WO2007147185A1 - Method for the production of an ice surface for ice rinks - Google Patents

Method for the production of an ice surface for ice rinks Download PDF

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Publication number
WO2007147185A1
WO2007147185A1 PCT/AT2007/000298 AT2007000298W WO2007147185A1 WO 2007147185 A1 WO2007147185 A1 WO 2007147185A1 AT 2007000298 W AT2007000298 W AT 2007000298W WO 2007147185 A1 WO2007147185 A1 WO 2007147185A1
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ice
water
added
substance
ppm
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PCT/AT2007/000298
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German (de)
French (fr)
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Thomas Loerting
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Universität Innsbruck
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Priority to US12/306,187 priority Critical patent/US20090301105A1/en
Priority to EP07718507A priority patent/EP2041234A1/en
Priority to CA002655336A priority patent/CA2655336A1/en
Publication of WO2007147185A1 publication Critical patent/WO2007147185A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/24—Materials not provided for elsewhere for simulating ice or snow

Definitions

  • the invention is based on a method for producing an ice surface for an ice rink according to the preamble of claim 1.
  • the ice quality of an ice rink plays in particular in speed competitions such. Speed skating an essential role.
  • the mechanical properties of the ice or the surface of the ice of the ice rinks can be controlled by various parameters, including the ice temperature, the relative humidity and the conductivity of the water forming the ice.
  • the object of the invention is thus to provide a cost-effective method for improving the quality of the ice for ice rinks.
  • the ice forming water is mixed with a substance, the ammonia, an alkali or alkaline earth metal hydroxide, a hydrogen halide, nitric acid, sulfuric acid, phosphoric acid, an alkali, alkaline earth metal ammonium salt of these acids or ammonium bicarbonate or a mixture of several of these substances is.
  • the water is preferably NH 3 , HF, HCl, HBr, HI; NH 4 I, NH 4 F, NH 4 Br, LiOH, NaOH, KOH, Ca (OH) 2 or a mixture of several of these substances added, since these cause the strongest effect of the possible dopants due to their physicochemical properties.
  • the substance added to the water is added in a concentration of up to 5 ppm, which requires only small amounts of the dopants and thus is inexpensive.
  • the maximum concentration of the substance added to the water does not exceed 20 ppm, since this ensures an environmentally friendly concentration which is harmless with regard to contamination by potentially harmful substances.
  • the substance added to the water can be added prior to freezing by admixing with the water in the form of dilute solutions, so that a homogeneous ice layer can be produced.
  • the substance added to the water can be added by treating the ice with liquid containing the additives after freezing, since this also improves the quality of the ice surface produced by undoped water in retrospect during the post-processing of the ice surface can be without having to re-create the ice surface.
  • the method according to the invention provides for selectively adding additives to ice production by freezing deionized water, ie to dope the water. This has the effect that properties such as the coefficient of adhesion or sliding friction or the hardness on the surface can be specifically controlled by these additives.
  • the addition can be done either by admixing with the water in the form of dilute solutions (before freezing) or by treating the ice with a liquid containing the additives (after freezing).
  • An adaptation of the currently used ice making machines is not necessary, since simply water instead of water, such as deionized water, tap water, distilled water, etc., can be used.
  • the doping of the water with 4 ppm NH 3 is described here.
  • a uniform doping with NH 3 can be achieved, for example, by interposing a metering valve which doses a dilute NH 3 solution into the tap water as a function of the flow rate. For example, one liter of a 4% NH 3 solution is added, which is metered in shall be. At a flow rate of 50 liters per minute, the metering valve should meter in 5 milliliters per minute for 200 minutes. This results in a dilution of 1: 10000, so that the tap water ultimately contains 4 ppm NH 3.
  • the ice must be given the time to freeze out homogeneously on the pre-cooled surface. You can use the protocols that Ice Masters currently use. The more time you give the ice, the smaller the cooling rates, the larger the crystals, the smoother the ice surface. Cooling faster, there are small crystals that collide and form interfaces ("triple junctions" or "grain boundaries") - the ice surface is rough.
  • a surface treatment of the ice by means of special ice making machines the method is suitable.
  • These machines which are used in about the 1/3 breaks of ice hockey games, usually have a water tank and a snow container. These machines collect the abraded snow, plan the top layer of ice and apply a new layer of water to the ice. If an appropriate amount of NH 3 is also mixed into the water tank of the machine, previously undoped ice benefits for the first time from the improved surface properties due to the doping or, in the case of ice already produced by doping, the optimized properties of the doped ice remain even after repeated ice-making.
  • 3 ppm HF cause a significant increase in the flow properties of the ice.
