Silica nanoparticles make Teflon tougher


Atomic force microscope image of 50-nm diameter silica nanoparticles on PTFE surface. Researchers at the University of Arkansas found that relatively low concentrations of the particles greatly improved PTFE wear resistance. Credit: M. Zou, University of Arkansas

Well known as a nonstick surface in applications from kitchen tools to aerospace and medical components, polytetrafluoroethylene (Teflon) is getting a boost in wear resistance thanks to silica nanoparticles.

According to this press release, researchers at the University of Arkansas (Fayetteville) treated PTFE films with silica nanoparticles to significantly reduce wear while maintaining low friction in tests.

In a comparison of PTFE surfaces impregnated with silica nanoparticles versus pure PTFE films and bare stainless steel, the researchers found the composite films had greatly improved wear characteristics. All PTFE coatings were produced by dip coating type 316 stainless steel substrates.

According to researcher Min Zou, associate professor, director of the university’s Nano Mechanics and Tribology Laboratory (NMTL), and holder of the 21st Century Professorship in Mechanical Engineering, workers tested PTFE surfaces with two concentrations of 50-nm diameter silica nanoparticles—1.7 and 3.3 wt.%—against a conventional PTFE surface and bare stainless steel.

“Linear reciprocating wear tests were performed by repetitively rubbing the test samples against a chrome steel ball under an applied pressure up to 0.5 GPa,” Zou explained in an e-mail message. “The pure PTFE film failed immediately under 0.5 GPa pressure, while the composite film with 3.3 wt.% silica lasted 300 cycles.”

Results of the initial study were published in Tribology Transactions, a journal of the Society of Tribologists and Lubrication Engineers (Park Ridge, Ill.). The paper received the Society’s Al Sonntag Award for the best paper published on solid lubricants.

Zou and her team have continued their research with further development of the silica–PTFE composite material as well as testing of other types of nanoparticles in thin PTFE coatings, she reports. “The durability of the film has been increased four times compared to what we reported in this paper. If adding an adhesive layer, durability is increased 70 times. “

NMTL has developed a variety of nanoengineered surfaces (NESs), which are engineered with nanoscale topographies and chemistries to reduce friction and wear in tribological applications, change wetting properties of surfaces for anti-fogging and self-cleaning properties, and facilitate cell adhesion and growth in biomedical applications. Zou welcomes collaborative opportunities on novel methods of fabrication, characterization, and applications of NESs.


Strong, tough, and uncrushable—How Mother Nature designs structural biological materials

Nature is replete with ingenious structures to make life not just possible, but better. The bony plates of seahorse skeletons, for example, slide past each other, giving the creature incredible flexibility. Materials scientists at the University of California, San Diego, are working to unlock the secrets. Credit: Joanna McKittrick, UCSD.

The Materials Genome Initiative boosted the idea of “materials by design” to the forefront, giving it a name and a cause—reduce the timeline from material discovery to manufacture by half. Without getting into theological or philosophical arguments, Nature may be way ahead of us on executing the idea of materials by design, and the “cause” is simple: survival.

Nature has designed some ingenious materials. Spider thread, for example, has amazing tensile and stretching properties. Abalone shells resist the erosion of ocean floor environments that polish materials with similar compositions into shiny, pretty baubles prized by artists. Why don’t bird beaks break? How is the structure of seahorse spines an advantage?

University of California, San Diego, researchers Marc Meyers and Joanna McKittrick, and Po-Yu Chen, now at National Tsing Hua University, Taiwan—recently wrote a review article in Science (subscription required) on the mechanics of structural biological materials. Specifically, they were looking for the connection between the structure and properties of biological materials, with an eye toward understanding how to engineer similar structures and properties in synthetic materials. Their review focused on three properties: strength under tension, toughness, and resistance to buckling/torsion.

