Nothing Special   »   [go: up one dir, main page]

WO2003068501A9 - Anti spalling glass construction - Google Patents

Anti spalling glass construction

Info

Publication number
WO2003068501A9
WO2003068501A9 PCT/US2003/004234 US0304234W WO03068501A9 WO 2003068501 A9 WO2003068501 A9 WO 2003068501A9 US 0304234 W US0304234 W US 0304234W WO 03068501 A9 WO03068501 A9 WO 03068501A9
Authority
WO
WIPO (PCT)
Prior art keywords
construction
accordance
glazing
glass
ballistic
Prior art date
Application number
PCT/US2003/004234
Other languages
French (fr)
Other versions
WO2003068501A1 (en
Inventor
Arturo Mannheim
Original Assignee
Agp Europ Gmbh
Idea Inc
Arturo Mannheim
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
Priority claimed from DE20202223U external-priority patent/DE20202223U1/en
Application filed by Agp Europ Gmbh, Idea Inc, Arturo Mannheim filed Critical Agp Europ Gmbh
Priority to AU2003213028A priority Critical patent/AU2003213028A1/en
Publication of WO2003068501A1 publication Critical patent/WO2003068501A1/en
Publication of WO2003068501A9 publication Critical patent/WO2003068501A9/en

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10128Treatment of at least one glass sheet
    • B32B17/10137Chemical strengthening
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B32B17/10045Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets with at least one intermediate layer consisting of a glass sheet
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10082Properties of the bulk of a glass sheet
    • B32B17/10119Properties of the bulk of a glass sheet having a composition deviating from the basic composition of soda-lime glass, e.g. borosilicate
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/1077Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing polyurethane
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00Layered products comprising a layer of synthetic resin
    • B32B27/36Layered products comprising a layer of synthetic resin comprising polyesters
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41WEAPONS
    • F41HARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H5/00Armour; Armour plates
    • F41H5/02Plate construction
    • F41H5/04Plate construction composed of more than one layer
    • F41H5/0407Transparent bullet-proof laminatesinformative reference: layered products essentially comprising glass in general B32B17/06, e.g. B32B17/10009; manufacture or composition of glass, e.g. joining glass to glass C03; permanent multiple-glazing windows, e.g. with spacing therebetween, E06B3/66