  • a skater "cuts" with his skid into the ice and thereby displaces ice from the groove, which normally comes to rest as "snow" on the ice surface.
  • the displaced ice flows much more back into the groove just created, so that firstly less snow comes to rest on the ice surface and secondly the extent of destruction of the ice surface is minimized.
  • the ice surface also gets softer in parallel. If 3 ppm NH 3 is used instead, the opposite effect occurs, the abrasion is intensified, the ice surface is more strongly destroyed and also harder.
  • NH 3 doped ice has a decisive advantage: nowadays Ice Masters adjust the hardness of the ice over the temperature. Soft ice (eg for skaters) are generated by "warm ice” (for example at -3 ° C) makes, during hard ice require that is cooled with a high energy consumption, for example, up to -10 ° C. Using NH 3 doped Ice, so you can produce harder ice even at higher temperatures energy-saving. For organizers of major speed skating events, it is still of great importance that national or continental or even Olympic and world records are run on their tracks. Ice cream, from which one can repel oneself better or on which one glides better, is very important here.
  • the method according to the invention is also suitable for controlling the sliding friction coefficient. So is measurable, that doping causes even cold on a -8O 0 C ice surface a water film which reduces friction. On undoped ice this Wasserhem disappears below about -25 ° C, so that deep-frozen ice is no longer slippery. It would also be conceivable that a dopant is found which greatly increases the sliding friction of ice by suppressing the water flow even at comparatively high temperatures.
  • Good ice surfaces are prepared over a period of several days, as this is the time needed to extract the thermal energy from the water molecules, form crystal nuclei, and achieve optimal crystal growth. Doping with a suitable additive can accelerate all three processes and thus reduce the production time or cost of an ice surface.
  • the investigated substances are incorporated directly into the ice grid up to a concentration of up to 5 ppm and change the formation of so-called D or L defects, the microscopic properties such as relaxation times, H-transfer times, electrical conductivity, etc. This leads to a change in the macroscopic properties.
  • Other substances such as larger inorganic molecules, organic molecules, etc. are not incorporated into the crystal lattice, but only in the lattice cavities or in the grain boundaries, often they are even ejected only over the surface and therefore do not change the microscopic and macroscopic properties of the ice ,
  • the list of substances that can be incorporated into the crystal lattice and are therefore suitable for doping includes ammonia, alkali and alkaline earth hydroxides, hydrogen halides, nitric acid, sulfuric acid, phosphoric acid, alkali metal, alkaline earth and ammonium salts of these acids and ammonium bicarbonate. Particularly preferred are NH 3 (ammonia), HF, HCl, HBr, HI; NH 4 I, NH 4 F, NH 4 Br, LiOH, NaOH, KOH, Ca (OH) 2 or mixtures thereof, which have the greatest potential or effect.
  • the concentration range which must be covered results from the concentration of the molecules directly incorporated (substitutionally) into the lattice and from the minerals already present in the tap water.
  • the limit for fluorides for example, 1.5 ppm, so that for a hard NH 3 doped ice surface first the softening effect of the fluorides must be compensated.

Abstract

Disclosed is a method for producing an ice surface for an ice rink by freezing water to which an inorganic substance is added. The inventive method is characterized in that the inorganic substance is ammonia, an alkali hydroxide or alkaline earth hydroxide, a hydrogen halide, nitric acid, sulfuric acid, phosphoric acid, an alkali salt, alkaline earth salt, or ammonium salt of said acids, ammonium hydrogen carbonate, or a mixture of several of said substances.

Description

Verfahren zur Herstellung einer Eisfläche für Eissportbahnen Method for producing an ice surface for ice rinks
Die Erfindung geht aus von einem Verfahren zur Herstellung einer Eisfläche für eine Eissportbahn nach dem Oberbegriff des Anspruchs 1.The invention is based on a method for producing an ice surface for an ice rink according to the preamble of claim 1.
Die Eisqualität einer Eissportbahn spielt insbesondere bei Schnelligkeitsbewerben wie z.B. Eisschnelllauf eine wesentliche Rolle. Die mechanischen Eigenschaften des Eises bzw. der Oberfläche des Eises der Eissportbahnen lassen sich über verschiedene Parameter steuern, unter anderem über die Eistemperatur, die relative Luftfeuchte bzw. die Leitfähigkeit des das Eis bildenden Wassers.The ice quality of an ice rink plays in particular in speed competitions such. Speed skating an essential role. The mechanical properties of the ice or the surface of the ice of the ice rinks can be controlled by various parameters, including the ice temperature, the relative humidity and the conductivity of the water forming the ice.
