Prince Rupert's drops (also known as Dutch tears or Batavian tears) [1] [2] are toughened glass beads created by dripping molten glass into cold water, which causes it to solidify into a tadpole-shaped droplet with a long, thin tail. These droplets are characterized internally by very high residual stresses, which give rise to counter-intuitive properties, such as the ability to withstand a blow from a hammer or a bullet on the bulbous end without breaking, while exhibiting explosive disintegration if the tail end is even slightly damaged. In nature, similar structures are produced under certain conditions in volcanic lava and are known as Pele's tears.
The drops are named after Prince Rupert of the Rhine, who brought them to England in 1660, although they were reportedly being produced in the Netherlands earlier in the 17th century and had probably been known to glassmakers for much longer. They were studied as scientific curiosities by the Royal Society, and the unraveling of the principles of their unusual properties probably led to the development of the process for the production of toughened glass, patented in 1874. Research carried out in the 20th and 21st centuries shed further light on the reasons for the drops' contradictory properties.
Prince Rupert's drops are produced by dropping molten glass drops into cold water. The glass rapidly cools and solidifies in the water from the outside inward. This thermal quenching may be described by means of a simplified model of a rapidly cooled sphere. [3] Prince Rupert's drops have remained a scientific curiosity for nearly 400 years due to two unusual mechanical properties: [4] when the tail is snipped, the drop disintegrates explosively into powder, whereas the bulbous head can withstand compressive forces of up to 664,300 newtons (67,740 kgf).
The explosive disintegration arises due to multiple crack bifurcation events when the tail is cut – a single crack is accelerated in the tensile residual stress field in the center of the tail and bifurcates after it reaches a critical velocity of 1,450–1,900 metres per second (3,200–4,300 mph). [5] [6] Given these high speeds, the disintegration process due to crack bifurcation can only be inferred by looking into the tail and employing a high-speed camera. This is perhaps why this curious property of the drops remained unexplained for centuries. [7]
The second unusual property of the drops, namely the strength of the heads, is a direct consequence of large compressive residual stressesup to —700 megapascals (100,000 psi)that exist in the vicinity of the head's outer surface. —[2] This stress distribution is measured by using glass's natural property of stress-induced birefringence and by employing techniques of 3D photoelasticity. The high fracture toughness due to residual compressive stresses makes Prince Rupert's drops one of the earliest examples of toughened glass.
It has been suggested that methods for making the drops have been known to glassmakers since at least the times of the Roman Empire. [8]
Sometimes attributed to Dutch inventor Cornelis Drebbel, the drops were often referred to as lacrymae Borussicae (Prussian tears) or lacrymae Batavicae (Dutch tears) in contemporary accounts. [9]
Verifiable accounts of the drops from Mecklenburg in North Germany appear as early as 1625. [10] The secret of how to make them remained in the Mecklenburg area for some time, although the drops were disseminated across Europe from there, for sale as toys or curiosities.
The Dutch scientist Constantijn Huygens asked Margaret Cavendish, Duchess of Newcastle to investigate the properties of the drops; her opinion after carrying out experiments was that a small amount of volatile liquid was trapped inside. [11]
Although Prince Rupert did not discover the drops, he was responsible for bringing them to Britain in 1660. He gave them to King Charles II, who in turn delivered them in 1661 to the Royal Society (which had been created the previous year) for scientific study. Several early publications from the Royal Society give accounts of the drops and describe experiments performed. [12] Among these publications was Micrographia of 1665 by Robert Hooke, who later would discover Hooke's Law. [4] His publication laid out correctly most of what can be said about Prince Rupert's drops—without a fuller understanding than existed at the time of elasticity (to which Hooke himself later contributed), and of the failure of brittle materials from the propagation of cracks. A fuller understanding of crack propagation had to wait until the work of A. A. Griffith in 1920. [13]
In 1994, Srinivasan Chandrasekar, an engineering professor at Purdue University, and Munawar Chaudhri, head of the materials group at the University of Cambridge, used high-speed framing photography to observe the drop-shattering process and concluded that while the surface of the drops experiences highly compressive stresses, the inside experiences high tension forces, creating a state of unequal equilibrium which can easily be disturbed by breaking the tail. However, this left the question of how the stresses are distributed throughout a Prince Rupert's drop.