Definitions

  • Armoured glazing constructions has as main objective to provide protection against ammunition of a defined type and energy/velocity characteristics.
  • the most important applications includes military and civil vehicles, cash & transit vehicles, marine ships, aircrafts and government buildings and all of these can be either flat or curved.
  • These glazing constructions and specially the transportation ones must comply with a series of basic functional requirements as a) high scratch/abrasion resistance b) high durability under environmental conditions b) free splinter projection (anti-spall) c) residual field of vision d)minimum weight e) minimum thickness and f) optical quality (free of distortions).
  • the anti-spall protection requirement is critical because the splinters projected to the internal environment to be protected have such a high energy that they are normally more devastating than even the bullet itself.
  • the glass industry has developed two basic ways to reduce the severity of this problem i) incorporating a polymeric ply adhered to the rear most face of the armour construction facing the environment to be protected which brings several difficulties in the manufacturing processes, in the optical performance (distortion and double vision effect) and in the scratch resistance of the armoured construction, in the chemical stability under a lot of substances and worst, in the durability of its surface by the small hardness and ii) Multi layered glass and plastic construction with an increased thickness (regularly 2 times thicker than the most efficient compositions available of i).
  • This invention covers new and improved cross sections based on one or more thin chemically strengthened glasses to improve the splinter projection protection performances, to optimise the ballistic behaviour of the glazing, to extend the life span of the product and to achieve a considerable reduction on the complexity of the actual manufacturing techniques which finally reflects on a lower production cost.
  • Coated PET is maybe less sensitive to chemical attack than Polycarbonate but its ballistic and splinters protection perfomiances a re far 1 ess e ffective t han P olycarbonate a nd t here i s n ot a c ross section advantage (in terms of weight and thickness) of using PET instead of Polycarbonate.
  • Another problem common to any polymeric splinter protection solution is that environmental conditions like ultraviolet solar radiation, temperature excursions and water vapour coming from the atmosphere may cause a durability issue causing a significant reduction in the material lifetime.
  • a buffer or cover plate usually being of soda lime glass must be used on top of the inner surface of said polymer within the manufacturing process (autoclave cycle) to achieve a relatively high flatness of the surface of said polymer and a good optical quality but, in the other hand, having an additional glass represents higher costs on raw materials, longer bending and autoclave processes and increased hand labour, reworks and rejected product on production, decreasing the productivity. All these reasons explain the need of having a ballistically efficient and mechanical and chemically durable solution for our transportation application.
  • Laminated anti-bandit glazing Cross section concept Single glazed composite element
  • This patent is related to security glazing for anti-bandit applications and all examples and embodiments are referred to this type of manual attacks as hammers, pick-axes, crowbars, b ricks, i t c an b e seen that the lower spall generated by the impacts on their preferred embodiments is rated between 13gr. and more than 200 gr.; it is important to understand that for BRG applications the weight for the total spall generated is more than 500 times lower, it is impossible to have a BRG construction with the level of spall shown on the mentioned patent, this spall would destroy the witness foil of the standard ballistic test and would cause as much injures as the caused by the bullet by itself. So, it is evident that the claimed construction of the mentioned patent is far away from the field of application of our invention.
  • the lowest thickness for its rearmost glass is 16% of the thickness of the thicker one in the composition; in our invention we are considering a thin glass with thickness less than 0,7mm and preferred 0,4mm whose thickness is much lower than 16% of the thickest glass on a typical construction (thickest glass on a BRG composition is ranged between 6 and 15mm).
  • underlay this invention is that an inorganic scratch resistant and chemically inert material has to be used as the protecting ply against splinter projection (anti spall or no spall layer) in order to achieve the durability requirements demanded by the transportation application and keeping an efficient ballistic performance (as for total thickness vs. ballistic resistance).
  • glass itself is the material to be used as the last inner layer in an armoured glazing construction. This is because glass has an abrasion, scratches and chemical resistance far superior to any polymeric, plastic material (see Table 1).
  • thermally tempered glass breaks in small fragments when broken but this is not a good solution for armoured ballistic glazing as splinter protection because:
  • the chemical strengthening process introduces in the glass a residual stress profile with a compression layer on the surfaces and an inner tensile area. Fragmentation after breakage can be controlled to some extent by controlling the ion-exchange process parameters resulting in suitable values of the compression layer depth (Case depth C D ), surface compression (Sc), and central tension ( ⁇ ) (see Figure 2).
  • the leading ideas in using thin CS glass in armoured constructions are :
  • Thermal tempering has the advantage to induce a compression layer of 20% of original glass thickness resulting in a pretty high inner central tension that means enough energy to generate tiny fragmentation upon glass breakage.
  • the compression layer depth introduced in soda-lime float glass by ion-exchange chemical strengthening is typically ranging from 10 ⁇ m to 50 ⁇ m. With a 30 ⁇ m compression layer depth on a 2 mm (2000 ⁇ m) glass the compression depth over thickness ratio is 1.5 % and the resulting fragmentation is coarse because of the low inner tensile stress.
  • a plastic core ply as an outer layer of the anti spalling construction that can be any low or high modulus polymer from Polycarbonate, to thick (0,13-25 mm) PNB to thick polyurethane (0,13-25 mm), to Polyethylene ionomer, Acrylic, EVA, Polyethylene thereftalate PET, to any ionomeric modification of said polymers like Surlyn (Sentry Glas Plus) that, in this case, it is not affected by surface scratch problems as an energy impact absorber and an inner (facing the internal environment in accordance with figures 3 a and 3b) controlled injury free splinter projection system consisting in a thin chemically strengthened glass layer or layers which may be treated with a coating process like silk-screening, CND, PND, Sputtering, sol-gel, painting or masking among others.
  • the different systems will be accordingly used for the different ballistic protection levels required.
  • the underlying concept of the invention is that the armoured glazing cross section should be divided in two parts:
  • Rearmost part facing the environment to be protected has mainly the purpose of absorbing the residual impact energy without splinter projection towards the environment.
  • a typical ballistic test (EN 1063) describe all the necessary conditions to perform the ballistic attack (Bullet type and weight, bullet velocity, number of strikes (typically 3) and striking distance, striking points - hit spacing (normally are the vertex of an equilateral triangle) samples number (typically 3 samples have to be tested), sample mounting system, and witness aluminium foil (0.02 mm thickness mass density 54 g/m 2 ).
  • a single thin glass layer will be considered in the cross section of the armoured glazing as the external layer facing the environment to be protected.
  • This ply will have the impact/bending strength sufficient to withstand the requested level of ballistic protection.
  • the ply will have a chemical strengthening process with its central tension being tailored to release injury free splinters without generating perforations on the aluminium witness foil of the respective standard(s) ballistic test(s) for the given ballistic level
  • the thin glass may be treated with a coating process like silk-screening, CND, PND, sputtering sol-gel, painting or masking among others, in order to keep a residual vision through the armoured construction after the first and subsequent shots based on the pre-defined ballistic level.
  • the single thin glass may have some of the following compositions: Soda Lime, Borosilicate or Aluminosilicate or may be a layer of Aluminium Oxynitride, Magnesium Aluminate, Aluminium Oxide or some other armour ceramic.
  • a system of multiple thin glass layers will be considered in the cross section of the armoured glazing as the external layer facing the environment to be protected.
  • Each ply of the system will have the impact/bending strength sufficient to withstand the requested level of ballistic protection.
  • the one or more plies of the embodiment will have a chemical strengthening process in order that the multiple plies system be tailored to release injury free splinters without generating perforations on the aluminium witness foil of the respective standard(s) ballistic test(s) for the given ballistic level .
  • one or more plies may be treated with a coating process like silk-screening, CND, PND, sputtering sol-gel, painting or masking among others, in order to keep a residual vision through the armoured construction after the first and subsequent shots based on the pre-defined ballistic level.
  • the thin glass plies system may have some of the following compositions: Soda Lime, Boro or Aluminosilicate or may be composed by plies o f Aluminium Oxynitride, Magnesium Aluminate, Aluminium Oxide or some other armour ceramic or their combination.
  • a s ystem c omposed b y s ingle o r m ultiple t hin g lass 1 ayers will be considered as the external layer facing the environment to be protected in the cross section of the armoured glazing coupled with an intermediate plastic energy absorber which may be composed by one or more plies of polymeric materials.
  • Each ply of the system will have the impact/bending strength sufficient to withstand the requested level of ballistic protection.
  • the central tension of the last ply facing the environment will be tailored to release injury free splinters without generating perforations on the aluminium witness foil of the respective standard(s) ballistic test(s) for the given ballistic level.
  • the front most section is a construction composed by one or more plies of inorganic components with an individual thickness between 0.03 and 25mm.
  • the layer or multiple layers of polymer connecting the rearmost section (single or multiple p lies chemically strengthened glass) to the intermediate and to the front most section should be with a thickness from 0.13 up to 12 mm and the polymeric material can be: PNB (Polyvinyl butyral), Polyurethane, Thermoplastic Polyurethane, Polycarbonate, Acrylic, EN A, Polyethylene Thereftalate, Polyester (PET), Polyethylene ionomer, Surlyn (Sentry Glas Plus), acrylic resin and any Ionomeric modification of said polymers.
  • PNB Polyvinyl butyral
  • Polyurethane Polyurethane
  • Thermoplastic Polyurethane Polycarbonate
  • Acrylic EN A
  • Polyethylene Thereftalate Polyester
  • PET Polyethylene ionomer
  • Surlyn Surlyn (Sentry Glas Plus)
  • acrylic resin any Ionomeric modification of said polymers.
  • a typical cross section of an armoured glazing is:
  • Example N°1B - A typical cross section of an armoured glazing without an Impact Energy Absorber is:
  • Another typical cross section of an armoured glazing is:
  • Another typical cross section of an armoured glazing is :

Landscapes

  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Joining Of Glass To Other Materials (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

There are disclosed glazing cross section constructions and the relevant concept for an transportation armoured ballistic construction having improved durability, anti spalling and ballistic performances. These constructions comprise one or more than one thin chemically strengthened glass plies that can be soda-lime, borosilicate or aluminosilicate. Said chemically strengthened glass ply will be manufactured with a suitable residual stress profile that prevent or limits the effect of splinters projection in case of ballistic impact and improve the overall ballistic performances of the glazing.