Es sind bereits verschiedene Verfahren zur Verbesserung der Eisqualität bekannt. Mechanische Unebenheiten bzw. Verunreinigungen im Eis werden durch Eispräparationsfräsen (ice resurfacing machines) geglättet bzw. entfernt. Um die Lufttemperatur bzw. -feuchte zu kontrollieren, werden Eissportbahnen in Eislaufhallen errichtet. Weiterhin ist es bekannt, durch Entsalzung und Entkalkung störende Natrium- und Kalzium-Ionen mittels eines Osmose-Systems aus dem Eis zu entfernen. Auch die Verwendung von deionisiertem Wasser bei der Eisbereitung anstatt des mineralhaltigen Leitungswassers zur Minimierung der durch die Ionen im Wasser bedingten Reibung ist bekannt.Various methods of improving ice quality are already known. Mechanical irregularities or impurities in the ice are smoothed or removed by ice resurfacing machines. In order to control the air temperature and humidity, ice rinks are built in ice rinks. Furthermore, it is known to remove by desalination and descaling interfering sodium and calcium ions by means of an osmosis system from the ice. Also, the use of deionized water in the ice making instead of the mineral-containing tap water to minimize the caused by the ions in the water friction is known.
Auch der Zusatz von verschiedenen organischen oder anorganischen Substanzen zum Wasser vor dem Gefrierprozess ist bekannt. Beispielsweise geht aus der Patentschrift DE 526 224 hervor, dass die zu beeisende Fläche mit einem Salzgemisch aus Natriumcarbonat und Natriumsulfat bedeckt wird, welches mit Wasser vermengt wird, bis ein höchstkristallwasserhaltiger Zustand des Salzes erreicht wird, und das Gemisch dann gefroren wird.The addition of various organic or inorganic substances to the water before the freezing process is known. For example, the patent specification DE 526 224 discloses that the area to be treated is covered with a salt mixture of sodium carbonate and sodium sulphate, which is mixed with water until a state of high crystallinity of the salt is reached, and the mixture is then frozen.
Nachteilig an den bekannten Verfahren zur Verbesserung der Qualität des Eises, insbesondere an den Osmose- und Deionisationsverfahren, sind dabei die hohen Installations- bzw. Wartungskosten.Disadvantages of the known methods for improving the quality of the ice, in particular the osmosis and deionization processes, are the high installation and maintenance costs.
Aufgabe der Erfindung ist somit, ein kostengünstiges Verfahren zur Verbesserung der Qualität des Eises für Eissportbahnen anzugeben.The object of the invention is thus to provide a cost-effective method for improving the quality of the ice for ice rinks.
Die Aufgabe wird durch die kennzeichnenden Merkmale des Anspruchs 1 in Verbindung mit den gattungsbildenden Merkmalen gelöst Erfindungsgemäß ist dabei vorgesehen, dass dem das Eis bildenden Wasser ein Stoff beigemischt wird, der Ammoniak, ein Alkali- oder Erdalkalihydroxid, ein Halogenwasserstoff, Salpetersäure, Schwefelsäure, Phosphorsäure, ein Alkali-, Erdalkalioder Ammoniumsalz dieser Säuren oder Ammoniumhydrogencarbonat oder eine Mischung mehrerer dieser Stoffe ist.The object is achieved by the characterizing features of claim 1 in conjunction with the generic features According to the invention it is provided that the ice forming water is mixed with a substance, the ammonia, an alkali or alkaline earth metal hydroxide, a hydrogen halide, nitric acid, sulfuric acid, phosphoric acid, an alkali, alkaline earth metal ammonium salt of these acids or ammonium bicarbonate or a mixture of several of these substances is.
Dadurch ist es möglich, den Gefrierprozess zu beschleunigen oder zu verlangsamen, gezielt eine harte oder weiche, eine mechanisch resistente, eine stark gleitfähige oder eher klebrige Eisfläche zu erhalten, welche in einfacher Weise auf bestehenden Eissportbahnen mit gängigen Vorrichtungen zur Aufbereitung der Eisfläche hergestellt und erhalten werden können, ohne aufwendige Installationen oder nachträgliche Installationen von teuren Geräten zu erfordern.This makes it possible to accelerate or slow down the freezing process, specifically to obtain a hard or soft, a mechanically resistant, a highly slippery or sticky ice surface, which is easily manufactured and maintained on existing ice rinks with common devices for processing the ice surface can be done without requiring expensive installations or subsequent installations of expensive equipment.
Weitere vorteilhafte Merkmale und Ausgestaltungsvarianten gehen aus den Unteransprüchen hervor.Further advantageous features and design variants will become apparent from the dependent claims.
