, 30 min treatment in 10% HNO 3 , rinsing with deionized water, dripping times 1, 5 to 2 h.
  • a nitric acid treatment for example, 30 min treatment in 10% HNO 3 , rinsing with deionized water, dripping times 1, 5 to 2 h.
  • a hydrophobic contact angle about 50 to 75 °
  • silanes for example, fluorosilanes (eg, perfluorododecyl-thethoxysilane), organically crosslinkable alkoxysilanes such as MEMO (3-methacryloxy-propyltrimethoxysilane) or amino-modified alkoxysilanes such as AMO (amino-propyltrimethoxysilane) can be used.
  • fluorosilanes eg, perfluorododecyl-thethoxysilane
  • organically crosslinkable alkoxysilanes such as MEMO (3-methacryloxy-propyltrimethoxysilane)
  • amino-modified alkoxysilanes such as AMO (amino-propyltrimethoxysilane)
  • the contact angle should therefore be small (for a good, even distribution of the jointing solution on the joining surface in the case of rapid hardening) or large (the latter preferably by silanization, which means a "push-on", ie a mutual movement) Joining materials, allowing longer, while slow hardening causes long adjustment times).
  • basic silicates are alkali silicate solutions (water glasses) of different composition (Na, K, Li) and concentration (1 to 30% by weight) or silica sols of different solids contents (eg 300/30 %, 200A / 40%, wherein the first number indicates the specific surface area of the SiO 2 and the second number indicates the SiO 2 content, based on 100 parts of silica sol) with additions of inorganic and organometallic compounds of the cations according to the invention.
  • Silica sols are aqueous, colloidally disperse solutions of amorphous silica in water.
  • the soluble alkali metal silicates hydrolyze in water as silica is a weak acid. They tend to condensation in solution.
  • soda or soda water glasses contain as main constituents SiO 2 and Na 2 ⁇ . They are the water glasses of greater technical importance.
  • the ratio of SiO 2: Na 2 O varies from 3.9 to 4.1 for water-based glasses containing siliceous acid, from 3.3 to 3.5 for neutral soda water glass, and from 2.0 to 2.2 for alkaline water glass.
  • the SiO 2 : K 2 O ratios are between 1: 1 and 3.9: 1.
  • the molar ratio SiO 2 : Li 2 O is between 2.5 and 4.5.
  • Monomolecular silica is only present in high dilution. If the OH concentration is reduced, more or less rapidly (depending on concentration and pH) higher condensed silicic acids are formed, which become more and more difficult to solubilize as the degree of condensation increases, ultimately resulting in a fixed addition at low temperatures.
  • Silica sols have a pH of about 10 (Table 4). Very good (solid) compounds were obtained with silica sols with a specific surface area of SiO 2 and with SiO 2 contents (based on 100 parts of silica sol) of 100/45%, 300/30% and 200A / 40% (A denotes the particular low alkali content of silica sol).
  • the joining or adjustment times should be greater than 1 min and should preferably be at least 3 min, so that even complicated components can be joined with high precision.
  • Exemplary base waterglass solutions are shown in Table 3.
  • the basic Fügeansen be changed by the additives of the invention so that an extension of the setting and hardening times of the joints occurs and thus the time available for fine adjustment to the necessary level (greater 1 to 5 min) is extended.
  • the inventors have surprisingly found that the duration of addition of each system increases with decreasing pH.
  • the constituents to be added according to the invention to the base materials each lower their pH. Conversely, can be shortened by increasing the pH by correspondingly more basic additives, the setting and curing time, which can be advantageous for simple geometries of the components to be joined in some situations.
  • the materials do this in different ways and, by the way, fulfill other, different tasks, which will be explained in more detail below.
  • water glass contains proportions of aggregated silica, so that low-temperature additions can occur directly with waterglass without acidification.
  • Water glass acts as a binder.
  • the setting mechanism is based on neutralization (by CO 2 of the air), dehydration and cooling.