Description

TITLE: ANTI SPALLING GLASS CONSTRUCTION
1. Description
2.1 - Field of the invention
Armoured glazing constructions has as main objective to provide protection against ammunition of a defined type and energy/velocity characteristics. The most important applications includes military and civil vehicles, cash & transit vehicles, marine ships, aircrafts and government buildings and all of these can be either flat or curved. These glazing constructions and specially the transportation ones must comply with a series of basic functional requirements as a) high scratch/abrasion resistance b) high durability under environmental conditions b) free splinter projection (anti-spall) c) residual field of vision d)minimum weight e) minimum thickness and f) optical quality (free of distortions).
The anti-spall protection requirement is critical because the splinters projected to the internal environment to be protected have such a high energy that they are normally more devastating than even the bullet itself. Along with the previous statement the glass industry has developed two basic ways to reduce the severity of this problem i) incorporating a polymeric ply adhered to the rear most face of the armour construction facing the environment to be protected which brings several difficulties in the manufacturing processes, in the optical performance (distortion and double vision effect) and in the scratch resistance of the armoured construction, in the chemical stability under a lot of substances and worst, in the durability of its surface by the small hardness and ii) Multi layered glass and plastic construction with an increased thickness (regularly 2 times thicker than the most efficient compositions available of i). By increasing the total thickness of the armoured construction, this prevents the breakage of the last glass layer because all the energy is absorbed in the previous layers. The main weaknesses of this solution are a much heavy, thicker and less functional construction, making this solution the less common in the market nowadays. S ummarizing, up to today no c onstructions gives an effective solution for the problem of having an efficient BRG construction achieving the mechanical durability and chemical stability requirements that demand the transportation application.
This invention covers new and improved cross sections based on one or more thin chemically strengthened glasses to improve the splinter projection protection performances, to optimise the ballistic behaviour of the glazing, to extend the life span of the product and to achieve a considerable reduction on the complexity of the actual manufacturing techniques which finally reflects on a lower production cost.
2.2 - Description of the prior art
It is known that splinter projection resulting from armoured glass after a ballistic impact is a major problem potentially producing injuries to people protected by the glazing itself. Splinters are projected as a result of the ballistic impact because, after breakage of the glass layer facing the not impacted side, glass fragments from this layer can be detached out and still having enough kinetic energy to be projected towards the internal environment ( see figure 1 f or t eπninology description). In this way, even if the object which caused the ballistic impact (a bullet for anti-bullet glazing or any massive element projected intentionally or accidentally towards the glazing) did not penetrate the glazing entering the environment to be protected, the glass splinters generated as a result of the impact may be potentially very dangerous. To prevent this problem several solutions have been used in the bullet resistant glass (BRG) applications all based on the substitution of the inner layer of the glazing construction with a polymeric material that can be a thick layer (normally Polycarbonate) or in other embodiments a plastic film (Polyethylene Thereftalate - PET) in any case laminated with the main glass layers cross section. This solution solve the spalling problem because it prevents splinters to be projected from the inside of the glazing. Even if this solutions may be effective towards the splinters projection other problems are generated because of the plastic/polymeric nature of the inner layer of the armoured glass cross section. Optical, mechanical, chemical compatibility and durability problems come out because of the physical and chemical properties of t hese i nner p lastic 1 ayers. T he m ost e ffective p rotection a gainst splinters projection is offered by Polycarbonate, this material has a great impact resistance and it is the most used solution in the armoured glass applications. Nevertheless Polycarbonate is very sensitive to scratches, abrasion effects and if not suitably coated in a very short time it can become hazy because of scratches and abrasions and also because of stress crazing induced by coupled mechanism of chemical attack (coming from solvent and chemicals o f sealants and adhesive materials used in glazing assembly) and tensile condition. Its surface cannot be re-generated, that means that an anti scratch coating has to be always considered when using Polycarbonate as an inner layer of an armoured glass. The other problem related to Polycarbonate is its great sensitivity to chemical attack from agents as solvents, lubricants and many chemicals. This chemical attack when coupled with a mechanical stress situation produce a crazing effect on the Polycarbonate surface (stress-crazing). The other problem connected with Polycarbonate is coming from the difference in the thermal expansion coefficient (TEC) with glass (Polycarbonate TEC =7*10_51/K ; Soda/Lime Glass TEC = 8 .9*1()-6 1 /K at room temperature) this means that lamination processes should be performed with suitable interlayer materials that compensate the differences in the TEC between the two materials and also is chemically compatible with the Polycarbonate (Polyurethane interlayers are normally used). This last point creates another problem because normally glass layers are laminated with PVB (Polyvinyl Butyrral film) which has in general a different lamination temperature of Polyurethane. Optical problems like images distortion and deformation and double images may arises from the need of polycarbonate as an inner splinter protection layer. All these problems make the Polycarbonate not supply completely all the properties required by its application as an anti spalling layer in transportation BRG glazing constructions .
Similar mechanical, optical and maybe at a less extent chemical problems result from the use of PET films as inner splinter protection layers. Coated PET is maybe less sensitive to chemical attack than Polycarbonate but its ballistic and splinters protection perfomiances a re far 1 ess e ffective t han P olycarbonate a nd t here i s n ot a c ross section advantage (in terms of weight and thickness) of using PET instead of Polycarbonate. Another problem common to any polymeric splinter protection solution is that environmental conditions like ultraviolet solar radiation, temperature excursions and water vapour coming from the atmosphere may cause a durability issue causing a significant reduction in the material lifetime.
In either ways, using Polycarbonate and/or PET, a buffer or cover plate, usually being of soda lime glass must be used on top of the inner surface of said polymer within the manufacturing process (autoclave cycle) to achieve a relatively high flatness of the surface of said polymer and a good optical quality but, in the other hand, having an additional glass represents higher costs on raw materials, longer bending and autoclave processes and increased hand labour, reworks and rejected product on production, decreasing the productivity. All these reasons explain the need of having a ballistically efficient and mechanical and chemically durable solution for our transportation application.