Vorteilhafterweise werden dem Wasser bevorzugt NH3, HF, HCl, HBr, HI; NH4I, NH4F, NH4Br, LiOH, NaOH, KOH, Ca(OH)2 oder eine Mischung mehrerer dieser Stoffe zugesetzt, da diese aufgrund ihrer physikalisch-chemischen Eigenschaften die stärkste Wirkung der möglichen Dotierungsstoffe hervorrufen.Advantageously, the water is preferably NH 3 , HF, HCl, HBr, HI; NH 4 I, NH 4 F, NH 4 Br, LiOH, NaOH, KOH, Ca (OH) 2 or a mixture of several of these substances added, since these cause the strongest effect of the possible dopants due to their physicochemical properties.
Weiterhin ist von Vorteil, dass der dem Wasser zugesetzte Stoff in einer Konzentration von bis zu 5 ppm zugesetzt wird, was nur geringe Mengen der Dotierungsstoffe erfordert und somit kostengünstig ist.Furthermore, it is advantageous that the substance added to the water is added in a concentration of up to 5 ppm, which requires only small amounts of the dopants and thus is inexpensive.
Von Vorteil ist weiterhin, dass die maximale Konzentration des dem Wasser zugesetzten Stoffs 20 ppm nicht übersteigt, da dadurch eine umweltschonende und in Bezug auf eine Kontamination durch möglicherweise gesundheitsschädliche Stoffe ungefährliche Konzentration gewährleistet ist.It is furthermore advantageous that the maximum concentration of the substance added to the water does not exceed 20 ppm, since this ensures an environmentally friendly concentration which is harmless with regard to contamination by potentially harmful substances.
Vorteilhaft ist, dass der dem Wasser zugesetzte Stoff durch Beimischung zum Wasser in Form verdünnter Lösungen vor dem Frieren zugesetzt werden kann, so daß eine homogene Eisschicht erzeugt werden kann.It is advantageous that the substance added to the water can be added prior to freezing by admixing with the water in the form of dilute solutions, so that a homogeneous ice layer can be produced.
Besonders vorteilhaft ist auch, dass der dem Wasser zugesetzte Stoff durch Behandlung des Eises mit Flüssigkeit, welche die Zusätze enthalten, nach dem Frieren zugesetzt werden kann, da hierdurch auch eine durch undotiertes Wasser hergestellte Eisfläche im Nachhinein bei der Nachbearbeitung der Eisoberfläche in ihrer Qualität verbessert werden kann, ohne die Eisfläche neu anlegen zu müssen. Bei der Eisbereitung für Schnelligkeitsbewerbe wie beispielsweise Eisschnelllauf ist es wünschenswert, den Reibungskoeffizienten der Eisoberfläche zu senken. Bislang wurde hauptsächlich eine Optimierung von Faktoren im Umfeld der Sportler betrieben, etwa die Bekleidung der Athleten (dünne, windschlüpfrige Häute als Anzug bzw. lange, dünne Kufen an den Schlittschuhen) oder eine Verringerung des Luftwiderstandes durch das Verlegen der Eissportbahnen in Hallen bzw. in Höhenlagen. Erst in den letzten 10 Jahren hat man begonnen, auch das Eis selbst in Betracht zu ziehen, um eine Verbesserung der Oberfläche des Eises und damit höhere Geschwindigkeiten zu erzielen.It is also particularly advantageous that the substance added to the water can be added by treating the ice with liquid containing the additives after freezing, since this also improves the quality of the ice surface produced by undoped water in retrospect during the post-processing of the ice surface can be without having to re-create the ice surface. When making ice cream for speed races such as speed skating, it is desirable to lower the friction coefficient of the ice surface. So far, an optimization of factors in the athlete's environment has been mainly pursued, such as the athletes' clothing (thin, wind-slippery skins as suit or long, thin runners on the skates) or a reduction in air resistance by laying the ice rinks in halls or in altitudes. Only in the last 10 years has one begun to consider the ice itself in order to achieve an improvement in the surface of the ice and thus higher speeds.