In a further study published in 2017, the team collaborated with Hillar Aben, a professor at Tallinn University of Technology in Estonia using a transmission polariscope to measure the optical retardation of light from a red LED as it travelled through the glass drop, and used the data to construct the stress distribution throughout the drop. This showed that the heads of the drops have a much higher surface compressive stress than previously thought at up to 700 megapascals (100,000 psi), but that this surface compressive layer is also thin, only about 10% of the diameter of the head of a drop. This gives the surface a high fracture strength, which means it is necessary to create a crack that enters the interior tension zone to break the droplet. As cracks on the surface tend to grow parallel to the surface, they cannot enter the tension zone but a disturbance in the tail allows cracks to enter the tension zone. [14]
A scholarly account of the early history of Prince Rupert's drops is given in the Notes and Records of the Royal Society of London, where much of the early scientific study of the drops was performed. [8]
The study of drops probably inspired the process of producing toughened glass by quenching. It was patented in England by Parisian Francois Barthelemy Alfred Royer de la Bastie in 1874, just one year after V. De Luynes had published accounts of his experiments with them. [8]
Since at least the 19th century, it has been known that formations similar to Prince Rupert's drops are produced under certain conditions in volcanic lava. [15] More recently researchers at the University of Bristol and the University of Iceland have studied the glass particles produced by explosive fragmentation of Prince Rupert's drops in the laboratory to better understand magma fragmentation and ash formation driven by stored thermal stresses in active volcanoes. [16]
Because of their use as a party piece, Prince Rupert's drops became widely known in the late 17th century—far more than today. It can be seen that educated people (or those in "society") were expected to be familiar with them, from their use in the literature of the day. Samuel Butler used them as a metaphor in his poem Hudibras in 1663, [17] [18] and Pepys refers to them in his diary. [19]
The drops were immortalized in a verse of the anonymous Ballad of Gresham College (1663):
And that which makes their Fame ring louder,
With much adoe they shew'd the King
To make glasse Buttons turn to powder,
If off the[m] their tayles you doe but wring.
How this was donne by soe small Force
Did cost the Colledg a Month's discourse. [20]
Diarist George Templeton Strong wrote (volume 4, p. 122) of a hazardous sudden breaking up of pedestrian-bearing ice in New York City's East River during the winter of 1867 that "The ice flashed into fragments all at once like a Prince Rupert's drop."
Alfred Jarry's 1902 novel Supermale makes reference to the drops in an analogy for the molten glass drops falling from a failed device meant to pass eleven thousand volts of electricity through the supermale's body.
Sigmund Freud, discussing the dissolution of military groups in Group Psychology and the Analysis of the Ego (1921), notes the panic that results from the loss of the leader: "The group vanishes in dust, like a Prince Rupert's drop when its tail is broken off."
E. R. Eddison's 1935 novel Mistress of Mistresses references Rupert's drops in the last chapter as Fiorinda sets off a whole set of them.
In the 1940 detective novel There Came Both Mist and Snow by Michael Innes (J. I. M. Stewart), a character incorrectly refers to them as "Verona drops"; the error is corrected towards the end of the novel by the detective Sir John Appleby.
In his 1943 novella Conjure Wife , Fritz Leiber uses Prince Rupert drops as a metaphor for the volatility of several characters' personalities. These small-town college faculty people seem to be placid and impervious, but "explode" at a mere "flick of the filament".
Peter Carey devotes a chapter to the drops in his 1988 novel Oscar and Lucinda .
The title-giving suite to progressive rock band King Crimson's 1970 third studio album Lizard includes both parts referring to a fictionalised version of Prince Rupert as well as an extended section called "The Battle of Glass Tears".