Some P atents c an b e found i n the P atent 1 iterature that c laims p artial solutions to this problem:
US Patent N° 3,864,204 (Shorr, Littell,1975) and its continuation US Patent 4,130,684 (Littell,Shorr, 1978)
Field of application : Armoured Anti Bullet Glazing Cross Section Concept : Single glazed composite element
They claim a three sections cross-section concept of their construction namely: the impact striking section, the transition section and the impact absorption section. They claim a glass as innermost sheet (in the impact absorption section) to minimize spall effect but they claim only one glass layer with a thickness of 1.98 mm (2 mm) and they do not mention even a normal chemical strengthening treatment. Our Patent introduces a different concept of multi-layered impact (anti-spall section), made of thin (< 0,7mm and preferred 0,4mm) specially chemically strengthened glasses. Today very thin (below lmm) glass is available and chemical strengthening possibilities are fully understood. So the elements that differentiate our patent with these two is the use of specially tailored chemically strengthened thin glass that solve efficiently (with a considerable lower thickness) the anti-spall problem in an armoured glass construction.
US PATENT 4,312,903 (Molari, 1982)
Field of application : Armoured Anti Bullet Glazing Cross section concept : Double glazed element
This patent is limited in all its parts to double glazed structures to solve the spall problem. Even if they consider to use partially thin glass l aminate ( 0.7 to 5 .1 mm) they never mention chemical strengthening. Also because of the double glazed structure it will be nearly impossible or at least impractical to consider it for curved armoured windscreens or sidelites and also this solution will present plenty of optical problems in armoured transportation applications.
US PATENT 4,595,624 (Greathead, 1986)
Field of application : Laminated anti-bandit glazing Cross section concept : Single glazed composite element
In US Patent 4595624 they speak of chemically strengthened glass as strength element and also relates it to the ability to reduce the spall problem, anyway there are s everal points to be considered:
This patent is related to security glazing for anti-bandit applications and all examples and embodiments are referred to this type of manual attacks as hammers, pick-axes, crowbars, b ricks, i t c an b e seen that the lower spall generated by the impacts on their preferred embodiments is rated between 13gr. and more than 200 gr.; it is important to understand that for BRG applications the weight for the total spall generated is more than 500 times lower, it is impossible to have a BRG construction with the level of spall shown on the mentioned patent, this spall would destroy the witness foil of the standard ballistic test and would cause as much injures as the caused by the bullet by itself. So, it is evident that the claimed construction of the mentioned patent is far away from the field of application of our invention.
In their claim 1 they speak of "a rearmost glass layer no more than 2 mm thick .." that means 1 layer. And also they claim (always on claim 1) that this rearmost glass "resists spalling" that means it does not break, while we allow breakage of this layer with no spall effect and this is only possible with a thickness less than 0,7 mm and a specially tailored stress profile.
They speak about producing the claimed composition using Polyvinyl Butyral as bonding material, it is important to understand that a composition that only uses Polyvinyl Butyral as an adherent is restricted to not use most of the commercial impact energy absorbers, as Polycarbonate, by the chemical uncompatibility, so, the last solution of having this kind of construction as a BRG is with an extremely heavy composition. It is evident that its invention is not designed for transportation BRG compositions.
Additionally, the lowest thickness for its rearmost glass is 16% of the thickness of the thicker one in the composition; in our invention we are considering a thin glass with thickness less than 0,7mm and preferred 0,4mm whose thickness is much lower than 16% of the thickest glass on a typical construction (thickest glass on a BRG composition is ranged between 6 and 15mm).
Finally they do not fully understand how the glass should be chemically strengthened to prevent significant spalling effect (thin glass with a very deep case depth).
US Patent 6,156,417 (Edwards, d'Hooghe, 2000)
Field of application : Anti-intrusion glazing (not armoured nor anti-bullet)
Cross section concept : Lightweight Single glazed composite element (thickness < 6 mm) This patent is outside our specific application field, even if they consider application of thin glass (0.7 to 2 mm) because they consider this only for weight reduction and not for armoured anti bullet no-spall applications.
They do not mention chemical strengthening at all.
US PATENT 6,265,054 Bl (2001)
Field of application : Lightweight automotive glazing
Cross section concept : Lightweight Single glazed composite element (thickness < 5 mm)
Even for this case the situation is similar as the one we discussed above for patent 6,156,417. Here they consider even to use thinned glass (0.5 mm) but again for weight reduction and not for armoured anti bullet no-spall applications. Chemical strengthening is not mentioned.
OtherPatents like DE 3421 571 related to the US 5,496,643 (Von Alpen) introduces traditional cross section designs with a rearmost layer of polycarbonate coated with a self healing polymer that again presents problems with abrasion resistance, chemical resistance and compatibility, o ur s olution b ased on a completely inorganic (chemically strengthened glass) rearmost layer(s) solve this problem and also present advantages about the problem of the different thermal expansion of the layers that should be compensated with some intermediate metallic film.
Traditional manufacturing techniques based on separate bending and laminating processes (because of the utilization of different materials for the plies and for the plastic interlayers) takes time and are pretty expensive, this new solution improve the logistic and economy of these manufacturing processes eliminating some critical passages as well as eliminates the need of an additional cover plate for the inner surface polymer reducing raw material costs, bending and autoclave processes and hand labour. It is an object of this invention to provide a new efficient solution for the splinters projection problem in transportation bullet resistant glass, optimising the anti spalling cross section design in terms of weight (mass per unit area) and thickness reduction, but without generating other mechanical (scratches, abrasion) or chemical durability (materials compatibility) or optical problems or problems on its production characteristics of transportation bullet resistant glasses.
2.3 - Brief Description of the Drawings
Figure 1 - Ballistic impact on an armoured glazing
Figure 2a - Residual Stress Profile of a Thick Chemically Strengthened Glass Figure 2b - Residual Stress Profile of a Thin Chemically Strengthened Glass Figure 3a- Cross Section of a Single Thin Chemically Strengthened Glass Ply Figure 3b - Cross Section of a Multiple Thin Chemically Strengthened Glass Plies system Figure 3c- Cross Section of Single or Multiple Thin Chemically Strengthened Glass Plies system coupled with an inner plastic impact energy absorber
2.4 - Summary of the Invention
The concept that underlay this invention is that an inorganic scratch resistant and chemically inert material has to be used as the protecting ply against splinter projection (anti spall or no spall layer) in order to achieve the durability requirements demanded by the transportation application and keeping an efficient ballistic performance (as for total thickness vs. ballistic resistance). In accordance with this invention, glass itself is the material to be used as the last inner layer in an armoured glazing construction. This is because glass has an abrasion, scratches and chemical resistance far superior to any polymeric, plastic material (see Table 1).