First, they note that there are seven distinguishing characteristics of structural biological materials: self assembly, multifunctionality, hierarchy (different structures at different scales for different purposes), hydration, mild synthesis conditions (low temperature and pressure in aqueous environments), constraints imposed by evolution and environment, and self-healing ability.

Biological materials fall into two broad structural categories: “soft” structures, which are non-mineralized, and “hard” structures, which are composites of minerals and fibrous organic biopolymers. Examples of the former include collagen, keratin, elastin, chitin, lignin, and others. Mineralized composites, the latter group, consist of a mineral reinforcement phase such as hydroxyapatite, calcium carbonate, or siica, embedded in a biopolymer matrix, such as collagen or chitin.

Examples from nature provide insights into the mechanics of structural biological materials. In a press release, McKittrick says, “Mother Nature give us templates. We are trying to understand them better so we can implement them in new materials.”

Besides properties, biological materials have secrets to reveal regarding processing. Exoskeletal animals, like abalones, grow their shells one layer at a time. McKittrick observes in the press release that 3D printing is basically the same concept. “You could build a material similar to the abalone shell using principles we learned from nature by printing layer upon layer of mineral deposits—and do it much faster than nature would.”

Like engineered materials, biological materials bring different properties to the task. “The mechanical behavior of biological constituents and composites is quite diverse,” the authors write. The stress-strain behavior of biominerals, for example, is linear. However, biopolymers behave in a nonlinear fashion, and are key contributors to the high tensile strength of biological materials. Deformation happens first with a stiffening process involving molecular uncoiling and unkinking. After the fibers are fully extended, the polymer backbone stretches and accommodates quite a lot of strain before rupture. Spider silk is a good example of a biopolymer that deforms, yet is strong.

If you are alive, you’ve got to be tough, too. According to the paper, “Toughness is defined as the amount of energy a material absorbs before it fails.” That is, tough materials can deform quite a lot and are strong. They employ several toughening mechanisms that take advantage of the nature of interfaces, for example, by interrupting crack propagation, deflecting cracks, or bridging gaps created by cracks. Examples of tough biological structures include lobster shells, antler bones, abalone nacre, and silica sponge.

Finally, Nature has tricks to share regarding structures that resist bending, torsion, and buckling and the necessary tradeoff between bending and buckling resistance. She does this with thin solid shells filled with lightweight foam or internal struts. This way structural integrity is maximized and the “weight penalty” is minimized. Examples from the plant world include bamboo and the giant bird of paradise stem. The animal world offers structures such as porcupine quills, feathers, and beaks. Skeletal bones, too, are structured with a solid external “cortical bone” sheath filled with a cellular “cancellous bone” core.

Besides structural biological materials, there are other familiar applications of bioinspired materials. For example, most are familiar with the invention of Velcro being inspired by the way plant burrs stuck to animal fur. Olympic sports fans may recall hearing about high-performance swimsuits (eventually banned from competition) that mimic the structure of shark skin and reduce drag in the water. New super-adhesive surgical tapes are designed after gecko foot structure.

“There are a tremendous number of examples of things we can’t do with traditional materials,” McKittrick says in the press release. She admits it will take time, “But they will be better.”

Who better than Mother Nature would know about genomes and design of materials!

If you are attending the PACRIM-GOMD conference in a few weeks, stop by ‘Symposium 23: Advances in Biomineralized Ceramics, Bioceramics, and Bioinstpired Designs,’ which McKittrick and Chen helped organize.

The paper is “Structural Biological Materials: Critical Mechanics-Materials Connections,” by Marc André Meyers, Joanna McKittrick, and Po-Yu Chen. Science, 15 February 2013 (DOI: 10.1126/science.1220854).


News from the glass and refractory ceramics worlds

• Austrian fireproof materials maker RHI is considering building a new plant in the United States, the company said, to join the growing number of European industrial firms attracted by cheap energy prices across the Atlantic. RHI said it would make a decision in the fourth quarter and could invest about €50 million to build or take over a plant.