Die Tatsache, dass eine quasi-flüssige Schicht auf dem Eis dessen bekannte Eigenschaften (rutschig, etc.) bedingt, ist seit Faraday 1850 bekannt. Die Abhängigkeit der Schichtdicke dieses dünnen Wasserfilms von der Temperatur ist das Ergebnis verschiedener Studien der letzten 50 Jahre. Unterhalb von ca. -25°C verschwindet dieser Wasserfilm, und das Eis wird "klebrig" (Zunge bleibt kleben etc.). Die Neuheit der Erfindung besteht darin, dass die Schichtdicke und somit die Eigenschaften des Eises durch eine gezielte Zugabe von Zusätzen im Spurenbereich bei jeder beliebigen Eistemperatur in die gewünschte Richtung, etwa einen niedrigeren Gleitreibungskoeffizienten, gesteuert werden kann.The fact that a quasi-liquid layer on the ice causes its known properties (slippery, etc.) has been known since Faraday 1850. The dependence of the thickness of this thin film of water on the temperature is the result of several studies over the past 50 years. Below about -25 ° C, this water film disappears, and the ice becomes "sticky" (tongue sticks, etc.). The novelty of the invention is that the layer thickness and thus the properties of the ice can be controlled in the desired direction, such as a lower coefficient of sliding friction, by a targeted addition of additives in the trace range at any desired ice temperature.
Das erfindungsgemäße Verfahren sieht dabei vor, bei der Eisherstellung durch Frieren von deionisiertem Wasser diesem gezielt Zusätze zuzugeben, das Wasser also zu dotieren. Dies bewirkt, dass Eigenschaften wie der Haft- bzw. Gleitreibungskoeffizient oder die Härte an der Oberfläche durch diese Zusätze gezielt gesteuert werden können. Der Zusatz kann entweder durch Beimischung zum Wasser in Form verdünnter Lösungen (vor dem Frieren) oder durch Behandlung des Eises mit einer Flüssigkeit, die die Zusätze enthält (nach dem Frieren) geschehen. Eine Adaption der derzeit verwendeten Eisbereitungsmaschinen ist nicht notwendig, da einfach statt Wasser verunreinigtes Wasser, beispielsweise deionisiertes Wasser, Leitungswasser, destilliertes Wasser etc., verwendet werden kann.The method according to the invention provides for selectively adding additives to ice production by freezing deionized water, ie to dope the water. This has the effect that properties such as the coefficient of adhesion or sliding friction or the hardness on the surface can be specifically controlled by these additives. The addition can be done either by admixing with the water in the form of dilute solutions (before freezing) or by treating the ice with a liquid containing the additives (after freezing). An adaptation of the currently used ice making machines is not necessary, since simply water instead of water, such as deionized water, tap water, distilled water, etc., can be used.
Im Folgenden wird das erfindungsgemäße Verfahren anhand der Durchführung des Verfahrens mit einem bevorzugten Zusatz näher erläutert.In the following, the method according to the invention will be explained in more detail with reference to the implementation of the method with a preferred addition.
Als Beispiel wird hier das Dotieren des Wassers mit 4 ppm NH3 beschrieben. Um eine Eisfläche mit 200 m2 und 5 cm Dicke herzustellen, benötigt man 10000 Liter Wasser. Diese werden typischerweise mittels eines Schlauchs, der an das Wasserleitungsnetz angeschlossen wird, auf eine gekühlte Fläche gespritzt. Eine gleichmäßige Dotierung mit NH3 kann zum Beispiel dadurch erzielt werden, dass ein Dosierventil zwischengeschaltet wird, welches in Abhängigkeit der Durchflussmenge eine verdünnte NH3 Lösung in das Leitungswasser dosiert. Man legt also zum Beispiel einen Liter einer 4%-igen NH3 Lösung vor, die eindosiert werden soll. Bei einer Durchflussrate von 50 Litern pro Minute soll das Dosierventil 200 Minuten lang 5 Milliliter pro Minute eindosieren. Dies führt zu einer Verdünnung von 1 : 10000, sodass das Leitungswasser letztlich 4 ppm NH3 enthält.As an example, the doping of the water with 4 ppm NH 3 is described here. To produce an ice surface with 200 m 2 and 5 cm thickness, you need 10000 liters of water. These are typically sprayed onto a cooled surface by means of a hose connected to the water mains. A uniform doping with NH 3 can be achieved, for example, by interposing a metering valve which doses a dilute NH 3 solution into the tap water as a function of the flow rate. For example, one liter of a 4% NH 3 solution is added, which is metered in shall be. At a flow rate of 50 liters per minute, the metering valve should meter in 5 milliliters per minute for 200 minutes. This results in a dilution of 1: 10000, so that the tap water ultimately contains 4 ppm NH 3.
Nun muss dem Eis die Zeit gegeben werden, auf der vorgekühlten Fläche homogen auszufrieren. Dabei können die Protokolle verwendet werden, die die Eismeister derzeit einsetzen. Je mehr Zeit man dem Eis gibt, je kleiner also die Kühlraten, desto größer die Kristalle, desto glatter die Eisoberfläche. Kühlt man schneller, gibt es kleine Kristalle, die aneinander stoßen und Grenzflächen ausbilden („triple junctions" bzw. „grain boundaries") — die Eisfläche wird rau.Now the ice must be given the time to freeze out homogeneously on the pre-cooled surface. You can use the protocols that Ice Masters currently use. The more time you give the ice, the smaller the cooling rates, the larger the crystals, the smoother the ice surface. Cooling faster, there are small crystals that collide and form interfaces ("triple junctions" or "grain boundaries") - the ice surface is rough.