  • the removal of water by increasing the temperature (up to 200 0 C, preferably below 100 0 C), vacuum or dehydrating chemical substances (eg silica gel) provoked.
  • aqueous silica sols the amorphous silica is stabilized with minor additions of NaOH. If the OH concentration is reduced by the addition of acidic additives, more or less rapidly condensed silicic acids (isopoly acids) are formed, which become increasingly less soluble with increasing degree of condensation (see above).
  • solutions of chemical compounds are added to the respective base bridging solution, singly or in combination (concentrations 1 to 50% by weight, preferably 1 to 35% by weight). These have an influence both on the properties of the jointing solution and on the subsequently formed solid compounds or the joined components.
  • concentration 1 to 50% by weight preferably 1 to 35% by weight.
  • boric acid H 3 BO 3 It is light in water when heated, sparingly soluble in the cold and is a weak acid. It serves to neutralize the basic water glass solution or slightly basic silica sols, delays their chemical reactions with the joining surfaces and the CO 2 of the air and the formation of water-insoluble boro-silicate bonds Si-OB from water-soluble alkali borates. This lengthens the joining and adjustment times. Additional stabilization and reinforcement of the joint is carried out by dehydration and transition into metaboric [B ⁇ 2] n at 70 0 C. Trimethyl borate B (OCH 3) 3 is hydrolyzed by water to form boric acid and methanol, resulting in the extension of the joining times as boric acid is formed during the joining process. b) B2O3. This compound dissolves in water exothermically to orthoboric acid H3BO3 (up to 5% by volume) c) trimethyl borate B (OCH 3 ) 3 C.
  • Al (OH) 3 can be formed, which aggregates to higher molecular weight particles, eventually leading to colloidal distribution, forming "Al (OH) 3 -GeIe" by dewatering to increase the stability of the Si addition -O-Al and to slow down the chemical hardening reaction Suitable for the present invention are:
  • Aqueous weakly basic ammonia solution NH 3 H 2 O is generally added as an additive to the cationic solutions used in order to prevent the formation of hydroxide precipitates by formation of soluble complex compounds (eg [Al (OH) 4 ] " , [Zn (NH 3 ) 4 ] 2+ ] in the pad solutions (not for Ti, Zr-Y containing solutions).
  • soluble complex compounds eg [Al (OH) 4 ] " , [Zn (NH 3 ) 4 ] 2+ ] in the pad solutions (not for Ti, Zr-Y containing solutions).
  • titanium oxide hydrate is an amphoteric compound which reacts only weakly basic, with removal of water form -O-Ti-O-Ti-O-chains, with dissolved Si species of the alkali silicates in the Fügelecten to longer curing times and solid compound or solid compounds -O-Si-O-Ti-O- to lead. Titanium oxide hydrate is poorly soluble in the aged state after the low-temperature joining in acids and alkalis. Especially suitable for the present invention are:
  • Titanium sulfate hydrate TiSO 4 ⁇ H 2 O b) TiO 2 in H 2 O, 1% by weight c) Tetraethyl orthotitanate d) Tertaisopropyl orthotitanate (titanium IV isopropylate) e) Titanium (IV) ethylate f) Titanium ( IV) butyl ortho-titanate g) titanium acetylacetonate
  • Zn (OH) 2 is amphoteric and tends to complex (e.g., with
  • Zinc compounds improve the chemical resistance of the jointing solution and retard hardening. According to the invention can be used in particular:
  • Zirconium compounds serve to improve the chemical resistance of the jointing solution and to delay the curing. Particularly suitable are: a) zirconium sulfate Zr (SO 4 ) 2 b) zirconium (IV) isopropoxide-isopropanol complex c) zirconium propylate 77% in n-propanol d) zirconium-2,4-pentanedionate e) zirconium-n- propylate f) zirconium (IV) acetonate 98% g) zirconium (IV) oxide in water 1% h) zirconium ethoxide i) zirconium nitrate Zr (NOs) 4 k) zirconium (IV) oxide chloride 8-hydrate.