Robert Hooke was an English polymath who was active as a physicist, astronomer, geologist, meteorologist and architect. He is credited as one of the first scientists to investigate living things at microscopic scale in 1665, using a compound microscope that he designed. Hooke was an impoverished scientific inquirer in young adulthood who went on to become one of the most important scientists of his time. After the Great Fire of London in 1666, Hooke attained wealth and esteem by performing more than half of the property line surveys and assisting with the city's rapid reconstruction. Often vilified by writers in the centuries after his death, his reputation was restored at the end of the twentieth century and he has been called "England's Leonardo [da Vinci]".
In biology, cell theory is a scientific theory first formulated in the mid-nineteenth century, that living organisms are made up of cells, that they are the basic structural/organizational unit of all organisms, and that all cells come from pre-existing cells. Cells are the basic unit of structure in all living organisms and also the basic unit of reproduction.
In mechanics, compressive strength is the capacity of a material or structure to withstand loads tending to reduce size (compression). It is opposed to tensile strength which withstands loads tending to elongate, resisting tension. In the study of strength of materials, compressive strength, tensile strength, and shear strength can be analyzed independently.
In materials science, fatigue is the initiation and propagation of cracks in a material due to cyclic loading. Once a fatigue crack has initiated, it grows a small amount with each loading cycle, typically producing striations on some parts of the fracture surface. The crack will continue to grow until it reaches a critical size, which occurs when the stress intensity factor of the crack exceeds the fracture toughness of the material, producing rapid propagation and typically complete fracture of the structure.
A material is brittle if, when subjected to stress, it fractures with little elastic deformation and without significant plastic deformation. Brittle materials absorb relatively little energy prior to fracture, even those of high strength. Breaking is often accompanied by a sharp snapping sound.
Shot peening is a cold working process used to produce a compressive residual stress layer and modify the mechanical properties of metals and composites. It entails striking a surface with shot with force sufficient to create plastic deformation.
In materials science and solid mechanics, residual stresses are stresses that remain in a solid material after the original cause of the stresses has been removed. Residual stress may be desirable or undesirable. For example, laser peening imparts deep beneficial compressive residual stresses into metal components such as turbine engine fan blades, and it is used in toughened glass to allow for large, thin, crack- and scratch-resistant glass displays on smartphones. However, unintended residual stress in a designed structure may cause it to fail prematurely.
Stress corrosion cracking (SCC) is the growth of crack formation in a corrosive environment. It can lead to unexpected and sudden failure of normally ductile metal alloys subjected to a tensile stress, especially at elevated temperature. SCC is highly chemically specific in that certain alloys are likely to undergo SCC only when exposed to a small number of chemical environments. The chemical environment that causes SCC for a given alloy is often one which is only mildly corrosive to the metal. Hence, metal parts with severe SCC can appear bright and shiny, while being filled with microscopic cracks. This factor makes it common for SCC to go undetected prior to failure. SCC often progresses rapidly, and is more common among alloys than pure metals. The specific environment is of crucial importance, and only very small concentrations of certain highly active chemicals are needed to produce catastrophic cracking, often leading to devastating and unexpected failure.
In materials science, fracture toughness is the critical stress intensity factor of a sharp crack where propagation of the crack suddenly becomes rapid and unlimited. A component's thickness affects the constraint conditions at the tip of a crack with thin components having plane stress conditions and thick components having plane strain conditions. Plane strain conditions give the lowest fracture toughness value which is a material property. The critical value of stress intensity factor in mode I loading measured under plane strain conditions is known as the plane strain fracture toughness, denoted . When a test fails to meet the thickness and other test requirements that are in place to ensure plane strain conditions, the fracture toughness value produced is given the designation . Fracture toughness is a quantitative way of expressing a material's resistance to crack propagation and standard values for a given material are generally available.