Auch für eine Oberflächenbehandlung des Eis mittels speziellen Eisbereitungsmaschinen eignet sich das Verfahren. Diese Maschinen, die etwa in den Drittelpausen von Eishockeyspielen eingesetzt werden, haben zumeist einen Wassertank und einen Schneebehälter. Diese Maschinen sammeln den abgeriebenen Schnee ein, hobeln die oberste Eisschicht ab und tragen eine neue Wasserschicht auf das Eis auf. Mischt man eine entsprechende Menge an NH3 auch in den Wassertank der Maschine, so profitiert vorher undotiertes Eis erstmals von den verbesserten Oberflächeneigenschaften durch die Dotierung bzw. bleiben bei bereits mittels Dotierung hergestelltem Eis die optimierten Eigenschaften des dotierten Eis auch nach mehrmaliger Eisbereitung aufrecht.Also for a surface treatment of the ice by means of special ice making machines, the method is suitable. These machines, which are used in about the 1/3 breaks of ice hockey games, usually have a water tank and a snow container. These machines collect the abraded snow, plan the top layer of ice and apply a new layer of water to the ice. If an appropriate amount of NH 3 is also mixed into the water tank of the machine, previously undoped ice benefits for the first time from the improved surface properties due to the doping or, in the case of ice already produced by doping, the optimized properties of the doped ice remain even after repeated ice-making.
Durch die Auswahl des Dopants bzw. der Dopantmischung und der Mischverhältnisse können verschiedene Eis-Eigenschaften optimiert werden:By selecting the dopant or the dopant mixture and the mixing ratios, different ice properties can be optimized:
Beispielsweise bewirken 3 ppm HF eine deutliche Erhöhung der Fließeigenschaften des Eises. Ein Schlittschuhläufer „schneidet" mit seiner Kufe in das Eis und verdrängt dadurch Eis aus der Rille, das im Normalfall als „Schnee" auf der Eisfläche zu liegen kommt. Im Falle einer Dotierung mit 3 ppm HF fließt das verdrängte Eis viel stärker in die gerade eben erzeugte Rille zurück, so dass erstens weniger Schnee auf der Eisfläche zu liegen kommt und zweitens das Ausmaß der Zerstörung der Eisoberfläche minimiert wird. Die Eisfläche wird parallel dazu auch weicher. Verwendet man stattdessen 3 ppm NH3 so kommt es zum gegenteiligen Effekt, der Abrieb wird verstärkt, die Eisfläche wird stärker zerstört und auch härter.For example, 3 ppm HF cause a significant increase in the flow properties of the ice. A skater "cuts" with his skid into the ice and thereby displaces ice from the groove, which normally comes to rest as "snow" on the ice surface. In the case of a doping with 3 ppm HF, the displaced ice flows much more back into the groove just created, so that firstly less snow comes to rest on the ice surface and secondly the extent of destruction of the ice surface is minimized. The ice surface also gets softer in parallel. If 3 ppm NH 3 is used instead, the opposite effect occurs, the abrasion is intensified, the ice surface is more strongly destroyed and also harder.