Vesuvius said it expects its 2013 revenue to fall following restructuring and disposals. Trading has been broadly flat this year and production of steel and foundry has been affected by difficult market conditions; production fell 5.0 percent in Europe and North America in the first four months of the year, offsetting a 6.4 percent growth in Asia.

Pretoria Portland Cement Company of South Africa plans to build a 1 million metric tons per year plant costing $200 million in the Democratic Republic of Congo. The South African cement producer aims to make at least 40 percent of its sales outside of South Africa by 2016.

• Australia’s CSR Ltd. has warned its Viridian glass division will be a continued drag on earnings in the year ahead, even after a reorganization and a $196 million provision booked in the latest financial year.

PPG Fiber Glass has sold its 50 percent interest in the PPG-Devold glass fiber joint venture to Hexagon Devold. The 50-50 joint venture was created in 2007 to manufacture glass fiber reinforcement fabrics for use in turbine blades for wind energy.

Ceramics and glass business news of the week

Owens Corning selects Constellation to develop 2.6-megawatt solar project for Delmar, N.Y., facility

Owens Corning and Constellation today announced the development of a 2.6-megawatt solar generation project that will supply clean energy to the company’s thermal and acoustical insulation plant in Delmar, N.Y. Scheduled for completion in late 2013, the solar project is designed to supply more than 6 percent of the plant’s annual electricity needs and will support Owens Corning’s 2020 Environmental Footprint Goals for energy use and greenhouse gas emissions reduction. “The Delmar Plant is committed to environmental sustainability and advancing both our plant and Owens Corning toward our 2020 sustainability goals,” says John Becker, Delmar plant leader for Owens Corning. “In addition, this project is part of our continuing efforts to implement innovative programs that improve and protect New York State’s environment, and have a positive impact on the state’s economy.” Constellation will finance, build, own and maintain the system. Electricity generated by the system will be purchased by Owens Corning under a 20-year power purchase agreement with Constellation.

Energy efficient materials market: New industry research report is now available

A recently added market report by Transparency Market Research on “Energy Efficient Materials Market—Global Industry Size, Share, Trends, Analysis And Forecasts 2012-2018″ is now available. Energy efficient materials are largely used for thermal insulation of buildings as a result of which, demand for these materials is on the rise. Thermal insulation is the most efficient and effective way to improve the energy utilization and efficiency in the building. This method will preserve the indoor heat during winter while keeping the building cool from inside in summers thus improving comfort and saving energy. Some important factors which are necessary for energy saving potential include thermal insulation, efficient lighting system, insulation of windows etc. The most common energy efficient material is fiber glass which is largely used in constructing energy efficient windows. Energy efficient materials industry has a huge market potential in developed countries of America and Europe however, this technology is expected to catch momentum in developing markets of Asia Pacific in near future owing to the increasing adoption of the concept of energy efficient homes. Energy efficient materials market is also driven by increasing consumer demand for operating various appliances and increasing standard of living. In America about 38 percent of total energy consumption is used for heating and cooling purpose in buildings while China accounts for 47.2 percent of total energy consumption.

US Silica exceeds sustainability targets in workplace safety, community investment and environmental protection

U.S. Silica exceeded all of its 2012 Sustainability Targets including those for workplace safety, community investment and environmental protection. The company released its third annual Sustainability Report, Connected, which provides a summary of the company’s goals and accomplishments over the past year. Under the guidance of the company’s Sustainability Council, the 2017 Bold Goals and Annual Targets are focused on three distinct areas: People, Planet and Prosperity. Building off of the company’s last two reports, Connected reflects U.S. Silica’s commitment to employees, neighbors, shareholders and the natural environment. It also underscores U.S. Silica’s leadership in sustainability efforts, ranging from tree plantings and wildlife preservation initiatives to financial and in-kind support for local charities and outreach groups.