  • Yttrium compounds serve to improve the chemical resistance of the
  • precipitation as hydroxide in the bridging solutions can be prevented by formation of complexes of different stability by addition of tartaric acid or citric acid.
  • the process preferably begins with a cleaning of the parts (bath cleaning or RCA cleaning) as described above by a pretreatment of the parts (bath cleaning or RCA cleaning) as described above by a pretreatment of the parts (bath cleaning or RCA cleaning) as described above by a pretreatment of the parts (bath cleaning or RCA cleaning) as described above by a pretreatment of the parts (bath cleaning or RCA cleaning) as described above by a pretreatment of the parts (bath cleaning or RCA cleaning) as described above by a pretreatment of the parts (bath cleaning or RCA cleaning) as described above by a pretreatment of the parts (bath cleaning or RCA cleaning) as described above by a pretreatment of the parts (bath cleaning or RCA cleaning) as described above by a pretreatment of the parts (bath cleaning or RCA cleaning) as described above by a pretreatment of the parts (bath cleaning or RCA cleaning) as described above by a pretreatment of the parts (bath cleaning or RCA cleaning) as described above by a pretreatment of the parts (bat
  • Joining surfaces eg with alkalis, acids, silanization.
  • Fügeants eg with metered pipette / syringe / dispensing needle by drop application and spin if necessary [spin coating]
  • the typical amount of applied Fügeans greater than or equal to 0.8 ul / cm 2 joining surface.
  • the joining is effected by placing a joining body on the other from above or pushing a joining body from the side. This is done, for example, by placing a drop on the lower sample and immersing the upper sample at the edge of the drop and then sliding it over the drop.
  • the joining surface between the samples fills by capillary action.
  • the joining partners are fixed (preferably under slight pressure, for example about 10 4 N / m 2 ) for about 15 minutes to about 12 hours at room temperature.
  • the subsequent rest periods are about 0.5 to 4 hours, in air or in a desiccator.
  • the short times are particularly suitable for small joining surfaces (a few cm 2 ), the long ones for rather larger areas (50-100 cm 2 ).
  • a careful and possibly vibration-free introduction of the bonded parts in a vacuum chamber or a drying oven is required.
  • the solvent water is slowly removed by a drying process. In the process, a chemical compound of the joining surfaces builds up.
  • This structure is preferably supported by vacuum (rough vacuum about 1 mbar is sufficient) at room temperature for about 3-10 days with or without the application of weights.
  • a heat treatment in the oven preferably at about 80 0 C, a maximum of 200 0 C follows. It takes a few minutes to two weeks.
  • Drying in vacuo has the advantage over normal atmosphere with usually about 50% relative humidity that the outside area around the joint surface is completely free of water vapor and a back reaction in which moisture / water diffuses into the joint surface from the outside is excluded.
  • the increased moisture gradient between joining surface and outer space drives the desiccation of the joining surface very efficiently and thus ensures good dehydration and high solidification in a short time.
  • dissolved, adsorbed or reactively formed gases that are mobile and reach the edge of the joining surface via diffusion processes are sucked out there by vacuum drying. This contributes to an increased quality of the connection and guarantees a trouble-free later Application of the bonded components in a vacuum (eg in space).
  • the diffusion and reaction processes in the joining zone can be effectively supported in the drying phase by infrared radiation.
  • approximately "black radiators” with a temperature of 250-500 centigrade are suitable as beam sources
  • the radiation is preferably directed to the center of the joining surface, and the power density is preferably set so that the samples do not substantially heat up on vacuum drying, ie the
  • Temperature preferably does not rise above 30 Celsius, but in no case above 50 Celsius.
  • the layer thicknesses of the joints can generally be between 10 nm and 2 ⁇ m with a focus at about 150 to 500 nm.
  • Fiber Bonding Fiber bonding consists mostly of SiO 2 glass fibers, which are extremely stable in "V-shaped" grooves with extremely low tolerances to be embedded. Often, these V-grooves are made by anisotropic etching of silicon. The natural (or artificial) oxidation of silicon at the surface provides an excellent bond surface for silicate bonding and the relative "low viscosity” bonding solution results in very good wetting of the fiber.