Table 1 - Abrasion resistance comparison in terms of Percent of Haze increase Abrasion Test - Taber Abraser 100 Cycles
Figure imgf000011_0001
Even though the above table shows a significant difference between glass and any of the mentioned polymers, when the Taber Abraser test is performed with more than 100 cycles (500 and 1000) the difference grows considerably.
It is known that thermally tempered glass breaks in small fragments when broken but this is not a good solution for armoured ballistic glazing as splinter protection because:
1. it prevents residual vision when broken,
2. it cannot be fully tempered down to a thickness below 2.5 mm (with these thickness splinters are still large enough to produce injuries when projected with high kinetic energy)
It is known that chemically strengthened glass by ion-exchange has a far superior impact resistance when compared with thermally tempered glass, and the ion-exchange process, which is a surface inter diffusion process, has no limitations in terms of glass thickness. This means that it is possible to produce very thin layers (thickness down to 0.03 mm) of chemically strengthened glass offering:
1. a superior impact resistance
2. a large bending capability without breaking
3. in case of breakage residual vision and breaking fragments can be tailored to avoid large splinters to be projected (only small tiny fragments and powder are generated)
The chemical strengthening process introduces in the glass a residual stress profile with a compression layer on the surfaces and an inner tensile area. Fragmentation after breakage can be controlled to some extent by controlling the ion-exchange process parameters resulting in suitable values of the compression layer depth (Case depth CD), surface compression (Sc), and central tension (τ) (see Figure 2). The leading ideas in using thin CS glass in armoured constructions are :
1. Having a chemically strengthened thin glass (less than 0,7mm and preferred 0,4mm thickness) as the inner layer, so that the construction have the mechanical durability and the chemical stability of a glass.
2. Use a thin CS glass as inner layer that breaks in very tiny fragments that produce no injury still maintaining a residual vision after breakage.
3. Use a system of CS layers as last layers in an armoured glazing construction that offers subsequent ballistic and splinters protection according to the requested levels.
4. Use a system of Chemically Strengthened layer(s) as an anti splinter projection construction, with thickness comparable and even smaller than the thickness nonnally used in actual anti spalling constructions, allowing the armoured construction be more efficient as for relation thickness / durability and ballistic performance.
The key point in obtaining the results is in the possibility of tailoring the residual stress profile in order to achieve the envisaged bending/impact strength and the fragmentation behaviour ( see figure 2 b). O riginal g lass s trength, s urface c ompression and c ase d epth controls the impact/bending strength while the internal tension and glass thickness control the fragmentation behaviour. Let us explain in more detail the effect on the fragmentation of thin Chemically Strengthened glass. Normally in laminated glazing glass plies have a minimum thickness of 2 - 2.5 mm. Down to 2 mm it is even no more possible to induce a residual stress profile by thermal tempering. Thermal tempering has the advantage to induce a compression layer of 20% of original glass thickness resulting in a pretty high inner central tension that means enough energy to generate tiny fragmentation upon glass breakage. The compression layer depth introduced in soda-lime float glass by ion-exchange chemical strengthening is typically ranging from 10 μm to 50 μm. With a 30 μm compression layer depth on a 2 mm (2000 μm) glass the compression depth over thickness ratio is 1.5 % and the resulting fragmentation is coarse because of the low inner tensile stress. If we reduce the glass thickness down to 0.5 mm (500 μm) the compression depth over thickness become 6 % and considering that surface compression will be increased of at least 3 times (300 MPa) over the surface compression of a t hermally t empered g lass ( 100 M Pa) w e g et a n i ncrease i n t he i nner t ensile 1 evel resulting in a tiny fragmentation behaviour upon glass breakage. From another point of view the increased ultimate tensile strength (MOR) of chemically strengthened glass (250 MPa) versus thermally tempered glass (150 MPa) allows a significant deformation of chemically strengthened glass without breakage. This effect of increased internal tensile stress (which generates the tiny fragmentation) can be understood and described (see figures 2a and 2b) as follows: let us consider in figure 2 a normal thick glass (3 mm - 3000 μm) chemically strengthened, with a compression layer depth of 30 μm. The inner part of the glass (2940 μm) will be interested by a pretty low tensile stress and, upon breakage, large fragments will be generated. Now, If we imagine to squeeze the glass thickness down to 0.5 mm (500 μm), as the compressed part of the near surface glass will remain the same (because ion-exchange is a surface inter diffusion process), the inner tensile region will be reduced to 500-60 = 440 μm against the original 2940. This will modify the inner tensile stress increasing it is a significant way and generating (upon glass breakage) tiny fragmentation.
Another approach which is covered by the present invention is to introduce a plastic core ply as an outer layer of the anti spalling construction, that can be any low or high modulus polymer from Polycarbonate, to thick (0,13-25 mm) PNB to thick polyurethane (0,13-25 mm), to Polyethylene ionomer, Acrylic, EVA, Polyethylene thereftalate PET, to any ionomeric modification of said polymers like Surlyn (Sentry Glas Plus) that, in this case, it is not affected by surface scratch problems as an energy impact absorber and an inner (facing the internal environment in accordance with figures 3 a and 3b) controlled injury free splinter projection system consisting in a thin chemically strengthened glass layer or layers which may be treated with a coating process like silk-screening, CND, PND, Sputtering, sol-gel, painting or masking among others. The different systems will be accordingly used for the different ballistic protection levels required. The underlying concept of the invention is that the armoured glazing cross section should be divided in two parts:
A. Front most part facing the impact, this part has the purpose to break or deviate the bullet and to have a first stopping power and consist of multi-plies of thick (2-25mm) annealed glass.
B. Rearmost part facing the environment to be protected, has mainly the purpose of absorbing the residual impact energy without splinter projection towards the environment.
As it can be easily understood this invention is related to the part B. of the cross section.
There are several ballistic requirements based on international standards like:
Comite Europeon de Normalization (EN - 1063), Underwriters Laboratory (UL - 752), and National Institute of Justice (NIJ - 0108.01).
Normally these requirements are assessed by ballistic tests described in the above mentioned standards. A typical ballistic test (EN 1063) describe all the necessary conditions to perform the ballistic attack (Bullet type and weight, bullet velocity, number of strikes (typically 3) and striking distance, striking points - hit spacing (normally are the vertex of an equilateral triangle) samples number (typically 3 samples have to be tested), sample mounting system, and witness aluminium foil (0.02 mm thickness mass density 54 g/m2).