EU tariffs aim to prevent Chinese ceramics dumping

(Reuters News) From whitewares to solar panels, ceramic products imported from China are about to become much more expensive for European consumers after the European Commission agreed to impose punitive duties on Chinese ceramic imports to counter what it says is dumping at artificially low prices. Imported Chinese whitewares are now subject to tariffs of between 13.1 and 36.1 percent, according to the EU’s official journal. The European Commission says ceramic tableware and kitchenware imports from China totaled €728 million in 2011. After an investigation of alleged dumping by Chinese producers of €21 billion of solar panels and components, the commission also imposed punitive tariffs of 47 percent on Chinese solar goods and said it is also ready to launch an investigation into Chinese imports of mobile telecom equipment.

NSL Analytical is testing out more space

Growth in industrial markets, more regulations and a shortage of skilled metallurgists all mean the same to NSL Analytical Services Inc.: more business. The independent commercial testing company recently invested more than $1.6 million to buy and renovate a new metallurgical laboratory in Warrensville Heights, Ohio, thus expanding that component of its business. At 11,500 square feet, the new building offers more than double the space of its old metallurgical lab, with more than $560,000 of that investment going to new microscopes, testing machines and other equipment. NSL Analytical, made up of a chemical testing lab and a metallurgical lab, has embarked on an aggressive growth plan in recent years, doubling its revenues and adding 17 employees since 2007, says company president Larry Somrack. He declined to share the company’s annual revenues, but cited the hiring increase as a sign of success. NSL is setting itself up to double its revenue again during the next three years, and Somrack says he plans to hire another 19 employees in the next three to five years. NSL currently has 66 employees. Somrack thinks opportunities exist to support that growth. A rise in regulations in recent years has led to a greater need for outside testing. Also, chief metallurgist Kevin Holland says in an email that he’s seen growth in the oil and gas industry and in manufacturing since the end of the recession.

CoorsTek chief spearheads African ‘impact investing’ fund

After spending years supporting charitable work in Africa, John Coors, chief executive of CoorsTek, the US ceramics manufacturing giant, reached the conclusion that philanthropy was not the answer to fostering economic development. A defining moment came in rural western Kenya about two years ago, when he and a team of doctors and dentists had to turn away lines of people seeking medical help at an orphanage they supported because they could not meet the demand. High quality global journalism requires investment. The experience was the catalyst for Mr Coors to come up with an alternative view, shifting from a charitable approach to capitalism. The result is an initiative that aims to attract investment from influential, wealthy families into a private equity-type fund that has an initial target of raising $300m to invest in sub-Saharan Africa. The One Thousand & One Voices (1K1V) project was launched at the World Economic Forum on Africa in Cape Town with the concept that money would be put to better use if it was invested in growing African businesses and boosting job creation.

3M reports first-quarter results; company posts sales of $7.6B

3M reports first-quarter earnings of $1.61 per share, an increase of 1.3 percent versus the first quarter of 2012. Sales rose 2.0 percent year-on-year to $7.6 billion, an all-time first-quarter record. Organic local-currency sales grew 2.1 percent and acquisitions added 1.7 percent to sales. Currency impacts reduced sales by 1.8 percent year-on-year. Operating income was $1.6 billion and operating income margins for the quarter were 21.6 percent. First-quarter net income was $1.1 billion and free cash flow was $670 million. “We achieved record first-quarter sales and solid operating margins in the face of a low-growth economic environment and the strong U.S. dollar,” said Inge G. Thulin, 3M chair, president and chief executive officer. “At the same time, we further strengthened the company through increased investments in innovation, commercialization and manufacturing.” The company paid $440 million in cash dividends to shareholders and repurchased $805 million of its own shares during the quarter.

Bioceramics: Opportunities and challenges

 

Chemical composition of Biolox delta, a zirconia-toughened alumina with small additions of chromium oxide and strontium aluminate. Credit: Pawar, IJACT

Last July’s 4th International Congress on Ceramics was the setting for multiple presentations on the use of advanced ceramics in various industries. Among the application areas covered were biology and medicine. This post is a recap of a paper on the topic from the May/June issue of AcerS’ International Journal of Applied Ceramic Technology.