Benötigt man eine sehr harte Eisfläche (z.B. für Eishockey-Spiele), so hat NH3 dotiertes Eis aber einen entscheidenden Vorteil: heutzutage stellen Eismeister die Härte des Eis über die Temperatur ein. Weiche Eisflächen (z.B. für Eiskunstläufer) werden erzeugt, indem man „warmes Eis" (z.B. bei -3°C) macht, während harte Eisflächen erfordern, dass man unter hohem Energieverbrauch z.B. bis auf -10°C kühlt. Verwendet man NH3 dotiertes Eis, so kann man härteres Eis schon bei höheren Temperaturen energiesparend herstellen. Für Veranstalter von Eisschnelllaufgroßveranstaltungen ist es weiterhin von großer Bedeutung, dass auf ihren Bahnen nationale bzw. kontinentale oder gar Olympia- und Weltrekorde gelaufen werden. Eis, von dem man sich besser abstoßen kann bzw. auf dem man besser gleitet, ist hier sehr wichtig. Das erfindungsgemäße Verfahren eignet sich auch, den Gleitreibungskoeffizienten zu steuern. So ist messbar, dass eine Dotierung dazu führt, dass selbst auf einer -8O0C kalten Eisfläche ein Wasserfilm entsteht, der die Gleitreibung senkt. Auf undotiertem Eis verschwindet dieser Wasserfüm bereits unterhalb von etwa -25°C, so dass tiefkaltes Eis nicht mehr rutschig ist. Denkbar wäre auch, dass ein Dopant gefunden wird, das die Gleitreibung von Eis stark erhöht, indem den Wasserfϊlm bereits bei vergleichsweise hohen Temperaturen unterdrückt wird.If you need a very hard ice surface (eg for ice hockey games), NH 3 doped ice has a decisive advantage: nowadays Ice Masters adjust the hardness of the ice over the temperature. Soft ice (eg for skaters) are generated by "warm ice" (for example at -3 ° C) makes, during hard ice require that is cooled with a high energy consumption, for example, up to -10 ° C. Using NH 3 doped Ice, so you can produce harder ice even at higher temperatures energy-saving. For organizers of major speed skating events, it is still of great importance that national or continental or even Olympic and world records are run on their tracks. Ice cream, from which one can repel oneself better or on which one glides better, is very important here. The method according to the invention is also suitable for controlling the sliding friction coefficient. So is measurable, that doping causes even cold on a -8O 0 C ice surface a water film which reduces friction. On undoped ice this Wasserfüm disappears below about -25 ° C, so that deep-frozen ice is no longer slippery. It would also be conceivable that a dopant is found which greatly increases the sliding friction of ice by suppressing the water flow even at comparatively high temperatures.
Gute Eisflächen werden in einem Zeitraum von mehreren Tagen präpariert, da dies die Zeit ist, die benötigt wird, um den Wassermolekülen die thermische Energie zu entziehen, Kristallkeime zu bilden sowie ein optimales Kristallwachstum zu erreichen. Eine Dotierung mit einem geeigneten Zusatz kann alle drei Prozesse beschleunigen und somit die Herstellungszeit bzw. -kosten einer Eisfläche senken.Good ice surfaces are prepared over a period of several days, as this is the time needed to extract the thermal energy from the water molecules, form crystal nuclei, and achieve optimal crystal growth. Doping with a suitable additive can accelerate all three processes and thus reduce the production time or cost of an ice surface.
Die untersuchten Stoffe werden bis zu einer Konzentration von bis zu 5 ppm direkt in das Eisgitter eingebaut und verändern über das Ausbilden sogenannter D- oder L-Defekte die mikroskopischen Eigenschaften wie Relaxationszeiten, H-Übertragungszeiten, elektrische Leitfähigkeit etc. Dies führt zu einer Veränderung der makroskopischen Eigenschaften. Andere Stoffe wie beispielsweise größere anorganische Moleküle, organische Moleküle etc. werden nicht in das Kristallgitter eingebaut, sondern lediglich in die Gitterhohlräume oder in die grain boundaries, vielfach werden sie sogar nur über die Oberfläche ausgestoßen und verändern die mikroskopischen und makroskopischen Eigenschaften vom Eis daher nicht.The investigated substances are incorporated directly into the ice grid up to a concentration of up to 5 ppm and change the formation of so-called D or L defects, the microscopic properties such as relaxation times, H-transfer times, electrical conductivity, etc. This leads to a change in the macroscopic properties. Other substances such as larger inorganic molecules, organic molecules, etc. are not incorporated into the crystal lattice, but only in the lattice cavities or in the grain boundaries, often they are even ejected only over the surface and therefore do not change the microscopic and macroscopic properties of the ice ,
Die Liste der Stoffe, die sich ins Kristallgitter einbauen lassen und daher zur Dotierung geeignet sind, umfasst Ammoniak, Alkali- und Erdalkalihydroxide, Halogenwasserstoffe, Salpetersäure, Schwefelsäure, Phosphorsäure, Alkali-, Erdalkali- und Ammoniumsalze dieser Säuren und Ammoniumhydrogencarbonat. Besonders bevorzugt sind dabei NH3 (Ammoniak), HF, HCl, HBr, HI; NH4I, NH4F, NH4Br, LiOH, NaOH, KOH, Ca(OH)2 oder Mischungen davon, welche das größte Potential bzw. den größten Effekt haben.The list of substances that can be incorporated into the crystal lattice and are therefore suitable for doping includes ammonia, alkali and alkaline earth hydroxides, hydrogen halides, nitric acid, sulfuric acid, phosphoric acid, alkali metal, alkaline earth and ammonium salts of these acids and ammonium bicarbonate. Particularly preferred are NH 3 (ammonia), HF, HCl, HBr, HI; NH 4 I, NH 4 F, NH 4 Br, LiOH, NaOH, KOH, Ca (OH) 2 or mixtures thereof, which have the greatest potential or effect.