2.5 - Description of the preferred embodiments
According with this invention there will be three general preferred embodiments : 1. Single chemically strengthened construction with controlled injury free splinter projection (facing internal environment according to Figure 3a) of an armoured cross section.
hi this embodiment a single thin glass layer will be considered in the cross section of the armoured glazing as the external layer facing the environment to be protected. This ply will have the impact/bending strength sufficient to withstand the requested level of ballistic protection. The ply will have a chemical strengthening process with its central tension being tailored to release injury free splinters without generating perforations on the aluminium witness foil of the respective standard(s) ballistic test(s) for the given ballistic level The thin glass may be treated with a coating process like silk-screening, CND, PND, sputtering sol-gel, painting or masking among others, in order to keep a residual vision through the armoured construction after the first and subsequent shots based on the pre-defined ballistic level. The single thin glass may have some of the following compositions: Soda Lime, Borosilicate or Aluminosilicate or may be a layer of Aluminium Oxynitride, Magnesium Aluminate, Aluminium Oxide or some other armour ceramic.
2. Multiple Thin Glass Chemically Strengthened plies system composing a construction with controlled injury free splinter projection (facing internal environment according to Figure 3b) of an armoured cross section.
In this embodiment a system of multiple thin glass layers will be considered in the cross section of the armoured glazing as the external layer facing the environment to be protected. Each ply of the system will have the impact/bending strength sufficient to withstand the requested level of ballistic protection. The one or more plies of the embodiment will have a chemical strengthening process in order that the multiple plies system be tailored to release injury free splinters without generating perforations on the aluminium witness foil of the respective standard(s) ballistic test(s) for the given ballistic level . hi this construction, one or more plies may be treated with a coating process like silk-screening, CND, PND, sputtering sol-gel, painting or masking among others, in order to keep a residual vision through the armoured construction after the first and subsequent shots based on the pre-defined ballistic level. The thin glass plies system may have some of the following compositions: Soda Lime, Boro or Aluminosilicate or may be composed by plies o f Aluminium Oxynitride, Magnesium Aluminate, Aluminium Oxide or some other armour ceramic or their combination.
3. Single or Multiple construction with controlled injury free splinter projection (as described in 1 and 2) Coupled with a polymeric impact energy absorber (according to figure 3 c).
In t his e mbodiment a s ystem c omposed b y s ingle o r m ultiple t hin g lass 1 ayers will be considered as the external layer facing the environment to be protected in the cross section of the armoured glazing coupled with an intermediate plastic energy absorber which may be composed by one or more plies of polymeric materials. Each ply of the system will have the impact/bending strength sufficient to withstand the requested level of ballistic protection. The central tension of the last ply facing the environment will be tailored to release injury free splinters without generating perforations on the aluminium witness foil of the respective standard(s) ballistic test(s) for the given ballistic level.
The decision of placing one layer of chemically strengthened glass or a multi ply system will v ary d epending on the level of ballistic protection requested and requirements to keep a residual vision through the armoured construction after the first and subsequent shots.
The front most section is a construction composed by one or more plies of inorganic components with an individual thickness between 0.03 and 25mm.
The layer or multiple layers of polymer connecting the rearmost section (single or multiple p lies chemically strengthened glass) to the intermediate and to the front most section should be with a thickness from 0.13 up to 12 mm and the polymeric material can be: PNB (Polyvinyl butyral), Polyurethane, Thermoplastic Polyurethane, Polycarbonate, Acrylic, EN A, Polyethylene Thereftalate, Polyester (PET), Polyethylene ionomer, Surlyn (Sentry Glas Plus), acrylic resin and any Ionomeric modification of said polymers.
Within the possible embodiments it should be considered a glazing construction wherein metallic substrates, plates, meshes or fibbers can be attached to the edge of said construction for protection purposes within that said region of the window.
hi the next table can be seen the average weight for the total spall generated in a BRG construction with different options for its anti spalling glazing construction. The test was performed in accordance with the standard ΝIJ 0108.01 for a given level of ballistic resistance.
Table 2.
Figure imgf000017_0001
* It is not specified the part A of the BRG composition
** Spall recollected over a distance of 15cm from the rearmost side of the sample to the aluminium foil
ATG - Annealed Thin Glass
PU- Urethane
CSTG(l) - Chemically Strengthened Thin Glass with a chemical strengthening process A (given by the process variables). CSTG(l) - Chemically Strengthened Thin Glass with a chemical strengthening process B (given by the process variables).
2.6 -Examples of Preferred Embodiments
Example N°1A -
A typical cross section of an armoured glazing is:
6AG / 0.76PVB / 6AG / 0.76PVB / 4AG / 2.5PU / 3PC
Total thickness = 22-23 mm
Example N°1B - A typical cross section of an armoured glazing without an Impact Energy Absorber is:
6AG / 0.76PNB / 6AG / 0.76PNB / 6AG / 0.76PNB / 6AG / 0.76PVB / 6AG / 0.76PNB / 6AG / 0.76PNB / 6AG
Total thickness = 45-46 mm
AG - Annealed Glass PNB - Polyvinil Butyrral PU- Urethane PC - Polycarbonate
All dimensions are in millimetres (mm). This glasses (1A. & IB.) has no-spall performances upon the standardized EΝ-1063 / B4 NS, 3 test shot (44 Magnum- Full Metal Jacket bullet - Impact Energy 1500 J). This cross sections can be substituted according to the present invention with: 5AG / 0.76 PNB / 5AG / 0.76PVB / 5 AG / 4SGP / 0.5CSTG
or with:
5AG / 0.76 PNB / 6AG / 0.76PVB / 4AG / 1.24PU / 3PC / 0,62PU / 0,5 CSTG
SGP - Sentry Glas Plus® (Surlyn Ionomer)
Total thickness = 20-21 mm
Example Ν°2 -
Another typical cross section of an armoured glazing is:
8AG / 0.76 PVB / 9AG / 0.76PNB / 8AG / 0.76PNB / 8AG / 2.5PU / 2.5PC
Total thickness = 39-40 mm
AG - Annealed Glass
PVB - Polyvinil Butyral
PU -Urethane
PC - Polycarbonate
CSTG - Chemically Strengthened Thin Glass
All dimensions are in millimetres (mm). This glass has no-spall performances upon the standardized EΝ-1063 / B6 NS, 3 test shot (7.62 NATO Full Metal Jacket bullet - Impact Energy 3400 J). This cross section can be substituted according to the present invention with:
8AG / 0.76 PVB / 12AG / 0.76PVB / 9AG / 1.9PU / 2.5PC / 1.2PU / 0.5CS / 0.76PVB / 0.5CSTG Total thickness = 37-38 mm
Example N°3 -
Another typical cross section of an armoured glazing is :
6*[9AG / 0.76 PVB] / 4AG / 2.5PU / 2.5PC
Total thickness = 72/73 mm
AG - Annealed Glass
PVB - Polyvinil Butyral
PU — Urethane
PC - Polycarbonate
CSTG - Chemically Strengthened Thin Glass
ATG - Annealed Thin Glass
All dimensions are in millimetres (mm). This glass has no-spall performances upon the standardized EN-1063 / B7 NS, 3 test shot (7.62 NATO Armoured Piercing - Impact Energy 3300 J). This cross section can be substituted according to the present invention with :
9AG / 0.76 PVB / 4*[12AG / 0.76 PVB] / 3AG / 1.9PU / 2.5PC / 1.2PU / 0.5CS / 2* [0.76PVB/0.5CSTG]
Total thickness = 71/72 mm