  • the fiber connector can be in the form of two half-shells or as a hollow cylinder into which the fiber is inserted before the bonding solution is applied and the composite is dried low viscosity of the Fügeaims very tailor-fit pairings are possible, which allow a small layer thickness of the bond and a good heat dissipation from the fiber to the ferrule and - compared to polymers - allow elevated temperatures.
  • the bonding layer to the ferrule can also be made "cloudy” by suitable solutions and can scatter or absorb parasitic radiation and dissipate the heat loss to the (possibly water-cooled) ferrule.
  • Transparent compounds of non-linear optical crystals LiNiO3, BaTiO3 or similar
  • prisms or glass lenses for optical modulators.
  • FIGS. 4a and 4b each show a laser crystal without or with an intermediate piece bonded to a heat sink.
  • the silicate bonding layer can comprise both the bonding of the laser crystal to the intermediate piece and the bonding of the intermediate piece to the heat sink.
  • thin SiO 2 layers (about 100 nm) may be applied by sputtering or similar thin-film techniques prior to the silicate bonding.
  • Stable compounds of laser crystals (Yb: YAG, Nd: YVO 4 or similar) with support materials such as sapphire or Si (or superficially oxidized Si) for stable support and heat dissipation in disk lasers.
  • the glass or glass ceramic surfaces to be joined are chemically activated by an inorganic aqueous solution or suspension with additives and firmly attached at low temperatures. All experiments take place in the clean room.
  • the components can u. a. from Zerodur from Schott, ULE from Corning, 25 silica glass (eg Lithosil) from Schott), BK7 or Borofloat glass from Schott. Typically, blanks of these materials were used with the following characteristics: diameter 25 mm, height 10 to 11 mm, polished on both sides and numbered consecutively by engraving.
  • the joining surfaces are additionally activated (30 min treatment in 10% HNO 3 , rinsing with DI water, dripping times 1, 5 to 2 h).
  • the period between cleaning / activation and joining should not be longer than 6 days, preferably ⁇ 1 day.
  • the ironing solution can be applied manually by means of a syringe, pipette, dispensing needle, but also e.g. by spin-coating or similar Procedure done. If necessary, drying can be carried out after application. This makes it possible to adjust the two parts to be joined “dry” and then in a moist environment (eg in water vapor) first to activate the solution and to react with the substrates, and then again a water removal / drying process. Process 20 as described below.
  • the joining of the parts to be joined is done by hanging up or pushing from the side. Anschmanend the joining parts are adjusted against each other. The joint cures to solid connection.
  • the water removal / drying can be done first at room temperature in air and / or in vacuum with or without weight. Preferably, a period of about 3 hours to about 6 days is suitable. This is followed by a thermal treatment in the oven at temperatures of about 60 to 110 0 C to stabilize the compound. 30 This can also be done in air or in a vacuum.
  • the properties of the activated glass and glass ceramic surfaces, the intermediate layer and the joint are characterized as follows:
  • ISC 1 Na water glass solution
  • Joining process central dripping of the joint solution with a pipette, adjustment time 1 min,
  • Exemplary embodiment 2 Low-temperature bonding of two BK7 blanks
  • RCA cleaning Joint solution ISC 5 (sodium water glass + boric acid, saturated solution)
  • RCA cleaning Fusing solution Silica sol Levasil 300/30% + 1% by volume tetraethyl orthotitanate (3%
  • Joining process centrifuge dropping of the bridging solution with a pipette, adjustment time 4 min, weight (100 g) for 5 min, drying in air for 20 min at room temperature and normal atmosphere, then 8 h heat treatment in a drying oven at 80 0 C and normal atmosphere.
  • Result Adjustment time up to 4 min using a base solution of silica sol (pH 10.1) and addition of a titanium-containing compound as well as stabilization of the bridging solution with (NH 4 ) 2 CO 3 .
  • the pH of the resulting bridging solution is 9.8.