Der Konzentrationsbereich, der abgedeckt werden muss, ergibt sich aus der Konzentration der direkt (substitutionell) in das Gitter eingebauten Moleküle sowie aus den bereits im Leitungswasser vorhandenen Mineralien. Der Grenzwert für Fluoride beträgt beispielsweise 1.5 ppm, so dass für eine harte NH3 dotierte Eisfläche zuerst der weichmachende Effekt der Fluoride kompensiert werden muss. Maximal 1.5 ppm zum Kompensieren plus 5 ppm, die höchstens substitutioneil eingebaut werden, ergeben einen Grenzwert für die Dotierung des Leitungswassers mit 6.5 ppm. Bezieht man eine Sicherheitsmarge mit ein, beträgt die maximale Konzentration 20 ppm, die einen Einfluss auf die makroskopischen Eigenschaften von Eis hat.The concentration range which must be covered results from the concentration of the molecules directly incorporated (substitutionally) into the lattice and from the minerals already present in the tap water. The limit for fluorides, for example, 1.5 ppm, so that for a hard NH 3 doped ice surface first the softening effect of the fluorides must be compensated. Maximum 1.5 ppm for compensation plus 5 ppm, the can be inserted substitution part, provide a limit for the doping of tap water with 6.5 ppm. Including a safety margin, the maximum concentration is 20 ppm, which has an influence on the macroscopic properties of ice.
Eine äquivalente Menge der vorgeschlagenen Substanzen befindet sich auch im Regenwasser, so dass von einer Giftigkeit nicht ausgegangen werden muss. Nach dem Auftauen der Eisfläche kann die Entsorgung des Wassers mit den zugesetzten Stoffen in einfacher und kostengünstiger Weise über die Kanalisation erfolgen. An equivalent amount of the proposed substances is also in the rainwater, so that no toxicity must be assumed. After thawing the ice surface, the disposal of the water can be done with the added substances in a simple and cost-effective way through the sewer.

Claims

Ansprüche claims
1. Verfahren zur Herstellung einer Eisfläche für eine Eissportbahn durch Gefrieren von Wasser, welchem ein anorganischer Stoff zugesetzt ist, dadurch gekennzeichnet, dass der dem Wasser zugesetzte Stoff Ammoniak, ein Alkali- oder Erdalkalihydroxid, ein Halogenwasserstoff, Salpetersäure, Schwefelsäure, Phosphorsäure, ein Alkali-, Erdalkalioder Ammoniumsalz dieser Säuren oder Ammoniumhydrogencarbonat oder eine Mischung mehrerer dieser Stoffe ist.A process for producing an ice surface for an ice rink by freezing water to which an inorganic substance is added, characterized in that the substance added to the water is ammonia, an alkali or alkaline earth hydroxide, a hydrogen halide, nitric acid, sulfuric acid, phosphoric acid, an alkali -, Alkaline earth or ammonium salt of these acids or ammonium bicarbonate or a mixture of several of these substances.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass dem Wasser bevorzugt NH3, HF, HCl, HBr, HI; NH4I, NH4F, NH4Br, LiOH, NaOH, KOH, Ca(OH)2 oder Mischungen mehrerer dieser Stoffe zugesetzt werden.2. The method according to claim 1, characterized in that the water is preferably NH 3 , HF, HCl, HBr, HI; NH 4 I, NH 4 F, NH 4 Br, LiOH, NaOH, KOH, Ca (OH) 2 or mixtures of several of these substances.
3. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass der dem Wasser zugesetzte Stoff in einer Konzentration von bis zu 5 ppm zugesetzt wird.3. The method according to claim 1 or 2, characterized in that the added water to the substance is added in a concentration of up to 5 ppm.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass die maximale Konzentration des dem Wasser zugesetzten Stoffs 20 ppm nicht übersteigt.4. The method according to claim 3, characterized in that the maximum concentration of the water added to the substance does not exceed 20 ppm.
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass der dem Wasser zugesetzte Stoff durch Beimischung zum Wasser in Form verdünnter Lösungen vor dem Frieren zugesetzt wird.5. The method according to any one of claims 1 to 4, characterized in that the added to the water substance is added by admixing with water in the form of dilute solutions before freezing.
6. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass der dem Wasser zugesetzte Stoff durch Behandlung des Eises mit einer Flüssigkeit, die die Zusätze enthält, nach dem Frieren zugesetzt wird. 6. The method according to any one of claims 1 to 4, characterized in that the added substance to the water by treatment of the ice with a liquid containing the additives is added after freezing.
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