Pele's tears are small pieces of solidified lava drops formed when airborne particles of molten material fuse into tearlike drops of volcanic glass. Pele's tears are jet black in color and are often found on one end of a strand of Pele's hair. Pele's tears is primarily a scientific term used by volcanologists.
Tempered or toughened glass is a type of safety glass processed by controlled thermal or chemical treatments to increase its strength compared with normal glass. Tempering puts the outer surfaces into compression and the interior into tension. Such stresses cause the glass, when broken, to shatter into small granular chunks instead of splintering into large jagged shards as ordinary annealed glass does. These smaller, granular chunks are less likely to cause deep penetration when forced into the surface of an object compared to larger, jagged shards because the reduction in both the mass and the maximum dimension of a glass fragment corresponds with a reduction in both the momentum and the penetration depth of the glass fragment.
Laser peening (LP), or laser shock peening (LSP), is a surface engineering process used to impart beneficial residual stresses in materials. The deep, high-magnitude compressive residual stresses induced by laser peening increase the resistance of materials to surface-related failures, such as fatigue, fretting fatigue, and stress corrosion cracking. Laser shock peening can also be used to strengthen thin sections, harden surfaces, shape or straighten parts, break up hard materials, compact powdered metals and for other applications where high-pressure, short duration shock waves offer desirable processing results.
A Bologna bottle, also known as a Bologna phial or philosophical vial, is a glass bottle which has great external strength, often used in physics demonstrations and magic tricks. The exterior is generally strong enough that one could pound a nail into a block of wood using the bottle as a hammer; however, even a small scratch on the interior would cause it to crumble.
Chemically strengthened glass is a type of glass that has increased strength as a result of a post-production chemical process. When broken, it still shatters in long pointed splinters similar to float glass. For this reason, it is not considered a safety glass and must be laminated if safety glass is required. However, chemically strengthened glass is typically six to eight times the strength of float glass. The most common trademark for this kind of glass is Gorilla glass.
Rubber toughening is a process in which rubber nanoparticles are interspersed within a polymer matrix to increase the mechanical robustness, or toughness, of the material. By "toughening" a polymer it is meant that the ability of the polymeric substance to absorb energy and plastically deform without fracture is increased. Considering the significant advantages in mechanical properties that rubber toughening offers, most major thermoplastics are available in rubber-toughened versions; for many engineering applications, material toughness is a deciding factor in final material selection.
Gorilla Glass, developed and manufactured by Corning, is a brand of chemically strengthened glass now in its ninth generation. Designed to be thin, light, and damage-resistant, its surface strength and crack-resistance are achieved through immersion in a hot potassium-salt ion-exchange bath.
Materials that are used for biomedical or clinical applications are known as biomaterials. The following article deals with fifth generation biomaterials that are used for bone structure replacement. For any material to be classified for biomedical applications, three requirements must be met. The first requirement is that the material must be biocompatible; it means that the organism should not treat it as a foreign object. Secondly, the material should be biodegradable ; the material should harmlessly degrade or dissolve in the body of the organism to allow it to resume natural functioning. Thirdly, the material should be mechanically sound; for the replacement of load-bearing structures, the material should possess equivalent or greater mechanical stability to ensure high reliability of the graft.
In metallurgy, peening is the process of working a metal's surface to improve its material properties, usually by mechanical means, such as hammer blows, by blasting with shot, focusing light, or in recent years, with water column impacts and cavitation jets. With the notable exception of laser peening, peening is normally a cold work process tending to expand the surface of the cold metal, thus inducing compressive stresses or relieving tensile stresses already present. It can also encourage strain hardening of the surface metal.
In materials science, toughening refers to the process of making a material more resistant to the propagation of cracks. When a crack propagates, the associated irreversible work in different materials classes is different. Thus, the most effective toughening mechanisms differ among different materials classes. The crack tip plasticity is important in toughening of metals and long-chain polymers. Ceramics have limited crack tip plasticity and primarily rely on different toughening mechanisms.