  • ULE is composed of SiO 2 and TiO 2
  • the titanium-containing compound results in higher joining strength (40 MPa instead of 30 MPa compared to a silica sol solution without Ti compound). This gives a stable joint with optically clear and transparent joining surface.
  • Fung solution lithium-waterglass solution + aluminum silicate solution (volume ratio 9: 1) + 5% by volume of ammoniacal solution (NH 3 H 2 O, 24% in water, company Fluka), pH of the bridging solution 11, 6.
  • Joining process central dripping of the joint solution with a glass rod, adjustment time 4 min, weight (400 g) for 60 min, drying in air at room temperature and normal atmosphere for 20 min, then 8 h heat treatment in a drying oven at 80 ° C. and normal atmosphere.
  • RCA cleaning Masterbatch solution 90% by mass Lithium-water glass solution (ISC 1) + 10% by mass Zinc acetate (pH of the bonding solution 11, 4)
  • Joining process centrifuge dropping of the bridging solution with a pipette, adjustment time 5 min, weight (100 g) for 5 min, drying in air for 20 min at room temperature and normal atmosphere, then 8 h heat treatment in a drying oven at 80 0 C and normal atmosphere.
  • Result Adjustment time up to 5 min by addition of zinc acetate to sodium waterglass solution, zinc acetate reacts with the strongly basic sodium silicate solution to zinc hydroxide.
  • Zn (OH) 2 is amphoteric and tends to complex formation in excess liquor, goes into solution and leads to a moderate reduction in the pH of the joint solution. This gives a stable joint, but no optically clear and transparent, but a partially milky joint surface.
  • the method is suitable for joints in which no optical passage through the joining surfaces is needed.
  • Joining process Joining by pushing in the parts to be joined, adjustment time 4 min, weight bearing (500 g) for 15 min in air at room temperature, then 72 h curing under vacuum (5 mbar) at room temperature, followed by heat treatment in a vacuum oven (5 mbar, 70 ° C.). Heating rate 20 K / h, 24 h). Result: The adjustment time was increased by dilution to 4 min, giving a firm joining with an optically clear and transparent joining surface, only occasional bubbles.
  • Joining process Joining by pushing in the parts to be joined, adjustment time 4 min, weight bearing (400 g) for 15 min in air at room temperature, then 72 h
  • Drying cabinet (80 0 C, 24 h).

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Structural Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Ceramic Products (AREA)

Abstract

L'invention concerne un procédé pour assembler au moins deux éléments de verre, de céramique et/ou de vitrocérame à l'aide d'une solution d'assemblage à base de verre soluble contenant des ions sodium, potassium et/ou lithium et/ou un sol de silice, ce procédé consistant à appliquer la solution d'assemblage sur les surfaces à assembler, entre les éléments à assembler, et à la solidifier à des températures peu élevées. Ce procédé est caractérisé en ce que la solution d'assemblage contient un additif choisi parmi l'acide borique, des composés du bore à partir desquels de l'acide borique peut se former par hydrolyse, des acétates d'aluminium, du silicate d'aluminium/NH3 /H2O, des composés de titane qui forment des cations hydroxo dans une solution aqueuse, des composés de zinc solubles dans l'eau, des composés de zircon solubles dans l'eau et des composés d'yttrium solubles dans l'eau, cet additif étant ajouté à raison d'une quantité apte à réduire le pH de la solution de verre soluble de base, et/ou en ce que l'application de la solution d'assemblage et l'assemblage des éléments à assembler et leur fixation sont suivis d'un séchage des éléments assemblés par élimination de l'eau à température ambiante, puis d'une trempe sous vide des éléments assemblés à une température comprise entre une température au-dessus de la température ambiante et 200°C.