According to author Vivek Pawar, a materials researcher at Smith and Nephew Inc. (Memphis, Tenn.), seven presentations at the event focused on bioceramics for orthopedic, tissue engineering, and dentistry applications, as well as on innovative manufacturing techniques and novel ceramic materials for use as bearing surfaces.

Pawar writes that the bioceramics used in hard or soft tissue replacement can be classified as bioactive glasses made mainly from calcium oxide, sodium oxide, phosphorus pentoxide, and silica; apatite-based ceramics made from synthetic hydroxyapatite and calcium phosphates; and ceramics that are used as bearing surfaces for orthopedic applications.

Since development of the first bioactive glass by Larry Hench more than 40 years ago, few alterations have been made to the materials’ composition. Pawar reports current research in the area focuses on developing compositions that maintain or increase bioactivity after crystallization during sintering. The goal is to develop low-density, easily machinable materials with fracture toughness greater than 1 MPa m1/2.

A new material aimed at meeting those criteria is a product called ‘Biosilicate’ from Vitrovita (São Carlos, Brazil), which is reported to have antimicrobial properties. In one study assessing the effectiveness of Biosilicate against a variety of microorganisms, the material displayed activity against all the bacteria except one, drastically reducing the number of viable cells in the first 10 minutes of contact.

Hydroxyapatite (HA) coatings are commonly used in orthopedic devices to promote bone in-growth on metallic implants. Pawar writes that current research focuses on increasing the material’s bioactivity by incorporating bioactive ions in the HA crystal structure. Researchers have investigated magnesium, strontium, silver, zinc, titanium, iron, sodium, and potassium cationic substitutions. Anionic substitutions considered include fluorine, chlorine, hydroxide, phosphate, and silicate ions. These ions perturb the HA crystal structure and change solubility. Current work is aimed at understanding how each of these ions affects bioactivity. Substitutions with silver, for example, have increased HA solubility and shown bactericidal effects.

Hip arthroplasty remains the predominant use for ceramic bearing surfaces in orthopedic implants, and materials used in this application have included alumina, yttria-stabilized zirconia, and zirconia-toughened alumina. Newer ceramic materials with higher strength and toughness than alumina and reduced risk of fracture include ‘Biolox delta‘ from CeramTec (Plochingen, Germany). A zirconia-toughened alumina with small additions of chromium oxide and strontium aluminate, the material is “being considered for challenging applications such as hip resurfacing femoral heads and knee femoral components,” Pawar writes.

Another potential bearing material is silicon nitride, which offers high strength and toughness, excellent wear resistance, imaging compatibility, affinity to bone, and an antibacterial surface. Produced by Amedica (Salt Lake City, Utah), Si3N4 is already being used in spinal devices.

In the article Pawar notes, “Although no significant clinical problems have been reported with these two materials, a long-term clinical followup will be required to evaluate the performance of these materials.”

Innovations in ceramic processing techniques are being driven by specific biomedical applications. For example, camphene freeze casting processes are being used to create a 3-D interconnected porous bioceramic scaffold with the aim of producing a bioactive glass scaffold with high strength and bioactivity.

Also proposed is a 3-D printing process for apatite-based ceramics using stereolithography. The method is said to enable production of customized solutions based on clinical needs. A limited clinical study of the technology for repair of large craniofacial bone defects is under way at 3DCeram (Limoges, France).

Finally, nanoceramics with particle sizes of 1 to 100 nm are the focus of considerable research. The unique properties of materials produced using nanoparticles—higher surface-to-volume ratios, no light scattering, and unique mechanical properties in composite form—have led to use in dental fillings and crowns. Bone grafting, bone cement, and bioactive ceramic applications also offer research opportunities. Pawar expects future research in this area will focus on development of methods to produce customized nanoceramics based on patient needs.