Claims

3. ClaimsWe claim
1. A transportation anti bullet glazing concept construction with controlled injury free splinter projection based on inorganic rearmost ply materials with scratch and abrasion resistance and chemical durability comparable to soda-lime glass with the central tension of the last ply facing the environment tailored to release injury free splinters without generating perforations on the aluminium witness foil of the respective standard(s) ballistic test(s) for a given b allistic level and an induced residual field of vision after impact and said construction having an optimised cross section design in terms of weight (mass per unit area) and thickness reduction upon a ballistic level specific requirement.
2. A glazing construction in accordance with Claim 1 wherein it is composed by one or more thin glass(es) and one or more of said glass(es) are chemically strengthened.
3. A glazing construction in accordance with Claim 2 wherein one or more of said glass(es) have a controllable bending /impact strength and fragmentation pattern.
4. A glazing construction in accordance with Claim 2 wherein the thickness of the said individual thin glasses are between 0.03mm and 0,7mm.
5. A glazing construction in accordance with Claim 2 coupled to an intermediate plastic polymeric film or layer(s) used as impact energy absorber
6. A glazing construction in accordance with Claim 3 coupled to an intermediate plastic polymeric film or layer(s) used as impact energy absorber
7. A glazing construction in accordance with Claim 4 coupled to an intermediate plastic polymeric film or layer(s) used as impact energy absorber.
8. A glazing construction in accordance with Claims 2, 3 or 4 wherein the inorganic components are treated with a coating process like silk-screening, CVD, PVD, sputtering, sol-gel, painting or masking among others, in order to keep a residual vision through the armoured construction after the first and subsequent shots based on the pre-defined ballistic level.
9. A glazing construction in accordance with any one of Claims 5 to 7 wherein the inorganic components are treated with a coating process like silk-screening, CVD, PVD, s puttering, sol-gel, painting or masking among others, in order to keep a residual vision through the armoured construction after the first and subsequent shots based on the pre-defined ballistic level.
10. A glazing construction as are claimed in any one of Claims 5 to 7 in which the intermediate plastic polymeric film(s) or layer(s) used as impact energy absorber is composed by one or more plies of polymeric materials with a total thickness between 0.13 and 25mm.
11. A glazing construction in accordance with Claim 10 with an outer construction composed by one or more plies of inorganic components.
12. A glazing construction in accordance with Claims 1 or 11 wherein the inorganic components can be Soda Lime or Borosilicate or Aluminosilicate glass plies or their combination.
13. A glazing construction in accordance with Claims 1 or 11 wherein the components can be Aluminium Oxynitride, Magnesium Aluminate, Aluminium Oxide or some other armour ceramic or their combination.
14. A glazing construction in accordance with Claims 1 or 11 wherein there can be one or more of said thin glass components having a hardened edge generated by a manufacturing process free from micro cracks on the thin glass edge.
15. A glazing construction in accordance with Claim 12 wherein said inorganic components have an individual thickness between 0.03 and 25mm.
16. A glazing construction in accordance with Claim 13 wherein said ceramic components have an individual thickness between 0.03 and 25mm.
17. A glazing construction in accordance with Claim 14 wherein inorganic components have an individual thickness between 0.03 and 25mm
18. A glazing construction in accordance with Claim .1 wherein metallic substrates, alloys, films and/or electronic processors can be included within the components of the construction for solar protection, defrosting, demisting, de-icing, touch screen and/or displays or monitors purposes.
19. A glazing construction in accordance with Claim 1 wherein metallic substrates, plates, meshes or fibbers can be attached to the edge of said construction for protection purposes within that said region of the window.
20. A glazing construction in accordance with Claim 1 wherein a double or triple glazing construction can be considered and said couple or triplet of single glazed elements can be accommodated on a non p arallel configuration to improve the ballistic performance of the construction.
PCT/US2003/004234 2002-02-13 2003-02-13 Anti spalling glass construction WO2003068501A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003213028A AU2003213028A1 (en) 2002-02-13 2003-02-13 Anti spalling glass construction

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
DE20202223U DE20202223U1 (en) 2002-02-13 2002-02-13 Chipproof glass construction
DE20202223.4 2002-02-13
US37413202P 2002-04-22 2002-04-22
US60/374,132 2002-04-22
US38328602P 2002-05-28 2002-05-28
US60/383,286 2002-05-28

Publications (2)

Publication Number Publication Date
WO2003068501A1 WO2003068501A1 (en) 2003-08-21
WO2003068501A9 true WO2003068501A9 (en) 2004-04-22

Family

ID=27738764

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2003/004234 WO2003068501A1 (en) 2002-02-13 2003-02-13 Anti spalling glass construction

Country Status (2)

Country Link
AU (1) AU2003213028A1 (en)
WO (1) WO2003068501A1 (en)