EP08862790A 2007-12-17 2008-12-12 Procédé d'assemblage basse température de verre et de matériaux analogues pour l'optique et la mécanique de précision Withdrawn EP2231544A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007060784A DE102007060784A1 (de) 2007-12-17 2007-12-17 Niedertemperaturverfahren zum Fügen von Glas und dergleichen für Optik und Präzisionsmechanik
PCT/EP2008/067442 WO2009077458A1 (fr) 2007-12-17 2008-12-12 Procédé d'assemblage basse température de verre et de matériaux analogues pour l'optique et la mécanique de précision

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Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102010016908B4 (de) 2010-05-11 2021-11-11 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zum silikatischen Bonden von beschichteten und unbeschichteten optischen Körpern
DE102011012835A1 (de) * 2011-02-22 2012-08-23 Friedrich-Schiller-Universität Jena Verfahren zum Fügen von Substraten
DE102011012834A1 (de) * 2011-02-22 2012-08-23 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verfahren zur Herstellung von Leichtbaustrukturelementen
US9086548B2 (en) 2013-09-30 2015-07-21 Corning Cable Systems Llc Optical connectors with inorganic adhesives and methods for making the same
KR20190130148A (ko) * 2017-05-12 2019-11-21 헤레우스 도이칠란트 게엠베하 운트 코. 카게 금속 페이스트에 의해 부품들을 연결하기 위한 방법
CN111876766A (zh) * 2020-07-14 2020-11-03 中国科学院海洋研究所 一种控制液滴自弹跳效应的超疏水表面的制备方法及其应用

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3069277A (en) * 1959-12-18 1962-12-18 Montedison Spa Aqueous dispersions of high molecular weight fibrils of amorphous silicates
US3178299A (en) * 1961-08-05 1965-04-13 Hoechst Ag Self-hardening water glass cement composition
DE2460543B2 (de) * 1974-12-20 1978-02-09 Grünzweig + Hartmann und Glasfaser AG, 6700 Ludwigshafen Kleber und bzw. oder beschichtungsmasse auf wasserglasbasis
GB1604388A (en) * 1977-08-03 1981-12-09 Bfg Glassgroup Fire screening panels
SU834069A1 (ru) * 1979-11-02 1981-05-30 Ленинградский Ордена Октябрьской Революциии Ордена Трудового Красного Знамени Texho-Логический Институт Им.Ленсовета Клей
US4347285A (en) * 1981-02-26 1982-08-31 H. B. Fuller Company Curable aqueous silicate composition, uses thereof, and coatings or layers made therefrom
DE3925462A1 (de) 1989-08-01 1991-02-07 Fraunhofer Ges Forschung Verfahren zur photoinitiierten steuerung der anorganischen netzwerkbildung beim sol-gel-prozess
US5360834A (en) * 1989-08-01 1994-11-01 Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschung E.V. Process for photoinitiated control of inorganic network formation in the sol-gel process
DE4115046A1 (de) * 1991-05-08 1992-11-12 Fraunhofer Ges Forschung Direktes substratbonden
US5565273A (en) * 1992-08-11 1996-10-15 Vetrotech Ag Transparent heat protection element
US6284085B1 (en) 1997-04-03 2001-09-04 The Board Of Trustees Of The Leland Stanford Junior University Ultra precision and reliable bonding method
US6548176B1 (en) 1997-04-03 2003-04-15 The Board Of Trustees Of The Leland Stanford Junior University Hydroxide-catalyzed bonding
DE19746558C1 (de) * 1997-10-22 1999-03-04 Sekurit Saint Gobain Deutsch Verfahren und Formring zum Biegen und Vorspannen von Glasscheiben
JP3681312B2 (ja) * 1999-08-16 2005-08-10 セントラル硝子株式会社 ガラス板成形用支持枠
AU2001273599A1 (en) 2000-06-20 2002-01-02 Schott Glass Technologies, Inc. Glass ceramic composites
DE102005000865A1 (de) 2005-01-05 2006-07-20 Schott Ag Verfahren zum Niedertemperatur-Zusammenfügen von Körpern und verfahrensgemäß hergestellte Erzeugnisse

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2009077458A1 *

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DE102007060784A1 (de) 2009-06-18
WO2009077458A1 (fr) 2009-06-25

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