Families Citing this family (33)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7348076B2 (en) 2004-04-08 2008-03-25 Saint-Gobain Ceramics & Plastics, Inc. Single crystals and methods for fabricating same
FR2869605B1 (en) * 2004-04-30 2007-04-06 Saint Gobain SHEET STRUCTURE WITH BALISTIC RESISTANCE
FR2876786B1 (en) * 2004-10-18 2007-01-12 Saint Gobain LAMINATED STRUCTURE RESISTANT TO PERFORATING PROJECTILES
EP2275771A1 (en) 2005-06-10 2011-01-19 Saint-Gobain Ceramics and Plastics, Inc. Transparent ceramic composite
US9162426B2 (en) * 2006-08-30 2015-10-20 Saxon Glass Technologies, Inc. Transparent armor systems, methods for making and methods for using
CN101516798A (en) 2006-09-14 2009-08-26 日本电气硝子株式会社 Sheet glass laminate structure and multiple sheet glass laminate structure
DE202007001565U1 (en) * 2007-02-02 2007-04-05 Isoclima Gmbh Armoured glass comprises at least one optically transparent sintered glass material made of aluminium oxynitride
MX2009012640A (en) * 2007-05-21 2010-02-12 Corning Inc Thermally-bonded glass-ceramic/glass laminates, their use in armor applications and methods of making same.
DE102007025893B4 (en) * 2007-06-01 2014-08-21 Schott Ag Glass-ceramic armor material and method of making armor with a glass-ceramic component
EP2030958B1 (en) * 2007-08-27 2013-04-10 Rohm and Haas Electronic Materials LLC Method for producing polycrystalline monolithic magnesium aluminate spinels
JP4998859B2 (en) * 2007-09-27 2012-08-15 日本電気硝子株式会社 Laminated glass and laminated glass member
WO2009145909A1 (en) * 2008-05-30 2009-12-03 Corning Incorporated Photovoltaic glass laminated articles and layered articles
FR2932411B1 (en) * 2008-06-12 2011-01-21 Saint Gobain INCREASED BULK RESISTANCE GLAZING
US7641965B1 (en) 2008-06-30 2010-01-05 E.I. Du Pont De Nemours And Company Transparent light-weight safety glazings
BRPI0914353B8 (en) 2008-10-31 2022-08-02 Dow Chemical Co safety laminate
DE102008043718B9 (en) 2008-11-13 2012-05-31 Schott Ag Highly transparent impact-resistant disc laminate comprising at least one slice of a lithium alumino-silicate glass-ceramic and its use
US9199873B2 (en) 2008-11-13 2015-12-01 Schott Ag Process for producing a highly transparent impact-resistant glass ceramic
MX2011006996A (en) 2008-12-31 2011-08-08 Du Pont Laminates comprising ionomer interlayers with low haze and high moisture resistance.
DE102010013641A1 (en) 2010-04-01 2011-10-06 Schott Ag Transparent glass-polymer composite
US8640591B2 (en) * 2010-06-30 2014-02-04 Corning Incorporated Transparent armor with improved multi-hit performance by use of a thin cover glass
US9616641B2 (en) * 2011-06-24 2017-04-11 Corning Incorporated Light-weight hybrid glass laminates
US10035331B2 (en) * 2011-06-24 2018-07-31 Corning Incorporated Light-weight hybrid glass laminates
DE102012105900A1 (en) * 2012-07-03 2014-01-09 Schott Ag Bullet resistant laminated glass
US20150202845A1 (en) * 2012-08-03 2015-07-23 Corning Incorporated Multi-layer transparent light-weight safety glazings
WO2014100309A1 (en) 2012-12-19 2014-06-26 E. I. Du Pont De Nemours And Company Cross-linkable acid copolymer composition and its use in glass laminates
US9703010B2 (en) 2013-02-08 2017-07-11 Corning Incorporated Articles with anti-reflective high-hardness coatings and related methods
CA2925022C (en) 2013-10-23 2018-07-17 Saint-Gobain Glass France Composite glass with at least one chemically tempered pane
US20150158986A1 (en) 2013-12-06 2015-06-11 E.I. Du Pont De Nemours And Company Polymeric interlayer sheets and light weight laminates produced therefrom
FR3031065B1 (en) * 2014-12-29 2019-08-30 Saint-Gobain Glass France GLAZING SHEET WITH SLIM-GLASS SHEET ANTI-ECLAT
KR102338547B1 (en) * 2016-03-30 2021-12-14 세키스이가가쿠 고교가부시키가이샤 Interlayer film for laminated glass and laminated glass
US11047650B2 (en) 2017-09-29 2021-06-29 Saint-Gobain Ceramics & Plastics, Inc. Transparent composite having a laminated structure
DE102020111381A1 (en) 2020-04-27 2021-10-28 GuS glass + safety GmbH & Co. KG Glass structure of a bulletproof glass composite pane
CN115257085B (en) * 2022-06-28 2023-09-26 杭州涛行科技有限公司 Toughened explosion-proof glass with safety buffering function

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1755395B1 (en) * 1968-01-29 1975-02-27 Saint Gobain Windshield for automobiles
US3864204A (en) * 1969-04-24 1975-02-04 Ppg Industries Inc Multilayered safety glass
GB1275653A (en) * 1969-08-15 1972-05-24 Glaverbel Articles of chemically tempered glass
US4663228A (en) * 1983-05-03 1987-05-05 Advanced Glass Systems Corp. Laminated safety glass
GB8321555D0 (en) * 1983-08-10 1983-09-14 Post Office Security glazing
US5002820A (en) * 1989-05-25 1991-03-26 Artistic Glass Products Laminated safety glass
EP0654344A1 (en) * 1993-11-24 1995-05-24 Sierracin Corporation Thin laminated heated glass face ply for aircraft windshields
US20030044579A1 (en) * 2001-08-25 2003-03-06 Nelson Bolton Anti-spalling laminated safety glass

Also Published As

Publication number Publication date
AU2003213028A1 (en) 2003-09-04
WO2003068501A1 (en) 2003-08-21

Similar Documents

Publication Publication Date Title
WO2003068501A9 (en) Anti spalling glass construction
JP6070969B2 (en) Multilayer transparent lightweight safety glazing
US8025004B2 (en) Transparent ceramic composite
EP2244988B1 (en) Lightweight transparent armor window
US9656913B2 (en) Transparent laminate which inhibits puncture by projectiles
WO2008147391A2 (en) Transparent ballistic resistant armor
EP2652433B1 (en) Sandwiched fiber composites for ballistic applications
US20180194114A1 (en) Lightweight automotive laminate with high resistance to breakage
CA2592452A1 (en) Optically transmissive armor composite
US20180207911A1 (en) Asymmtetric glazing laminates with high impact resistance
JP6328109B2 (en) Penetration resistant laminated glass
US12128650B2 (en) Hybrid asymmetric automotive laminate
WO2022003650A1 (en) Hybrid asymmetric automotive laminate
DE102012210906B4 (en) Security glazing and their uses
US20100300276A1 (en) High-performance bulletproof glazing
US20120174755A1 (en) Optically transmissive armor composite and method of manufacture
Zang et al. Laminated glass
US20100126336A1 (en) Optically transmissive armor composite and method of manufacture
CN2714562Y (en) High strength bullet-proof laminated glass
DE20202223U1 (en) Chipproof glass construction
US20220242098A1 (en) Hybrid flex armoured composites
WO2023170609A1 (en) Armored glass with improved aesthetics and daylight opening
EP3853018A1 (en) Ballistic resistant insulated glazing units
WO2020058439A1 (en) Ballistic resistant insulated glazing units
WO2004055468A1 (en) Bulletproof transparent plate

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SC SD SE SG SK SL TJ TM TN TR TT TZ UA UG US UZ VC VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LU MC NL PT SE SI SK TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
COP Corrected version of pamphlet

Free format text: PAGES 1/4-4/4, DRAWINGS, REPLACED BY NEW PAGES 1/4-4/4

122 Ep: pct app. not ent. europ. phase
NENP Non-entry into the national phase in:

Ref country code: JP

WWW Wipo information: withdrawn in national office

Country of ref document: JP